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Chemical processes in viscous materials

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Chemical processes in viscous materials
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Barnes, Mark Jay, 1962-
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xi, 137 leaves : ill. ; 28 cm.

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Catalysts ( jstor )
Cobalt ( jstor )
Gas flow ( jstor )
Hydrogen ( jstor )
Oxidation ( jstor )
Oxygen ( jstor )
Polymers ( jstor )
Propylene ( jstor )
Solvents ( jstor )
Sulfides ( jstor )
Catalysis ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Membranes (Technology) ( lcsh )
Polymers ( lcsh )
Transition metal catalysts ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis (Ph. D.)--University of Florida, 1989.
Bibliography:
Includes bibliographical references (leaves 130-136)
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Typescript.
General Note:
Vita.
Statement of Responsibility:
by Mark Jay Barnes.

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CHEMICAL PROCESSES IN VISCOUS MATERIALS


BY

MARK JAY BARNES















A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


1989




CHEMICAL PROCESSES IN VISCOUS MATERIALS
BY
MARK JAY BARNES
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1989


TO MY FAMILY WHOSE SUPPORT NEVER FALTERED


ACKNOWLEDGEMENTS
The most cherished and remembered things which a person can obtain
in his lifetime are those which require sacrifice and dedication to
achieve. The pursuit of knowledge is certainly no exception to this
definition. If exception be taken with this definition, it is due to
the implication that sacrifice and dedication are contributed only by
the individual. On the contrary, an education would be impossible to
achieve without the sacrifice and dedication of a large number of
people.
First and foremost I wish to express my gratitude to my family.
Their continued support and encouragement have given me the opportunity
to fulfill what was once a dream. My parents, Avery and Marilyn, have
instilled in me a sense of security which can never be taken away. From
them I have learned what happiness is, from where it comes, and how it
can be obtained. To my brothers and sister-in-law, Douglas, Curtis, and
Robin, I owe my love of science. It was they who pointed me in the
right direction and taught me to never be apprehensive of the
unexpected. To my grandparents I am indebted for all their generosity
and support.
I would also like to thank my teachers who have instilled in me a
love for chemistry, Glenn Vogel, Heinz and Judy Koch, Harry Sisler, and
most importantly Russell "Doc" Drago. It is truly an inspiration to
i i i


know a person who loves and enjoys his work as much as he does. I would
also like to thank Ruth Drago for making Florida my home away from home.
I would also like to thank all of my friends. There are too many
to list, but there are those who have influenced me greatly in one way
or another. Included in this list are the past and present residents of
the "Thunderdome": Todd "Spud" Gillespie, Stephen "Julio" Brooks, Mark
"Chin" Hail, Gerald "Citrus Connection" Grnewald, and Donald "Bueller"
Ferris. I would also like to extend my gratitude to past and present
members of the Drago Group, in particular, Maribel Lisk, Robert Taylor,
Larry Chamusco, Edward Getty, Cindy Getty, Shannon Davis, Richard Riley,
and especially Ngai Wong, who has been a good friend and source of
information for many years. Lastly, I would like to express my
gratitude to my girl friend, Kaneez Rizvi. I owe a considerable portion
of my sanity to her for the love and understanding she has given me.


TABLE OF CONTENTS
page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vi
LIST OF FIGURES viii
ABSTRACT x
CHAPTERS
IGENERAL INTRODUCTION 1
IICOBALT(11)-FACILITATED TRANSPORT OF DIOXYGEN IN A
POLYSTYRENE MEMBRANE 4
Introduction 4
Experimental 16
Results and Discussion 21
IIIDEMONSTRATION OF THE FEASIBILITY AND VERSATILITY OF
MEMBRANE REACTORS 43
Introduction 43
Experimental 58
Results and Discussion 62
IVHETEROGENEOUS HYDROFORMYLATION OF PROPYLENE USING SUPPORTED
RHODIUM CATALYSTS IN A CONTINUOUS GAS FLOW REACTOR 80
Introduction 80
Experimental 87
Results and Discussion 91
VSUMMARY 115
APPENDIX
COMPUTER PROGRAM 117
REFERENCES 130
BIOGRAPHICAL SKETCH 137
v


LIST OF TABLES
Tab! e page
2-1. Permeation data for PS/[P]-CoSDPT (16.4%)
membrane 22
2-2. Separation data for a series of polystyrene
blank membranes 27
2-3. Separation data for a series of nickel blank
membranes 28
2-4. Difference in oxygen partial pressure for a
series of PS/[P]-CoSDPT membranes 32
2-5. Difference in oxygen partial pressure for a
series of PS/[P]-CoBr^SDPT membranes 33
2-6. Difference in oxygen partial pressure for a
series of PS/[P]-Co3FSDPT membranes 34
2-7. Difference in oxygen partial pressure for a
series of PS/[SG]-CoSDPT membranes 35
2-8. Comparison of the difference in oxygen partial
pressures obtained with increased cobalt
loading in PS/[P]-CoSDPT 38
3-1. Hydroformylation of propylene with
RhH(CO) (PPh3)3 66
3-2. Oxidation of 1-butene 67
3-3. Butyl sulfide membrane conversion data for
various ruthenium catalyzed oxidations by 0? at
1 atm. and 90C 71
3-4. Butyl sulfide membrane turnover data 72
3-5. Butyl sulfide solution reaction conversion data
for various ruthenium catalyzed oxidations by
02 at 90C 74
3-6. Hydrogen peroxide formation 78
v:


4-1. Temperature effect upon propylene
hydroformylation activity using RhH\SG 94
4-2. Selectivity as a function of time in the
hydroformylation of propylene with RhH\SG 96
4-3. Effect of gas flow on the hydroformylation of
propylene with RhH\SG 100
4-4. Effect of gas pressure on the hydroformylation
of propylene with RhH\SG 103
4-5. Effect of gas ratios on the hydroformylation of
propylene with RhH\SG 105
4-6. Catalyst comparison at 80C 109
4-7. Catalyst comparison at 100C 112
vi i


LIST OF FIGURES
Figure page
2-1. Molecular orbital diagram.
a) Dioxygen; b) Dioxygen adduct of cobalt(II).. 7
2-2. Polystyrene supported N,N'-bis(salicylidene-
imino)di-n-propylamine cobalt(II), [P]-CoSDPT.. 10
2-3. Schematic representation of the dual mode
sorption concept 13
2-4. [P]-CoSDPT reaction scheme 19
2-5. Schematic diagram of the gas permeation
experimental set up 20
2-6. Plot of the natural log of oxygen partial
pressure differential as a function of time
for a PS/[P]-CoSDPT, (16.4%), membrane 24
2-7. Plot of the natural log of nitrogen partial
pressure differential as a function of time
for a PS/[P]-CoSDPT, (16.4%), membrane 25
2-8. Oxygen partial pressure as a function of time,
a) Experimental curve, b) Calculated
non-facilitated curve, c) Calculated
reference curve (a = 1.00) 30
2-9. Contributions to permeation mechanism 40
2-10. Schematic representation of a metal facilitated
transport mechanism due to site to site
interaction 41
3-1. Read and Dudley mechanism for the oxidation of
terminal alkenes with RhH(CO) (PPh2)3 49
3-2. Proposed mechanism for the oxidation of
terminal alkenes using a
rhodi um( 111 )/copper( 11) co-catalyst 51
vi i i


3-3.
Alternative mechanism for the oxidation of
terminal alkenes using a
rhodium(III)/copper(II) co-catalyst 52
3-4. Sulfide oxidation catalysts:
a) [Ru(0)2(dmp)2](PF6)2 and
b) [Ru30(prop)6(H20)3r 55
3-5. Anthraquinone autoxidation process 56
3-6. Reactor membrane apparatus 61
3-7. Hydrogen peroxide membrane reactor 76
4-1. Associative and dissociative hydroformyl at ion
reaction mechanism 84
4-2. Gas flow reactor schematic 90
4-3. n-Butanal activity as a function of temperature
in the hydroformylation of propylene with
RhH\SG 95
4-4. Comparison of hydroformylation activity in the
production of n-butanal and isobutanal with
RhH\SG 97
4-5. Effect of gas flow on the n-butanal activity in
the hydroformylation of propylene with RhH\SG.. 99
4-6. Effect of gas pressure on the n-butanal
activity in the hydroformylation of propylene
with RhH\SG 102
4-7. Effect of gas ratios on the n-butanal activity
in the hydroformylation of propylene with
RhH\SG 104
4-8. n-Butanal activity for RhH\SG and Rh(tfa)\SG... 107
4-9. Butanal activity as a function of time in the
hydroformylation of propylene with RhH\SG\PC at
100C 113


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
CHEMICAL PROCESSES IN VISCOUS MATERIALS
By
Mark Jay Barnes
August 1989
Chairman: Russell S. Drago
Major Department: Chemistry
Polymer membranes, in which transition metal complexes have been
dispersed, have been used to facilitate both oxygen enrichment of air
and traditional homogeneous catalytic reactions. The former is a
demonstration of facilitated transport of oxygen through a glassy
polymer. The latter includes the demonstration of a wide variety of
reactions within the polymer environment.
Selective gas permeation through a polymer membrane has become an
attractive alternative for conventional gas separation processes. The
incorporation of additives that modify permeation properties has been
the focus of this research effort in an attempt to enhance the
separation ability of the polymer membranes. This effort involves the
use of metal complexes to facilitate the transport of gases in a polymer
membrane. Specifically, the main objectives investigated were the
incorporation of supported cobalt (II) schiff base complexes into
polystyrene membranes and the demonstration of metal promoted
x


enhancement of oxygen permeation in the separation of air. Back
calculation using a nickel blank to provide an average separation factor
allows for the determination of metal promoted enrichment using the
nitrogen permeability coefficient as an internal standard. These
results are presented and a transport mechanism discussed.
The use of a polymer environment as the medium for chemical
reactions has resulted in a novel approach to heterogenizing homogeneous
catalytic reactions. The feasibility of this process has been
demonstrated by the hydroformylation of propylene and the oxidation of
terminal alkenes. A specific application of the process involves the
use of ruthenium catalysts dispersed in composite polymer membranes for
the oxidative decomposition of butyl sulfide, a mustard agent simulant.
The formation of hydrogen peroxide using the anthraquinone autoxidation
process is another application which has been achieved. Results from
the above mentioned reactions are presented and discussed.
The development of solid supported rhodium catalysts for
heterogeneous hydroformylation reactions has resulted in the production
of straight chain aldehydes with high selectivity. Use of these
catalysts in a pressure-gas flow reactor is demonstrated and discussed.
XI


CHAPTER I
GENERAL INTRODUCTION
Historically, applications of polymer membrane technology have
been dominated by separation processes. The two biggest contributors to
this field are reverse osmosis desalination processes and industrial gas
separations. Many smaller scale applications which utilize membrane
1 2
technology are currently being investigated. Drug production and
delivery, fermentation, basic chemicals synthesis, hydrogenations and
dehydrogenations represent only a portion of these applications. The
types of membranes employed are as widely varied as their applications.
Ceramic, metallic, glass, inorganic, and polymeric membranes have been
used as process media. Also of interest is the engineering design in
which they are used. Integrated or "hybrid" processes are being
developed which combine a membrane separation unit with an existing
7 8
separation process such as cryogenic separation. Layering or
combining the different membrane types may provide systems which allow
chemical reaction and product-reactant separation within the same unit.
The work presented in this dissertation is associated with
combining membrane technology and transition metal reaction chemistry.
The use of polymers and catalysts in conjunction has previously been
widely investigated in an attempt to heterogenize known homogeneous
Q 1 O
catalysts. For the most part, the polymer is used as a support to
which the catalyst is covalently attached. These insoluble
1


2
functionalized catalysts are then used under "normal" solution chemistry
conditions. Alternatively, membrane reactors are systems in which the
polymer is used as the medium for reaction. The polymer functions, in
essence, as the solvent for the reaction.
The concept of membrane reactors is relatively new. Wolynic and
co-workers first published work in this area which dealt with a
catalytic liquid membrane reactor used for the production of
acetaldehyde from ethylene and oxygen.Since that time most
membrane reactor work has been concentrated in two areas. Membrane
bioreactors have been shown to be effective in enzyme catalysis^
and porous ceramic and glass membranes have been used as inorganic
o c.
membrane reactors. In the latter case, hydrogenation and
dehydrogenation reactions are the main processes being attempted.
Catalysis with nation membranes has also been reported.^19 Nation
possesses a chemically resistant, perfluorinated, polymeric backbone
with highly acidic sulfonic acid groups. Its general structure is shown
below. It has been used as a super acid catalyst, catalyst support,
electrocatalyst, and a gas diffusion membrane.
[(CF2-CF2)n-CF-CF2]x
(0CF2CF)m0CF2CF2S03H
Even though a considerable amount of work has been conducted in
the area of membrane reactors, little of it has actually been achieved


3
with the use of organic polymers. The work presented here is an attempt
at filling this void. Specifically, this study involves three areas of
membrane chemistry. The first process investigates the ability of a
transition metal complex to affect the permeation properties of a
polymeric membrane. The second is concerned with how transition metal
complex reactivities are influenced by dispersion in an organic polymer
"solvent" environment. The last area examined deals with dispersing
transition metal complexes in a non-volatile viscous material which is
coated on an inorganic oxide support for the purpose of creating a
heterogeneous gas phase reaction process.


CHAPTER II
COBALT(11)-FACILITATED TRANSPORT OF DIOXYGEN
IN A POLYSTYRENE MEMBRANE
Introduction
The separation of air into its primary components, oxygen and
nitrogen, is of major industrial significance. Today, two main
commercial processes are used to achieve separation, cryogenic
20-22 po pc
fractional distillation of air and pressure swing adsorption.
Both processes have been employed extensively in the last century for
the production of high purity oxygen and nitrogen.
Many applications, however, do not require high purity oxygen but
can instead use oxygen enriched air. This market includes waste water
treatment facilities, the pulp and paper industry, fermentation
processes and numerous medical applications to name a few. Selective
pc po
gas permeation through a polymer membrane provides an alternative
separation method which is becoming increasingly more important in the
29 30
production of oxygen enriched air.
The past ten years have seen the advent of membrane based
separation units. The first commercial venture into the field was
initiated by the Monsanto Corporation. It utilized a polysulfone hollow
pq
fiber membrane system and was called "The Prism Process." Since that
time many types of membranes have been increasingly employed for
separation purposes, and recently, are being used in conjunction with
4


5
31 32
the traditional air separation processes. These hybrid systems
have been shown to be an economically attractive alternative in the
production of pure oxygen and nitrogen. The fact that membrane
separation units are economically competitive with existing processes,
coupled with the unlimited number of applications, has resulted in an
explosion in the amount of research being carried out in this field.
Interest is mainly twofold. Most attention is focused on finding new
applications for membrane separation units and developing new, or
modifying existing, polymers for these applications.The use of membranes
for gas separations is based upon the phenomenon that different
permeates will have varying rates of permeation through membranes. One
of the first references to a membrane separation procedure is credited
33
to Thomas Graham, who, in 1864, used a dialyzer to separate a solution
into its components. He became known as the father of gas separations
when he published his famous paper "On the Molecular Mobility of
Gases''^ in 1863, which resulted in the formulation of Graham's Law, and
3C
later published a paper dealing with the separation of gases. Since
that time many others have made considerable contributions in the areas
of membrane chemistry and gas separations, but because of the size and
scope of this work, it will not be mentioned in this chapter.
Alternately, a more detailed insight into the properties which affect
membrane permeation will be presented.
Ideally, a permselective polymer membrane should have good
mechanical strength, high selectivity, and high flux (rate of gas
permeation). However, the later two are inversely related. A polymer
membrane which has a high selectivity will have a relatively slow flux


6
and vice versa. Attempts to either increase the rate of permeation in
highly selective membranes or enhance the selectivity of highly
permeable membranes have been the focal point of most research efforts.
The work presented in this chapter represents an undertaking in the
latter area of modification.
The incorporation of additives to modify permeation properties has
been directed towards improving membranes that are highly permeable and
poorly selective. A recent approach to this concept involved enhancing
the transport of dioxygen by encapsulating a metal complex-containing
solution in a porous polymer membrane resulting in excellent
selectivity. This liquid-membrane, oxygen-enrichment process
utilizes cobalt(II) chelate complexes. The role of the cobalt complex
is to act as a carrier by reversibly binding dioxygen and thus increase
the oxygen permeability of the membrane. In systems such as these, the
most important aspects to be considered are the processes which occur at
the carrier site. Essentially, these processes are attributed to the
reversible binding ability of the cobalt(II) complex and can be
explained by extrapolating our knowledge of similar processes which
occur with cobalt(II) complexes in solution.
The ability of the metal center to bind dioxygen and the factors
which affect the interaction between the two can be complex. As shown
in figure 2-la, molecular oxygen in its ground state is a triplet, 2^

molecule with two unpaired electrons residing in the 7r molecular
orbitals. Since it is kinetically unfavorable for one of the electrons
to change spin, dioxygen is typically unreactive towards diamagnetic
compounds. Its ability to bind with transition metal complexes results


Figure 2-1.
Molecular orbital diagram.
a) Dioxygen; b) Dioxygen adduct of cobalt(II).


8
primarily from spin orbital coupling, which lessens the severity of a
spin change. The spin pairing modeldeveloped by Drago and Corden
describes this metal-dioxygen bonding scheme and is shown in figure 2-lb
using a simplified molecular orbital diagram. It involves the pairing
of the unpaired dz electron of cobalt(II) with an unpaired 7r electron
of dioxygen which results in the formation of an end on bonded
cobalt(II)-dioxygen adduct.
The stability of the cobalt-oxygen sigma bond is directly related
to the ligand field strength of the complex. By increasing the ligand
2
field strength around the cobalt metal center, the energy of the dz
orbital used in bond formation is increased. Therefore during dioxygen
adduct formation, more energy is given off resulting in a more stable
cobalt-oxygen sigma bond. This is a critical property since if the bond
formed is too stable, the ability to dissociate the dioxygen adduct is
hindered. If the bond formed is too weak, the complex will have poor
oxygen affinity. Thus a compromise is required to have a suitable
carrier.
In 1938, Tsumaki reported the first synthetic complex capable of
reversibly binding dioxygen, N,N'-bis(salicylidene)ethylenediamine
cobalt(II). This complex, better known as cobalt(II) salen, is shown
below. Since that time, many cobalt(II) schiff base complexes have been
v_/


9
reported which are capable of reversibly binding dioxygen.
Unfortunately, deactivation of the metal complexes has hindered their
development. Deactivation, for the most part, is brought about by
either oxidation of the ligand system or irreversible oxidation of the
metal center. An example of the latter would be the formation of a
/-peroxodimer complex. Attempts to achieve a stable oxygen carrier have
been directed using two different approaches. Sterically constrained
metal carrier complexes and supported metal carrier complexes have
received the greatest attention. Often, schiff base complexes which
indicate promise as carriers are the focus of such modification. This
is the case in the work presented in this chapter.
One of the best examples cited which has the ability to bind
dioxygen reversibly is N,N'-bis(salicylideneimino)di-n-propylamine
cobalt(II), CoSDPT (figure 2-2 with P replaced by H), in 1:1 DMSO and
a-butyrolactone solvent encapsulated in a 130 / thick microporous nylon
6,6 membrane.42 At 25C, an air mixture containing 88% oxygen was
produced in a single pass through this membrane. A schematic diagram of
this system is illustrated below. Although the process appears quite
MEMBRANE


10
Figure 2-2.
R H B r F
Polystyrene supported N,N'-bis(salicylideneimino)di-
n-propylamine cobalt(II), [P]-CoSDPT.


11
remarkable, the removal of the volatile solvent by gas flow has hindered
its commercial development. The work presented in this text illustrates
the ability to reversibly bind and facilitate the transport of dioxygen
through a polymer membrane using this complex supported on polystyrene.
A few reports of facilitated transport of dioxygen by carriers in
membranes have appeared^^ using unsupported complexes that can be
viewed as being dissolved in the polymer.
The concept of a facilitated transport mechanism has been a
controversial subject in membrane separations. Therefore, a brief
mathematical description of permeation in a polymer membrane is
necessary. According to Fick's Law of diffusion, shown below, the flux,
J = DSAP/1
J, of a penetrant can be determined from its diffusion coefficient, D;
solubility, S; and pressure differential, P, across a membrane of
thickness 1. The permeability of the gas, P, is dependent upon both its
solubility and diffusivity in the respective membrane.
P = DS
Generally, sorption and transport in a glassy polymer such as
polystyrene is best explained by a dual mode model. Using this model,
two simultaneous processes in the membrane are predicted to occur. The
first is associated with dissolution in the dense region of the polymer
and follows Henry's Law where CQ is the concentration, KQ is the Henry's


12
law constant which characterizes sorption of the penetrant, and P is the
pressure of the penetrant. The second process is associated with
distribution in the gaps or "holes" of the polymer and is best explained
by a Langmuir isotherm where CH is the concentration, C^' the Langmuir
CH = Ch'BP / (1 + BP)
sorption capacity, and B the affinity of the penetrant for the gaps in
the polymer. Using these simple equations, the total concentration of
the penetrant can be described as the sum of the two individual
C = CD + CH
concentrations. This can be seen schematically in the concentration
versus pressure graph shown in figure 2-3. The overall solubility
isotherm can similarly be described as the sum of the solubility
expressions of each model. The permeability of the penetrant
S = Kd + Ch'B / (1 + BP)
can now be expressed as the diffusivity and solubility associated with
each individual mode where Dq and represent the diffusivities of the
Henry's mode and Langmuir mode respectively.


13
c
Figure 2-3.
P
P
Schematic representation of the dual mode sorption
concept.


14
P = KdDd + C|_|'BDh / (1 + BP)
The model presented is representative of a nonfaci1itated process
and must therefore be modified to explain the contributions made by a
facilitated transport mode. This can be done by initially applying
Langmuir kinetics to describe the equilibrium obtained when oxygen binds
to solid metal complexes. The resulting expression can then be
rearranged to indicate the fraction of oxygenated sites, X, with
X / (1 X) = KPq2
X = KPq2 / (1 + KPq2)
respect to the equilibrium constant, K, and dioxygen partial pressure.
The fraction of oxygenated sites should be directly related to the
solubility of dioxygen associated with these sites. Therefore, a new
solubility isotherm may be written to express the total solubility of
dioxygen in a membrane capable of facilitating dioxygen transport.
Similarly, a new expression describing dioxygen permeability according
to the three modes of transport can be formulated where represents
the diffusivity associated with the metal sites.
S = KD + [Ch'B / (1 + BP)] + [KP / (1 + KP)]
P = KqDq + [Ch'BDh / (1 + BP)] + [KPDm / (1 + KP)]


15
The results presented in this work represent a new approach to
enhancing the permeation properties of polymer membranes and
establishing a novel method and mechanism of transport. The goal of
this research was to demonstrate this novel mode of transport as well as
to develop a process that accurately accounted for the quantities of
dioxygen associated with both facilitated and nonfaci1itated transport.
To achieve this, a metal complex that reversibly binds dioxygen is
covalently attached to polystyrene. Though the pure complexes in the
solid state do not bind dioxygen, they do bind dioxygen in the solid
state when covalently linked to a polymer. The dispersion of the
metal complex on highly crosslinked polystyrene into a polystyrene film
resulted in the selective permeation of dioxygen through the membrane.
This membrane system differs from the liquid membranes in that the metal
complexes are bound to the polymer. Since the cobalt complexes are not
mobile, the mechanism is unlike that proposed for isotropic polymers or
AO
liquid membranes as demonstrated in the Bend Research system.
Recently, this system has been extended to cobalt(II) porphyrin
and Schiff base compl exes In all reports^^4,46-51 of
facilitated transport in solid polymer membranes, the demonstration of
facilitated transport by metal complex binding of dioxygen is dependent
upon the critical selection of a blank. Incorporation of a material in
a polymer film can function to change the structure of the membrane and
the permeability of gases leading to enrichment by a process other than
facilitated transport. The results of this study are significant for
they provide strong support for a facilitated transfer mechanism using
metal complexes to bind simple gas molecules. A procedure for the


16
evaluation of the experimental permeation data is reported that
eliminates imperfections including solvent entrapment that surely exist
in the test and blank films.
Experimental
Complexes studied were prepared using reagents which were either
purchased or synthesized using the procedures listed below. An overall
reaction scheme is shown in figure 2-4 for the preparation of the
polystyrene supported complexes. Solvents used in this work were
purified by distillation, stored over 4A molecular sieves under a
nitrogen atmosphere, and degassed prior to use when necessary.
Characterization of the complexes was conducted using a Perkin Elmer
Plasma II Emission Spectrometer, and Bruker ER 200D-SRC Electron Spin
Resonance Spectrometer. Elemental analyses were conducted by the
University of Florida Department of Chemistry Microanalysis Service, and
Galbraith Laboratories.
Polystyrene Supported Dipropylenetriamine, P1-DPT
Polystyrene beads (90% chloromethylated, 4% divinyl benzene
crosslinked) were donated by Sybron Corporation. Polystyrene bound
45
dipropylenetriamine was prepared according to the literature.
Experimental analysis: %C = 67.41, %H = 6.64, %N = 7.60. Theoretical
analysis: %C = 72.83, %H = 10.19, %N = 16.98.
Polystyrene Supported Bis(3-(salicylideneaminolpropyl)amine, TP1-SDPT
The polymer bound pentadentate ligand was prepared according to
46
the literature. The 3,5-dibromo and the 3-fluoro substituted


17
sal icy1 aldehyde derivatives were prepared in a similar manner.
Experimental analysis: %C = 75.97, %H = 7.19, %N = 7.84. Theoretical
analysis: %C = 76.45, %H = 7.30, %N = 9.22.
rPl-CoSDPT. -Co BroSDPT and -Co3F$DPT
Cobalt was incorporated into the [P]-SDPT type complexes by
slurrying excess cobalt(II) acetate with the appropriate resins in DMF
under argon at room temperature for two days. The polymer supported
cobalt complexes were filtered, washed with DMF and dried under vacuum
at 80C. Experimental analysis of [P]-CoSDPT: %Co = 0.15. Theoretical
analysis: %Co = 11.50. Overall analysis indicated greater than 95% of
the chloromethylated polystyrene had been converted to the [P]-SDPT and
that 1.15% of the SDPT ligand contained cobalt. The low loading of
cobalt was ideal for this study because site isolation inhibits
formation of the /j-peroxo dimer. EPR studies showed an intense cobalt-
dioxygen signal which was used to monitor reversible binding of O2.
Silica Gel Supported CoSDPT, -CoBroSDPT and -Co3FSDPT
Silica gel supported dipropylenetriamine was prepared as reported
CO
in the literature. The silica supported Cobalt(II)SDPT complexes were
prepared from [SG]-DPT in an analogous manner to the polystyrene bound
analogues. Experimental analyses were not obtained.
PI-NiSDPT, -NiBroSDPT, and \SGI-NiSDPT
The analogous nickel complexes were prepared in the same manner as
reported for the cobalt complexes. Analyses were not obtained.
Membrane Preparation and Characterization
The membranes employed in this study were prepared using a casting
technique. Polystyrene was dissolved in an appropriate solvent, such as


18
toluene or methylene chloride. The viscous polymer solution was then
poured into a leveled circular form. Evaporation of solvent at room
temperature resulted in the formation of homogeneous polymer membranes.
Membranes containing the supported metal complexes were prepared
in a similar manner by grinding the complex into a fine powder (< 1/x in
diameter), adding it to the polymer solution, and then casting the
solution in a mold. After solvent evaporation had occurred, the
membrane's thickness was determined with a vernier caliper to the
nearest hundredth of a millimeter. The weight percent of the added
complex in the membrane was determined after each permeation experiment
by redissolving the polymer film, isolating and drying the supported
complex and then weighing it.
Permeation Apparatus
Permeation experiments were carried out with an apparatus designed
by Ken Balkus.^ The cell was designed to support the membrane and
prevent rupturing when a pressure gradient was applied to the membrane.
A schematic of the permeation setup is shown in figure 2-5.
Permeation Procedure
The following section describes a typical experimental permeation
procedure. A polymer membrane was secured between the two chambers of
the apparatus, after which the membrane deformed to the shape of the
o-rings used to secure its seal. The lower chamber of the cell was
placed under vacuum for approximately six to twelve hours prior to the
start of the experiment to remove any excess solvent or O2 that may have
been trapped in the film during preparation. The lower chamber was then
closed off under vacuum and an initial pressure measurement taken.


19
NH(CH2CH2CN)2
*
CH2-IJ(CH2CH2CN)2
BHy THF
H2-M(CH2CH2CH2NH2)2
Figure 2-4
[P]-CoSDPT reaction scheme.


20
Figure 2-5.
Schematic diagram of the gas permeation experimental
set up.


21
Periodically, the lower chamber was monitored manometrically to
determine the extent of gas permeation and quantitatively to determine
its dioxygen ( also referred to as oxygen) content. The latter analysis
was carried out using gas samples taken from the lower chamber with a
100 /il gas tight syringe and analyzed by a Varian 3700 gas chromatograph
equipped with a thermal conductivity detector. The column employed was
an 8 foot, 1/8 inch O.D., stainless steel column containing 5A molecular
sieves heated to 30C.
Since the gas sample taken was at a reduced pressure, it was
diluted with air while being withdrawn from the sampling port. From the
percent oxygen of the injected sample determined by the GC, the actual
percent oxygen in the lower chamber was calculated using the equation
shown below, where Pg is the pressure of the lower chamber in mmHg, P^
(Pl)(0l) + (PH PL)(0H) = (PH)(0D)
is atmospheric pressure, Og is the percent oxygen in the lower chamber,
0^| is the percent oxygen in the atmosphere, and 0g is the percent oxygen
as determined by the GC. Using this method, the standard deviation
between samples was typically on the order of 0.1%.
Results and Discussion
The evaluation of the cobalt containing membranes is based upon a
comparison of experimental permeation data with data obtained from an
appropriate blank. Permeation data for a typical PS/[P]-CoSDPT membrane


22
are shown in table 2-1. The percent oxygen was calculated as previously
described and the percent enrichment is the difference between the
percentage of oxygen in the lower chamber and that of air, which is
assumed to be 21.0%.
Tabl e
2-1.
Permeation
data for PS/[P]-CoSDPT
(16.4%)
membrane.
Time
(hr)
Total
Pressure
(mmHq)
FI ux
(mmHq/hr)
Partial
Oxygen
(mmHq)
Pressure
Nitrogen
(mmHq)
Percent
Oxvqen
Percent
Enrichment
5
36.0
7.20
10.56
25.44
29.3
8.3
18
71.0
3.94
23.77
47.23
33.5
12.5
24
92.0
3.83
29.78
62.22
32.4
11.4
29.5
99.0
3.35
32.97
66.03
33.3
12.3
42
118.0
2.81
40.27
77.73
34.1
13.1
According to Henry's Law, permeation of a gas through a membrane
is a first order kinetic process. This is shown mathematically below,
where P is the permeability coefficient (cm (STP)cm/cm s mmHg), 1 is the
film thickness (cm), A is the film area (cm ), Vcei-j is the volume of
the lower chamber (cm ), (P^ P^) is the partial pressure differential
across the membrane (mmHg), R is the gas constant (6.24 x 10^
cm mmHg/molK), and T is the temperature (K). Assuming PH is constant
dP
RTA
P(Ph P,)
22414Vcell
dt
1


23
throughout the experiment, the equation can be rearranged and integrated
to give a new equation from which a plot of 1 n(- P|_) versus time
should yield a straight line, indicating a first order process.
1 n(P[_| PL)
-RTA
22'414Vcell 1
t +
constant
This analysis was carried out using the computer program detailed
in Appendix A. Using this program, the permeability coefficients for
both oxygen and nitrogen can be obtained from the slope of the lines
plotted from their respective partial pressures in table 2-1. Graphs of
these analyses are shown in figures 2-6 and 2-7. Values of 4.38 x 10
_1f) O o
and 1.92 x 10 cm (STP)cm/cm s mmHg are obtained respectively.
However, in the cobalt complex containing films, it is obvious that a
slightly curved line is obtained rather than a linear one. This
indicates that the permeability coefficient of oxygen is varying with
the partial pressure of oxygen in the lower chamber. Therefore, oxygen
permeation through the membrane is deviating from a first order process
due to contributions from facilitated transport.
To better demonstrate and quantify the contributions resulting
from facilitated transport, the cobalt containing films must be compared
to an appropriate blank. Analogous nickel(II) complexes do not bind
oxygen, since they have no unpaired electrons, and are similar in
structure to the cobalt complexes resulting in membranes with similar
morphology and free space volumes. Although free volume is difficult to
reproduce in glassy polymers because of air pockets and filler


In (Ph-Pl)
24
TIME (hrs.)
Figure 2-6. Plot of the natural log of oxygen partial pressure
differential as a function of time for a
PS/[P]-CoSDPT, (16.4%), membrane.


In (Ph-Pl)
25
Figure 2-7. Plot of the natural log of nitrogen partial pressure
differential as a function of time for a
PS/[P]-CoSDPT, (16.4%), membrane.


26
aggregation, the nickel complexes are the best simulation for the
unoxygenated cobalt containing films and, therefore, are ideal blanks.
Analysis of the polystyrene and nickel blanks is best made by observing
the ratio of PQ2 to PN2- This value is known as the separation factor,
a, and describes the effectiveness of a membrane for permselectivity.
The a values for both polystyrene and nickel blank membranes are
reported in tables 2-2 and 2-3 respectively.
Certainly, all films contained minor defects, some more severe
than others. An extensive amount of data was collected for a large
number of films. In several instances pinholes were present in the
original film or leaks developed as the experiment progressed. In order
for a run to be found acceptable, it was required that the first data
point have as an upper limit, a value of flux times length, ( J x 1),
below 7.0 (torr-mm/hr) at the start of the experiment. A second
requirement was that in each experiment the flux must decrease as
(PH P|_) decreases i.e., as time increases. This criterion was used to
discard data sets in which leaks developed during the experiment. A
series of 11 films of polystyrene selected by these requirements and
with varying thicknesses was studied yielding a mean oxygen permeability
coefficient of 3.1 x lO'1^ cm^(STP) cm/(cm^s mmHg) with a standard
deviation of +0.8 x 10~* This permeability coefficient is
approximately one order of magnitude greater than those previously
53 57
reported. This is not surprising since polystyrene is a glassy
polymer and the method of membrane preparation will affect the transport
58 59
properties of the membrane. Systematic errors introduced by the
apparatus or sampling technique may also contribute to the deviation.


27
Table 2-2. Separation data for a series of polystyrene blank
membranes.
1 (mm)
J1
(torr-mm/hr)
Pts.a
a
0.371 .073
1.7
3F
2.52 .02
0.542 .124
2.3
4M
1.37 .02
0.50 .00
3.4
6F
2.14 .02
0.164 .05
4.3
4M
1.40 .01
0.150 .052
1.5
4M
1.72 .01
0.250 .052
1.2
5M
2.19 .04
0.110 .028
1.0
7F
2.27 .02
0.131 .048
1.9
9F
2.34 + .03
0.989 .16
5.4
5F
1.97 .05
1.567 .30
4.3
4F
2.76 .20
0.238 .051
1.5
3M
1.03 .16
Avg. a = 1.97 S.D. = 0.17
a number of data points in the data set. E, M, F designate the
time span of the experiment where E is less than 12 hrs., M is
less than 29 hrs., and F is greater than or equal to 29 hrs.


28
Table 2-3. Separation data for a series of nickel blank
membranes.
rPl-NiSDPT
1st Cycle
J1
WT
%
l(i
mm
)
(torrmm/hr)
Pts.a
a
20
0.457
+
.119
4.8
4E
1.79
+ .
.01
15
0.681
+
.059
3.1
5M
2.05
+ .
02
10
0.423
+
.103
4.0
5E
1.57
+ .
02
Avg.
a = 1.80
S.D. =
0.17
ULL
-NiBr2SDPT
1
st Cycle
20
0.432
+
.12
3.9
5E
2.26
+ .
03
20
0.700
+
.168
5.2
5M
1.80
+ .
12
15
0.600
+
.160
3.0
6M
1.94
+ .
06
10
0.628
+
.138
4.4
5M
1.79
+ .
08
Avg.
a = 1.95
S.D. =
= 0.13
2nd Cycle
25
0.709
+
.159
3.5
4M
2.12 .
02
rSGl-NiSDPT
25
0.694
+
.105
4.5
5M
1.77
+
.05
20
0.666
+
.114
3.0
5M
1.73
+
.01
15
0.730
+
.079
4.7
4M
2.00
+
.04
Avg.
a = 1.83
S.D. =
0.10
1 number
of data
points
in
the data set.
E, M, F
designate
the
.ime
span
of the
experi
ment
where E is less than
12 hrs
M
i s
ess
than
29 hrs.
, and
F i s
greater than
or equal
to 29
hrs.


29
The permeabilities were also determined from a gas mixture rather than a
single component gas penetrating through the membrane. The few studies
reported with permeations of gas mixtures through glassy polymers show
deviations in permeabilities of pure penetrants versus those of the
mixture.Although deviations from the literature values exist, the
important point to be considered is that all films were similarly made
and evaluated so that consistent data could be obtained and compared.
Using PN2 as an internal standard ensures that the cobalt complex-
containing membranes can be compared with their respective blanks and
the difference in oxygen partial pressures can be attributed to metal
promoted enhanced oxygen permeability and not to film preparation or
defects. To illustrate the enrichment that is obtained by facilitated
transfer, the partial pressure of oxygen in the lower chamber has been
plotted as a function of time for PS/[P]-CoSDPT (16.4% functionalized
ligand with 0.15% cobalt) membrane (figure 2-8). The change in nitrogen
partial pressure with time for this film is used as an internal standard
to calibrate the permeation experiment. The average a value from the
PS/[P]-NiSDPT blanks is used to calculate the oxygen partial pressure
corresponding to this nitrogen pressure for an identical membrane in
which facilitated transport does not occur and a first order kinetic
process is observed. Since the cobalt complex does not bind nitrogen
and facilitate its transport, this affords an ideal blank. This
calculated pressure of oxygen is representative of all diffusion
mechanisms other than facilitated transport and is also plotted in
figure 2-8. The difference between the curves represents the enrichment
obtained by a cobalt(II) facilitated transport mechanism. Again this


OXYGEN PARTIAL PRESSURE (mm
30
cn
Figure 2-8. Oxygen partial pressure as a function of time.
a) Experimental curve, b) Calculated non-facilitated
curve, c) Calculated reference curve (a = 1.00).


31
analysis was conducted using the computer program listed in appendix A.
Figure 2-8 also contains a reference curve indicating the oxygen partial
pressure which would be present if no permselectivity were achieved,
i.e. a = 1.00.
By analyzing the data using the blank nickel a values and nitrogen
permeability coefficients from the cobalt containing membranes,
systematic errors in measuring the enrichment of oxygen (such as
membrane thickness and imperfections) are cancelled out. This is
verified experimentally with the nickel blanks themselves, where a is
independent of film thickness. It was also observed in the nickel data,
that percent loading and variation in substituents on the phenyl ring
did not influence the a values within the experimental standard
deviation of + 0.2. The reaction chamber can be evacuated after 25
hours and the experiment cycled a second time with no change in a.
Table 2-4 contains the differences in partial pressures of oxygen
between the cobalt facilitated and back-calculated non-facilitated
curves (as plotted in figure 2-8) for a series of cobalt complex
containing membranes. The differences were determined graphically at
three different reaction times: when the back-calculated
D
non-facilitated partial pressure of oxygen, Pg^ was 15, 20, and 25
torr. The polymer bound CoSDPT complex shows an enrichment of oxygen
over the non-faci1itated process. The increasing oxygen partial
pressure at the three different reaction times can be explained by the
variance in its permeation coefficient. Early in the experiment, the
oxygen permeation coefficient is largest leading to an increase in the
difference in Pg^. Later in the experiment, the increased Pg^ value in


32
Table 2-4. Difference in oxygen partial pressure for a series of
PS/[P]-CoSDPT membranes.
TP1-CoSDPT
1st Cycle
Difference
in P02
(torr)
J1
P B
K02
P B
*02
P B
k02
WT%
1 (mm)
(torr*mm/hr)
15
20
25
44
0.261 .144
2.4
3.7
N. A.
N.A.
18.6
0.357 .065
2.6
1.0
2.5
2.6
16.4
0.687 .124
4.9
2.3
4.1
4.9
Avg. P02 =
2.3
3.3
3.8
S.D. =
1.0
1.1
1.6
2nd Cycle
17.2
0.677 .044
5.1
4.2
5.0
5.9
16.4
0.687 .124
2.5
2.8
3.6
4.2
Avg. PQ2
3.5
4.3
O
LT)
S.D. =
1.0
1.0
1.2
3rd Cycle
16.4
0.687 + .124
2.9
2.6
3.2
3.6
4th Cycle
0.687 .124 4.4 -2.4 -3.5 -3.9
16.4


33
Table 2-5.
Difference in oxygen partial pressure
PS/[P]-CoBr2SDPT membranes.
for a
series of
TPl-CoBroSDPT
1st Cycle
J1
Difference
P02
p1nBP02
r(K
(torg)
P02
WT%
1 (mm)
(torr-mm/hr)
15
20
25
7.4
0.528 .072
3.7
2.9
3.9
4.0
6.76
0.671 .047
6.7
2.6
3.5
4.4
Avg. PQ2 =
2.8
3.7
4.2
S.D. =
0.2
0.3
0.3
2nd Cycle
20.20
0.640 .051
5.8
-5.8
-4.5
-5.6
12.62
0.747 .074
3.7
-4.0
N.A.
N.A.
Avg. PQ2 =
-4.9
-4.5
-5.6
S.D.
1.3


34
Table 2-6.
WT%
24.6
16.47
6.42
6.30
24.6
6.30
Difference in oxygen partial pressure for a series of
PS/[P]-Co3FSDPT membranes.
r PI-Co3FSDPT
1st Cycle
J1
1(mm) (torr*mm/hr)
0.359
+
.050
2.3
0.506
+
.075
4.4
0.625
+
.085
5.9
0.541
+
.051
3.8
Avg
P02 =
S.D. =
2nd Cvcl
0.359
+
.050
1.4
0.541
+
.051
2.4
Avg. PQ2 =
S.D. =
Difference
in P02
(torr)
P 8
*02
P 8
*02
P 8
*02
15
20
25
6.0
7.1
7.9
1.0
0.6
0.0
3.0
4.0
4.4
5.4
5.0
5.0
3.8
4.2
4.3
1.3
1.6
1.9
-2.1
N.A.
N.A
0.5
1.0
1.3
-0.8
1.0
1.3
1.8


35
Table 2-7. Difference in oxygen partial pressure for a series of
PS/[SG]-CoSDPT membranes.
SGI-CoSDPT
1st Cycle
WT%
1 (mm)
J1
(torr*mm/hr)
Difference in Pg^ (torr)
p B p B p B
r02 02 02
15 20 25
14,
.9
0.
.533
+
.097
5.6
1.0
2,
.1
2,
.5
10,
.0
0,
.807
+
.70
6.4
2.8
3,
.0
3,
.2
6,
.56
0,
.571
+
.082
4.8
1.6
1,
.5
0,
.9
4,
.6
0.
.614
+
.077
6.1
2.6
3.
.1
3,
.0
2
0.
.492
+
.028
4.9
1.3
2.
J5
2,
.6
Avg.
P02 =
1.9
2,
.5
2.
.4
S.D. =
0.4
0,
.3
0.
.4
2nd
Cvcl e
16.
.5
0.
.647
+
.051
4.2
4.0
N.
.A.
N.
.A.
14.
.9
0.
.533
+
.097
3.2
2.5
3.
.2
2.
.5
10.
.0
0.
.807
+
.70
5.6
2.0
2.
.2
2.
.5
Avg.
P02 =
2.8
2.
.7
2.
.5
S.D. =
0.7
0.
.7
0.
,0
Lower Surface Studies
16.
1
0.
384
+
.037
4.6
0.7
0.
,0
-0.
5
1.
87
0.
358
+
.062
2.7
-1.0
-1.
6
-1.
5
Avg.
P02 =
-0.2
-0.
8
-1.
0
S.D. =
1.2
1.
1
0.
7


36
the lower chamber approaches the value of the complex and the
facilitated transport of oxygen decreases. Eventually the cobalt
complex is fully oxygenated and does not facilitate oxygen transport.
At this point in time, no subsequent enrichment occurs, i.e. the
experimental PQ2 curve and blank back-calculated curves become parallel
(figure 2-8). This is observed in all cases with the different cobalt
complexes.
Second and third cycle experiments with PS/[P]-CoSDPT membranes
produced similar enrichments in comparison with the original experiment.
The fourth cycle showed a loss of enrichment presumably because of
formation of a -peroxo complex or oxidation of the cobalt(II) complex.
While cycling experiments were not conducted on the nickel blanks with
much regularity, those that were conducted resulted in similar a values
and indicate no serious loss in separation ability. To confirm that the
observed enrichment of oxygen was due in part to the reversible binding
of oxygen and not just its desorption from the complexes already formed
during preparation of the membranes, the maximum amount of oxygen that
could possibly be bound to the cobalt centers was calculated to be
considerably less than that observed in the permeation reactions.
Facilitated transport is also demonstrated for polymer bound
CoB^SDPT and Co3FSDPT with slightly higher enrichment values
respectively (tables 2-5 and 2-6). However, in these cases the second
cycle no longer showed any enhancement, again presumably because of
formation of a /-peroxo complex or oxidation of the cobalt(II) complex.
When CoSDPT was covalently attached to silica gel (0.5 mi 11imoles/g) and
added to a polystyrene membrane, a smaller degree of oxygen enrichment


37
was obtained (table 2-7). Second cycles of these membranes resulted in
similar enrichments.
Attempts to achieve higher loadings of cobalt in the
functionalized polymer were moderately successful. Data reported in
tables 2-4 through 2-7 are from functionalized complexes which contain
approximately 0.30% cobalt. Using more strenuous reaction conditions
(elevated temperature and longer reaction time), loadings of 0.70% and
5.1% cobalt in P-CoSDPT were obtained. Permeation experiments and
cycling of the membranes were carried out as reported. Comparison data
are reported in table 2-8. The results indicate that with a moderate
increase in loading (0.70%), an initial increase in enrichment is
obtained; however, subsequent cycles are somewhat less, indicating
deactivation of the metal complex due primarily to increased loading.
It is not unexpected then that a loading of 5.1% had a small amount of
enrichment since approximately one out of every two ligand sites was
occupied. Expectedly, this should lead to a greater chance of metal-
metal interaction and increased formation of /-peroxodimers.
The incorporation of phenol (4% by weight) into the 5.1% cobalt
loaded membrane resulted in lowering the oxygen enrichment for the film
(Pq2B 15 = -1.7, Pq2B 20 = -2.3, and Pq2B 25 = -2.7 torr). It was
thought that the addition of a hydrogen bonding complex such as phenol
might stabilize the complex from deactivation. However, it appears that
it prevents reversible oxygen binding and distorts the membrane's
morphology.
The use of a more rubbery polymer, poly(butyl methacrylate), in
place of polystyrene did not result in increased facilitated transport


38
Table 2-8. Comparison of the difference in oxygen partial
pressures obtained with increased cobalt loading in
PS/[P]-CoSDPT.
Difference in Pg^ (torr)
Cobalt
Loadinq
Cvcl e
P2B
15
Pn 8
po2
20
Pn B
P2
25
0.30%
1
2.3
3.3
3.8
2
3.5
4.3
5.0
3
2.6
3.2
3.6
4
-2.4
-3.5
-3.9
0.70%
1
3.6
4.5
5.7
2
2.0
2.0
2.8
3
2.0
2.2
2.3
5.1%
1
0.8
1.4
N.A,
2
2.4
2.5
2.9


39
enrichment. Instead, it was observed that the experimental oxygen
partial pressure was essentially the same or slightly lower, (oxygen
enrichment at 15 = -1.0, Pg 20 = -0.5, and Pg 25 = -0.25 torr),
than the back-calculated non-faci1itated partial pressure. This is
explained by the fact that a blank poly(butyl methacrylate) membrane
without any additives has a high permselectivity (a = 2.2). Any
enrichment obtained with the addition of [P]-CoSDPT is overshadowed by
the increased permeability of oxygen. It is possible that this may
result in fully oxygenating the cobalt complexes at very low oxygen
pressures. This effectively blocks a facilitated transport mechanism.
In this case the complexes act as fillers and alter the permeability of
the membrane accordingly. Essentially, the rubbery polymer's diffusion
mechanism dominates that of the facilitated transport.
The mechanism of oxygen transport involved in the PS/[P]-CoSDPT
membranes described above is unlike that in liquid membranes. For
oxygen permeation using supported metal complexes in solid polymer
membranes, at least five individual processes are involved. These are
shown in figure 2-9. They include within the non-faci1itated process:
solubility of the gas, diffusion of the gas, and desorption of it from
the polymer. The facilitated path also involves oxygen binding to the
metal complex, oxygen transfer to cobalt sites through the polymer, and
deoxygenation of the metal complex. On the high pressure side, the
attainment of equilibrium for oxygen solubility at the polymer interface
is an exothermic process, as is oxygen binding to the metal center.
These are not viewed as rate determining in the transport process. The
importance of the metal center in the diffusion process is much more


40
Figure 2-9.
Contributions to permeation mechanism.


41
Figure 2-10. Schematic representation of a metal facilitated
transport mechanism due to site to site interaction.


42
complex. It is proposed that the cobalt complexes transport oxygen via
a site to site transfer (figure 2-10). The oxygen bound to cobalt is in
equilibrium with oxygen that is soluble in the polymer maintaining a
reservoir of free oxygen through the film. Cobalt-oxygen complexes on
the low pressure side dissociate oxygen into the gas phase and replace
it by binding oxygen from a neighboring reservoir. This necessitates a
dispersion of the oxygen carriers throughout the membrane as opposed to
having them only on the lower surface. The latter configuration showed
no oxygen enrichment (table 2-7--Lower Surface Studies).
In conclusion, a procedure was developed for ascertaining
facilitated transfer of oxygen that uses the permeation of nitrogen in
the sample membrane as an internal standard. Using this, it has been
demonstrated that supported cobalt complexes incorporated into a
polystyrene membrane enhance the permeation of oxygen. Having
accomplished these objectives, extension of the process using higher
cobalt(II) loadings and rubbery polymers has failed to produce a more
attractive system.
The mechanism of facilitated transport in this system differs from
that in liquid membranes where diffusion of the entire complex carries
oxygen across the membrane. A site to site transfer is proposed here
and this mechanism requires that some of the cobalt be deoxygenated in
the membrane. The value for CoSDPT in solution is reported*^ to be
6.715 x 10^ mmHg at 295 K. A more stable adduct forms in the
polymer, and its Pj,^ value determines the partial pressure of oxygen
that can be attained on the lower pressure side before metal facilitated
enhancement ceases.


CHAPTER III
DEMONSTRATION OF THE FEASIBILITY AND VERSATILITY
OF MEMBRANE REACTORS
Introduction
The previous chapter discussed some of the recent technological
and commercial developments which have occurred in membrane separation
processes over the past decade. The achieved results have subsequently
spawned a new area of membrane development and application. Membranes
are no longer being used only for separations. Increasingly, they are
being extended to biochemical process applications, petrochemical
1 2
operations, and inorganic membrane reactors.
Similarly, the work presented in this chapter has been sparked by
the demonstration of transition metal complexes supported in liquid and
polymer membranes for gas separations^'^^"^. The concept of
permselective transport of gases by such systems has led to the use of
similar membranes, or films, to catalyze reactions of gaseous
substrates. A process such as this might lead to a facile separation of
products from the catalyst. Additionally the selective removal of the
products can shift an equilibrium system.
Even though much research is being conducted within this rapidly
expanding area, the application of polymeric membrane reactors to pre
existing commercial homogeneous processes has been widely neglected.
The objective of this research was twofold. The first was to
43


44
demonstrate the feasibility of a polymeric membrane reactor using well
characterized catalytic reactions. The second was to apply the
knowledge gained in obtaining the first goal to more reactions which
utilize the advantages of a membrane reactor. The hydroformyl at ion of
propylene and the oxidation of 1-butene using transition metal compounds
supported in polystyrene, poly(butyl methacrylate), and composite
polystyrene/silicone gum rubber membranes were studied for demonstration
purposes. The oxidation of mustard agent simulants and the formation of
hydrogen peroxide were studied for application purposes.
The use of insoluble, polymer bound transition metal complexes to
9-12
catalyze homogeneous reactions has been reported. A polymeric
membrane reactor, however, utilizes a polymer medium for the reaction
environment. This novel method of reaction has not been explored and
thus investigation of its feasibility, illustration of its versatility,
and elucidation of the factors which influence reactivity are warranted.
The concept of using membranes for reaction stems from attempts to
combine multiple processing steps and thus achieve economically more
attractive systems. The ability to conduct a reaction within a membrane
along with the membrane's inherent ability for separation might
eliminate several purification steps which might otherwise be necessary.
To achieve this goal, layering or combining different membrane types may
provide systems which allow chemical reaction and product-reactant
separation within the same process unit. Hollow fiber membranes may
offer another attractive pathway for improving these processes. These
membranes consist of bundles of hollow fibers (10-1000 iim in diameter)


45
O
and provide extremely high surface area per unit volume,(e.g. 500 m in
3
a 0.3 m reactor).
An important aspect to be considered when investigating the
feasibility of membrane reactors is how a reaction at the transition
metal center is affected by the surrounding polymer environment. As in
any discipline, the most useful information is obtained by comparing
experimental systems and results with well characterized processes. In
this case, using analogous solution chemistry as a basis for comparison
gives an accurate determination of the properties associated with
reaction in a membrane. Therefore, a brief description of the reactions
employed will be presented. A more thorough description of
hydroformylation follows in chapter 4.
Hydroformylation is the term applied to the process whereby an
alkene reacts with carbon monoxide and hydrogen to form an aldehyde.
This is shown schematically below. The reaction does not proceed in the
absence of catalysts. Typically the catalysts or catalytic precursors
employed are metal carbonyls, with cobalt and rhodium being the most
widely used. The formation of butanal from propylene is the primary
reaction of industrial significance.
0
II
ch3ch2ch2ch
ch3ch = ch2
RhH(CO)(PPh3)3
H2, CO 1 RTn 65C
>
+
0
\\
CH-
CH
I
CHCH
3


46
Commercially, the straight chain isomer, n-butanal, is more
desireable than the branch chain isomer, isobutanal. This is mainly
because of the greater number of uses and applications for n-butanal.^
The hydroformylation reaction, or oxo process as it is known
industrially, is carried out under a variety of conditions. Typical
requirements when using a cobalt catalyst are total pressures of 200 to
300 atmospheres and temperatures of 120 to 170C.^ Use of a rhodium
catalyst results in much less severe reaction conditions. Rhodium
65
catalysts are active at room temperature and pressure. Equally as
important is the selectivity of products produced. Cobalt carbonyl
catalysts will produce a straight to branch ratio up to three to one,
while modified rhodium carbonyl catalysts can produce selectivities as
high as thirty to one. The relatively high activity achieved under
mild reaction conditions makes rhodium an ideal catalyst for membrane
reactor demonstration.
Hydridocarbonyl tri stri phenyl phosphine rhodium(I), RhH(CO) (PPh^,
was the complex chosen to catalyze the reaction in a polymer membrane.
First reported in 1968 by Wilkinson and co-workers,^"^ this
homogeneous solution catalyst was shown to be active at 25C and less
than 1 atmosphere pressure. It is a precursor to the proposed active
catalytic species, RhH(CO) (PPh^, and has been shown to be one of the
more active precursors. It is an ideal catalyst for demonstration
purposes.
The second system chosen to demonstrate the reactor membrane
process was that of an oxidation reaction. The word oxidation can be
used to describe many things. Equally as diverse as the applications


47
and definitions are the products and mechanisms by which oxidation
reactions occur. The aspect of this work is limited to a small portion
of the area of oxidations and therefore the scope of material presented
will be focused only upon pertinent information. There are, however,
72-75
many reviews and references on this broad subject which are
available.
Specifically, the oxidation of terminal alkenes to their
respective methyl ketones, as shown below, was studied. This reaction
was ideal since it offered a different type of reaction scheme from that
of hydroformylation, yet was possible to achieve under mild conditions -
- a necessity for laboratory purposes. It also is a process which has
been widely studied and well characterized and thus affords an excellent
example for demonstration purposes.
CH3CH2CH = CH2
CflTRLYST
0e 1 Bin. 40C
>
0
ch3ch2cch
3
The oxidation work presented in this chapter is based upon two
different catalyst systems which have received considerable attention
over the past twenty years. One of the first examples of selective,
non-radical alkene oxidations using molecular oxygen was demonstrated by
Dudley and Read in 1972. It involved a stoichiometric oxidation of a
terminal alkene in the presence of RhH(CO)(PPh^)^ or RhCl(PPh3)3 and
produced a moderately high selectivity for ketone formation relative to
aldehyde. Subsequent work indicated that an equivalent quantity of


48
triphenylphosphine oxide was produced.^ The system was made catalytic
with the incorporation of excess triphenylphosphine ligand. The
selectivity of the system indicates that the reaction does not proceed
by a free radical pathway. The mechanism proposed for this process is
shown in figure 3-1. It essentially involves coordination of olefin,
formation of a peroxo species, nucleophilic attack of the peroxo ligand
on the coordinated olefin to produce a five-membered peroxymetal1ocycle
followed by reductive elimination of the peroxymetal1ocycle intermediate
and its subsequent decomposition to the observed products.
Another catalytic system which was found to produce selectivities
in excess of 98% for methyl ketone formation was reported by Mimoun and
79
co-workers in 1978. It involves the use of a 2:1 ratio of
copper(11)/rhodium(111) co-catalyst. The system is unique. Not only
does it produce a high selectivity to methyl ketone, but also it
involves the incorporation of both atoms of dioxygen in ketone product
while exhibiting a zero order dependence for dioxygen. At 40C, greater
than 100 turnovers in four hours were achieved. It was demonstrated
that the incorporation of a small quantity of isopropyl alcohol
increases the activity of the reaction and results in an initial
formation of acetone as a byproduct. Typically the catalyst precursors
used were RhClj'X^O and CutNOj^^.SH-jO. However many others were also
employed.
80-82
Subsequent work on this system by Drago and co-workers has
shown that in the absence of a copper(II) co-catalyst, only one oxygen
atom is incorporated into the ketone and that acetone and water are
continuously produced. It was also demonstrated, that in the absence of


49
PPh i O
+
MeCOCHjR
PPh,
/ 1
0} (~ch2r
rch2
0 CH
0 C H 2
+ X
PPh,
Figure 3-1.
78
Read and Dudley mechanism for the oxidation of
terminal alkenes with RhH(CO)(PPh^)3


50
oxygen, either hydrogen peroxide or tertiary butyl hydroperoxide could
be used as the oxidant. This was shown in both the systems with and
82
without copper(II) co-catalyst. Proposed mechanisms based upon these
observations are shown in figures 3-2 and 3-3.
The previously discussed reactions were utilized for demonstration
purposes. Based upon the strategies and successes achieved, more
advantageous systems were studied. Because of the high cost of
producing and using membranes, an advantage must be gained over existing
traditional technology in order to employ membranes in these reaction
processes. Two reactions which might provide these advantages were
tested. The first of these, the oxidation of alkyl sulfides to
sulfoxides and sulfones with oxygen is shown below. The development of
reactor membranes for this purpose is of particular importance. Their
use as self decontamination systems is being actively investigated by
the United States Army Chemical Research Development and Engineering
Center. Alkyl sulfides are simulants for mustard gas agents and new
routes to their decomposition are being investigated. Reactor membranes
which can oxidatively decompose alkyl sulfides are being studied for
their use as a polymer "self-decontaminating film" on tanks and other
weaponry.
(CH3CH2CH2CH2)2S
CPTRLYST
>
0
II
C CH3CH2CH2CH2)2S
II
(CH3CH2CH,CH2)2S
3 2
0
2 am. Oj
90C


51
RhC!
rtf
Rh -O-C-H
ch3chr'oh
= CHR
Figure 3-2.
Proposed mechanism82 for the oxidation of terminal
alkenes using a rhodium(111)/copper(11) co-catalyst.


52
RhCU
l/J-'CH3CHR'OH
H+A f R#
u
Rh -O-C-H
CH-
H
2Cu
k
, Rh
""'N
CH3CRb
2Cu
III
H*
2Cu"
>^Rh
CH3CRO Rh' r HOH
^\/^ + 2Cu-j^i-2Cu" Rh-O-O-H
R //"* Op + 2H
Rh-O-C-H
ch3
h3cro^
H
ch2=chr
Cu
R
R-C-CH3
O.
Rh O
l\ ^
h-c-c-h
I >
H R
R
RhrO-O-C-H
V 1
ch2=chr ch3
Rh-O-O-C-H
CH3
CH p=CHR
Kn-u-
A
Figure 3-3.
82
Alternative mechanism for the oxidation of terminal
alkenes using a rhodium(111)/copper(11) co-catalyst.


53
The selective oxidation of sulfides to sulfoxides using transition
metal catalysts has been the object of an extensive quantity of
oo oc
research. Most of this reported work utilizes alkyl
07 OQ QQ Q7
hydroperoxides or hydrogen peroxide as the oxidant and results
in the formation of sulfones as a byproduct. The use of O2 or air with
these transition metal catalysts, in most cases, results in similar
product formation. Ledlie and co-workers used RuClj^xh^O to
97
catalyze the oxidation of butyl sulfide. Later, Riley utilized
ruthenium(II) dimethyl sulfoxide catalysts in similar systems and
proposed two possible mechanisms whereby a ruthenium(11)/ruthenium(IV)
cycle operated.^8-10 These are shown in the equations la and b, and 2.
"Ru(11)" + 02 <--=
=--> "Ru(IV)"
+ o22'
(la)
SR2 + H2C)2 + ROH <===
=> S(0)R2 +
H20 + ROH
(lb)
"Ru(IV)-SR2" + h2o <--=
=> "Ru( II)"
+ S(0)R2 + 2H+
(2)
The demonstration of ruthenium-oxo complexes in the catalysis of a
variety of organic substrate oxidations^^ indicated that such
catalysts might be suitable sulfide oxidation catalysts. Subsequently,
Drago and co-workers have shown both cis-dioxo bis(2,9-dimethyl-1,10-
phenanthrol ine) rutheni um(VI )hexafl uorophosphate, [Ru(0)2 (dmp) 2] (Pfr6)2
and the trimer trisaquo-oxo-hexapropianato-trisruthenium(III)
propionate, [RUgOfpropJgiHgOJg] (prop), to be capable of oxidizing butyl
sulfide to butyl sulfoxide^'^ in acetonitrile under relatively mild


54
reaction conditions of 100C and 2 atmospheres of oxygen. The catalysts
are shown in figure 3-4a and b respectively.
The second application of membrane reactors is focused on the
formation of hydrogen peroxide. The commercial production of hydrogen
1 08
peroxide is accomplished by the anthraquinone autoxidation process or
by direct combination of hydrogen and oxygen. Presently, there is a
rapidly expanding market for hydrogen peroxide. It was estimated that
365 million pounds of were used in 1987 for many different
applications. The largest of these included chemical production, pulp
and paper processes, and environmental purposes. It is estimated that
in 1992 590 million pounds will be utilized per year. In order to
keep up with such a rapidly expanding need, many companies are being
forced to expand and modernize their existing plants or to develop new
methods for production.
The anthraquinone autoxidation process was first commercially
operated in Germany during World War II. While many new processes have
been developed, all retain the basic features of the Riedl-Pfleiderer
108
process shown in figure 3-5. The process involves catalytically
reducing an anthraquinone to its corresponding anthraquinol which is
then oxidized in air to reform the anthraquinone and produce hydrogen
peroxide. The process has remained essentially the same for almost
fifty years. Little improvement has been achieved in the numerous
separation and purification steps which are required to maintain an
active system.
The hydrogenation portion of the reaction requires a chemically
stable, water insoluble, nontoxic solvent with a high flash point


55
b)
Figure 3-4.
(pp6)2
Sulfide oxidation catalysts: a) [RuCO^idmp^] (p^6)2
and b) [Ru20(prop)g(H20)3]+.


56
+ H202
Figure 3-5.
Anthraquinone autoxidation process.


57
and low volatility. Typically, a 50:50 mixture of benzene and Cg
secondary alcohols is used. One of the major problems associated with
this system involves maintaining a soluble working material. Reduction
is carried out using slightly elevated partial pressures of hydrogen at
temperatures under 100C and conversion is limited to 50% to minimize
anthraquinone-deactivating secondary reactions. Catalysts which have
been utilized for this process step include supported Raney nickel and
pal 1 adi um. ^
The oxidation of the resulting anthrahydroquinol is easily
accomplished without the aid of a catalyst. The rate is dependent upon
the pressure of oxygen and temperature of the reaction. The most
critical portion of this step is in the removal of the reducing catalyst
and the subsequent phase boundary surface area between the organic
solvent and water used for extraction. Regeneration of the working
solution is required to remove all inactive anthraquinone derivatives
formed as well as any aqueous solution retained in the system.
A second method used for hydrogen peroxide production could be
considered to be in its infancy by comparison with the anthraquinone
process. Only within the past ten years has the ability to directly
combine hydrogen and oxygen to produce hydrogen peroxide become
109
available. While little has been reported of its mechanistic detail,
the procedure involved is rather straightforward. The reaction is run
in an aqueous medium using palladium on adsorbent carbon as a
hydrogenation catalyst with superatmospheric pressures (200 to 4000
psig) of hydrogen and oxygen. The reaction is conducted under mild
temperatures (0 to 50C) and produces an aqueous solution which is


58
approximately 20% by weight. The use of an all-aqueous reaction
medium provides a safer reaction process since it does not produce
mixtures of H2O2 and an organic component. Application of these
processes to membrane reactors may similarly produce a system which
reduces the number of process steps required to maintain an active
system while operating under safer reaction conditions.
The primary goal of this project was to demonstrate the ability to
achieve reaction within a polymer environment and, based upon the
achieved success, apply the process to reaction systems which would be
advantageous for one reason or another to carry out within a membrane.
The work presented supports this objective. The process developed is an
extension of pre-existing catalyst technology and is not an attempt at
discovering new catalysts.
Experimental
The complexes studied and/or used in this work were prepared from
reagents which were either purchased or previously synthesized. The
following procedures can be used to prepare these compounds. The
solvents used were purified by storage over 4A molecular sieves under an
atmosphere of nitrogen. Characterization of the complexes was conducted
using a Nicolet 5DXB FTIR Spectrometer. Identification and
quantification of reaction samples were conducted using a Varian Model
3700 gas chromatograph, a Hewlett-Packard 5890A gas chromatograph in
connection with a Nicolet 5DXB FTIR Spectrometer and a Varian Model 3400
gas chromatograph in connection with a Finnigan Mat Model 700 Ion Trap


59
Detector. Elemental analyses were conducted by the University of
Florida Department of Chemistry Microanalysis Service.
Hvdridocarbonvltris(triphenylphosphine)rhodium( I), RhH(CO) (PPhj)^
Hydridocarbonyl tris(triphenyl phosphine)rhodium(I), RhH(CO) (PPh^)^,
was prepared according to the literature.111 Experimental analysis:
%C = 71.8, %H = 5.12, %N = 0.00. Theoretical analysis: %C = 71.9,
7oW = 5.05, %N = 0.00. Melting point 120 122C (lit. 121 -122C). Ir
analysis (nujol mull): Rh-H: 2041 and 785 cm"1 (lit. 2040 and 786 cm"1),
C=0: 1918 cm"1 (lit. 1923 cm'1).
Tri fl uoroacetatotri s (tri phenyl phosphine) rhodium! I), RhlOoCCF-,) (PPh^K
Trifluoroacetatotris(triphenylphosphine)rhodium(I),
Rh(02CCF2)(PPh3)3 was obtained from Dr. Cindy Getty and Steve
112 113
Showalter. It can be prepared from RF^^CCFj)^ according to a
method similar to that reported by Drago and Telser.11^
Pioxo-bis(2.9-dimethyl -1,10-phenanthrol inelruthenium(VI) hexafluoro-
phosphate, Ru(0)o(dmp)ol(PF^lo
[Ru^^dmp^] (PFg^ was obtained from Dr. Cindy Bailey. It can
be prepared with moderate difficulty from the oxidation of
[Ruidmp^F^O^]^ with ceric ammonium nitrate, (NH^CeiNOj)^.1^11 1 ^
Trisaquohexapropionatotrisrutheniumnil) propionate.
IRu30 (prop) 6XH2Q131,( prop).
The ruthenium trimer [RujOiprop^F^O^] (prop) was obtained from
Dr. Shannon Davis. It can be prepared from RuCl^xF^O.1 lf>
Membrane Preparation
The membranes employed in this study were prepared using a casting
technique. The appropriate polymer was dissolved in a suitable solvent,


60
most often toluene or methylene chloride. The transition metal complex
to be used for a specific reaction was then dissolved in the same
solvent and added to the viscous polymer solution. The resulting
solution was then transferred to an aluminum foil form. Evaporation of
the solvent at room temperature resulted in the formation of uniform
polymer membranes with an average thickness between 0.5 and 1.0 mm.
These were used without further treatment.
Permeation Apparatus
The apparatus used for the membrane reactions, (shown in
figure 3-6), was designed to provide support of the membrane under
experimental reaction conditions. The film is supported both on the low
and high pressure sides by stainless steel metal frits {bn pore size).
Temperature of the reaction is controlled by a Variac and thermal tape
in conjunction with a temperature controller.
Permeation Procedure
A typical permeation experiment is described in the following
paragraph. The membrane to be used is secured between the two chambers
of the reactor using o-rings and the two parts screwed together to
ensure a proper seal. Both chambers are evacuated for approximately 1
hour to remove any excess solvent trapped in the membrane. The lower
and upper chambers are then closed off under vacuum and the upper
chamber filled with one atmosphere of the reactants. The gases permeate
through the membrane during which time reaction occurs. The products
and unreacted substrates then desorb from the film into the evacuated
chamber. Periodically, both chambers are monitored to determine the
extent of reaction. This is done using FID gas chromatography using a


61
5 micron pore size
Figure 3-6.
Reactor membrane apparatus.


62
2.5m stainless steel column packed with either porapak Q or
diethyleneglycol adipate. GC-FTIR, and GC-MS were also run to confirm
all of the product identities.
Results and Discussion
Hydroformvlation of propylene
The hydroformylation of propylene was the first reaction attempted
in order to demonstrate the reactor membrane process. The reaction was
carried out at 65C using a 1:1:1 gas mixture of the reactants hydrogen,
carbon monoxide, and propylene at a total pressure of 1 atmosphere with
a polystyrene membrane which contained 2.14 x 10^ moles of
RhH(CO)(PPh2)3. The pressures in the two chambers equilibrated over a
period of three days. Gas samples were taken periodically, however with
a decreasing pressure gradient, it is impossible to report the data on
an activity curve as would normally be done with a catalytic run.
Alternatively, the amount of product produced within a given period of
time is reported. In this case, 4.7 x 10^ moles of butanal and
6.6 x lo'10 moles of isobutanal was produced in 72 hours. While it is
true that this is an extremely small quantity of product and represents
a very small amount of conversion, it is, never-the-1ess important since
it is the first demonstration of reaction within a polymer environment.
There are many factorss which might account for the low
conversion. First, it must be considered that the reactants are gases
and therefore their concentrations in the membrane are appreciably less
than those of an analogous solution. The interaction of substrate and


63
catalyst is reduced because of this lower concentration of reactants.
It is entirely possible that within the polymer, there is little
catalyst substrate interaction occurring as a result of the reactants
permeating through the film relatively rapidly. This is heightened by
the slow diffusion of reactants within the film and the immobility of
the catalyst. It is likely that a large fraction of the reactants pass
through the film via pores and channels without ever coming into contact
with the catalyst. Coupled with this problem is the fact that three
different reactants must make contact with the catalyst for reaction to
occur.
Considering this, a possible way to improve upon the extent of
reaction would be to alter the diffusion and solubility characteristics
of the gases in the polymer. To accomplish this, a different polymer
was chosen for the reaction medium. Poly(butyl methacrylate), PBM, was
the polymer chosen to demonstrate how the diffusion and solubility
characteristics of the polymer could influence the reaction
characteristics. Pure PBM has a glass transition temperature (Tg) of
27C whereas the corresponding value for polystyrene is 100C. PBM is a
rubbery polymer under reaction conditions and its diffusion and
solubility properties are considerable different than of polystyrene,
PS, a glassy polymer under the same reaction conditions.
Using reaction conditions identical with the previously mentioned
_ C
reaction, in conjunction with 3.9 x 10 moles of catalyst contained in
-8
the PBM film, 1.1 x 10 moles of butanal was produced with only trace
quantities of isobutanal present. This is a remarkable observation
since it demonstrates just how great an effect the polymer medium can


64
have on the reaction. This result can be likened to running a solution
reaction in which two entirely different solvents are utilized. Perhaps
the most important observation is not in the increased activity, but
rather in the drastic improvement in selectivity that is achieved.
The use of a different polymer shows that the extent of reaction
can be altered by changing the diffusion and solubility properties of
the polymer. It was thought that a greater extent of reaction might be
obtained through optimization of the reaction conditions. This can be
accomplished through two means. The first involves the addition of
excess ligand. The second pertains to increasing the reaction
-
temperature and pressure. This is carried out using 2.4 x 10 moles of
RhH(CO)(PPh^)3 in conjunction with five times as much triphenyl phosphine
in a PBM film at 100C. A pressure of two atmospheres of synthesis gas
(H2 and CO), in a 1:1 ratio, is placed on both sides of the membrane and
left for a period of two days. At the start of the reaction, 2.0 mL of
propylene was injected into the upper chamber creating a small pressure
differential (50 mmHg). This experimental setup ensures complete
saturation of the membrane with synthesis gas and the partial pressure
of propylene is used to facilitate its permeation through the membrane.
Within twenty four hours, 2.2 x 10~^ moles of butanal are produced with
trace amounts of isobutanal also observed.
The best results are achieved using a system that contains
Rh(2CCF2)(PPh3)3 in PBM with a fivefold excess of ligand under the same
reaction conditions reported previously. It produces 8.1 x 10^ moles
of butanal and trace amounts of isobutanal. This catalyst had
112
previously been studied and shown to be efficient for the


65
hydroformylation of liquid substrates in solution. In this reported
case, a five molar excess of triphenylphosphine in neat 1-hexene
produced 225 turnovers and a 4.3 to 1 ratio of straight to branch chain
aldehyde. Comparison of the polymer and solution reaction mediums
reveals that they have similar dielectric constants. A summary of the
membrane reactions is shown below in table 3-1.
Oxidation of 1-butene
The second system studied for demonstration purposes resulted from
a serendipitous discovery. When air accidently leaked into the initial
hydroformylation system described above, the rapid production of acetone
from propylene was observed. This product formation appeared to occur at
a much faster rate than that of the hydroformylation products. This
discovery led to attempting the oxidation of terminal alkenes to their
respective methyl ketones for the demonstration of reactor membranes.
Again the first membrane studied is a PS film that contains
. 5
3.9 x 10 moles of RhH(CO)(PPh^)3. Reaction conditions employed were
slightly milder than those of the hydroformylation systems. Temperature
is maintained at 40C and a 1 atmosphere mixture of and 1-butene is
charged into the upper chamber. After three days, 7.9 x 10 moles of
2-butanone is produced selectively. Data for this reaction and others
similar in nature are reported in table 3-2. The first thing observed
with this demonstration reaction is that under milder conditions, a
substantially larger quantity of product is produced relative to the
similar hydroformylation system. This indicates, as expected, that
different types of reactions are influenced to varying extents by the
surrounding environment.


66
Table 3-1. Hydroformyl ation of propylene with RhH(CO)(PPh^)3
Membrane
Moles
Catalvst
Mol es
Butanal
Turnovers3
Butanal
Moles
Isobutanal
Turnovers3
Isobutanal
PSb
2.14xl04
O
r <
1
O
r1
X
2.2xl0'6
6.6xl0'10
3.1 x 10'6
PBMb
3.9 xlO"5
l.lxlO'8
2.8xl0'4
trace

PBMC
2.4 xlO6
2.2x10*7
9.2xl0'2
trace

PBMd
2.4 xlO'6
8. lxlO7
3.4X10'1
trace
a turnover is moles of product/mole of catalyst.
b reaction conditions are 65C, 1 atm. H2, CO, and propylene
(1:1:1 mix) in the upper chamber, and reaction time is three days.
c membrane contains 1.2x10~^ moles triphenylphosphine at 100C.
Both chambers contain 1 atm. of H2, CO (1:1 mix). Upper chamber
contains an additional 2.0 mL of propylene (1 atm. pressure).
Reaction time is one day.
d Rh(O2CCF2)(PPh^)3 catalyst in place of RhH(CO)(PPh^)3 under
identical conditions to note c. Reaction time is one day.


67
Table 3-2. Oxidation of 1-butene.
Membrane
Catalvst
Conditions3
Mol es
2-butanone
( x 10y)
Turnovers
2-butanone
( x 1041
PS
RhH(CO)(PPh3)3
7.9
2.0
PS
RhH(CO)(PPh3)3
2nd cycle
14.
3.6
PBM
RhH(CO)(PPh3)3
12.
3.1
PBM
RhH(CO)(PPh3)3
2nd cycle
47.
12.
PBM
RhH(CO)(PPh3)3
60C
24.
6.2
SGR/PS
Rh(111 )/Cu(11)b
200.
25.
PBM
Rh(III)/Cu(11)b
60C
160.
20.
PBM
RhH(CO)(PPh3)3
1-hexene
240.
62.
a standard reaction conditions: 3.9x10"^ moles catalyst at 40C
with 1 atm. O2 and 1-butene (1:1 mix). Reaction time is three
days.
b 8.0x10^ moles RhCl^xh^O and 1.6xl0'4 moles Cu(N03)22.5H20.


68
The same quantity of catalyst as was used in the previous reaction
was supported in a PBM film. Under similar reaction conditions, an
increase in the amount of product was observed. In this case,
g
1.4 x 10 moles of 2-butanone was produced. Cycling experiments were
conducted by reevacuating each system and refilling the upper chambers
with reactants. Essentially all membranes are saturated with reactants
at the start of the second cycle. This results in almost a twofold
increase in the production of 2-butanone for the polystyrene system and
nearly a fourfold increase with poly(butyl methacrylate). Again this is
best explained by the theory that saturation of the membranes with
reactants has occurred resulting in increased catalyst-substrate
interaction. Improved reactivity is the end result of this increased
interaction. Raising the reaction temperature to 60C while using the
PBM/RhH(CO)(PPh^)3 membrane also improves reactivity in the butene
system. This is expected for a temperature dependent reaction.
Another reaction using the liquid substrate 1-hexene was conducted
to verify that higher substrate concentration within the membrane would
indeed result in increased reactivity. Five drops of the substrate was
placed on the film and the reaction run with the same quantity of
catalyst and reaction conditions. In three days, 2.40 x 10~'7 moles of
2-hexanone are produced selectively. This lends support to the idea
that the reactivity of the membrane can be increased dramatically under
more solution-like reaction conditions.
Based upon the observed results, a mechanistically different
reaction was attempted. It involved the use of a Rh(III)/Cu(II) co
catalyst system in the oxidation of terminal alkenes. A silicone gum


69
-5 -4
rubber polymer containing 8.0 x 10 moles of RhCl3*xH20 and 1.6 x 10
moles of Cu(N03)2*2.5H20 along with a approximately 1.0 ml of
isopropanol was layered on a polystyrene blank membrane. This resulted
in the production of 2.0 x lo-*7 moles of 2-butanone in 72 hours. The
same catalyst system contained in a PBM film at 60C was not quite as
reactive (1.60 x 10"^ moles in 72 hours). These observations show that
mechanistically different reactions such as this can be very active.
This supports the conclusion that the reaction type itself plays a large
part in determining the extent of reaction within the polymer framework.
Oxidation of butyl sulfide
Based upon the successes achieved in the above reactions,
attention next turned towards processes in which membrane use may be
more economically attractive. The catalytic oxidation of the simulant
butyl sulfide is studied with (1) Ru(Cl)2(Pph^)3, (2)
[Ru(0)2(dmp)2](PF6)2, and (3) [Ru30(prop)6(H20)3](prop) in
polystyrene/silicone gum rubber composite membranes. Composite catalyst
membranes are obtained by evaporating a catalyst/silicone gum
rubber/toluene solution onto a preformed blank polystyrene film. The
ruthenium membrane oxidations of butyl sulfide are carried out by
coating the upper side (the side exposed to the higher pressure) of the
films with a small amount of the liquid substrate. The top chamber of
the reactor is then filled with 30 psi 02 and the bottom chamber is
closed off under vacuum. Temperature of the reaction is maintained at
90C. The pressures within the two chambers equilibrate over a period
of two days. The gas which collects in the bottom chamber is determined
to contain large percentages of butyl sulfoxide, butyraldehyde, and


70
propionaldehyde, along with a small quantity of unreacted butyl sulfide.
Trace quantities of 1-butene and 1,2-epoxybutane are also observed using
GC-MS.
In all membrane reactions, the total amount of products formed
appears to be substantially smaller in comparison with solution data. A
better method of analysis in this particular case would be to compare
the percentage conversion of butyl sulfide. In analyzing these membrane
reactions, the percent conversion is based upon the amount of butyl
sulfide and products which have passed through the membrane and not on
the original amount exposed to the film. This is the most relevant mode
of analysis since the employment of these materials as self
decontaminating films focuses only on the gases which permeate the film
and their relative amounts.
Table 3-3 lists the mole percent conversion for each of the
composite membrane catalysts systems. It should be noted that a
modified reactor design employing a smaller film with less catalyst is
used in the phenanthroline derivative system. In light of this, a
better judge of the membrane activities is made by comparing turnovers
of the respective catalyst membranes. A turnover is defined as the
number of moles of product produced per mole of catalyst. This gives an
accurate representation of the reaction assuming that an excess amount
of substrate was exposed to each film. Turnover data is presented in
table 3-4 and indicates that the ruthenium trimer is the best overall
catalyst employed in the membranes. Evidence which supports the th ry
that a large quantity of substrate may never come in contact with the


71
Table 3-3. Butyl sulfide membrane conversion data for various
ruthenium catalyzed oxidations by 0? at 1 atm. and
90C.
Mole Percent
Reaction Butyl Butyl
Time (hrs) Sul fide Sulfoxide Butanal Propanal
Total
Conversion
Ru(Cl)2(PPh3)3
0
24
2.8
11.3
40.0
45.9
97.2
48
1.9
15.5
40.0
42.6
98.1
0
24
[Ru30(prop)6(H20)3](prop)
10.8
1.4
2.0
85.8
89.2
42
3.6
0.2
0.3
95.9
96.4
n
[Ru(02)2
(dmp)2](PF6)2
24
85.6
1.2
13.2
--
14.4
48
78.0
2.6
19.4
trace
22.0


72
Table 3-4. Butyl sulfide membrane turnover data.
Turnovers
( x 102)
Catalvst
Butyl
Sulfoxide
Butanal
ProDanal
Total
Ru(Cl)2(Pph3)3
0.27
0.97
1.11
2.35
[Ru30(prop)6(H20)3](prop)
1.00
1.49
63.70
66.19
[Ru(0)2(dmp)2](PF6)2
0.40
4.68

5.08
Turnover data are reported at a reaction time of 24 hours based on
data in table 3-3.


73
catalyst in the membrane is obtained by comparing tables 3-3 and 3-4.
It is apparent that a larger conversion percentage can be obtained by
increasing the catalyst loading in the membrane and thus increasing the
extent of interaction between substrate and catalyst.
Comparison of the membrane data can be made to their solution
analogues*06 as well. Reported mole percent conversions of butyl
sulfide for the three ruthenium catalysts in solution under similar
reaction conditions is presented in table 3-5. The relatively high
percentage of conversion compared to solution studies indicates that
reactor membranes may prove to be useful as self decontamination
systems. The data obtained is very encouraging and indicates that the
catalyst is active when incorporated into a polymer network. Though the
activity of the membranes is lower than the solution systems, based on
the amount converted per unit time, the high conversion of material
passing through film is a desired result.
Formation of hydrogen peroxide
The production of hydrogen peroxide has been accomplished by the
anthraquinone autoxidation process and by direct combination of hydrogen
and oxygen. The application of these two systems to membrane reactors
is yet another process which has shown membrane reactors to be a
versatile process. One part of this research incorporates the basic
reaction scheme outlined in the introduction. As noted earlier, a major
drawback associated with the anthraquinone autoxidation process is
maintaining a soluble system. Several reaction and separation steps are
needed to maintain an active process. This work represents a novel


74
Table 3-5.
Butyl sulfide solution reaction conversion data for
various ruthenium catalyzed oxidations by 0? at
90C.
Mole Percent
Reaction
Time (hrs)
Butyl
Sul fide
Butyl
Sulfoxide Butanal
Total
ProDanal Conversion
Ru(Cl)2(Pph3)3
0
100
- -
0
12
49.7
50.3
50.3
36
40.9
59.1
59.1
[Ru30(prop)6(H20)3](prop)
0
97.4
2.6
2.6
12
77.2
22.8
22.8
37
59.7
40.7 0.6
41.3
[Ru(02)2(dmp)2](PF6)2
0
99.3
0.7
0.7
12
72.1
25.9 2.0
27.9
36
69.1
28.1 2.8
30.9
Source
of data is
reference 106.


75
approach aimed at minimizing the number of required process steps while
maintaining the solubility and stability of the working material in both
its oxidized and reduced states. This would result in a more
economically attractive system. The reaction is conducted by
incorporating the catalytic system into a rubbery polymer membrane, PBM,
which is used as the medium for reaction. The second system under
investigation, the direct combination of oxygen and hydrogen, is
performed by incorporating a palladium catalyst into a PBM membrane and
using it as the reaction medium.
Flat reactor membranes are formed from poly(butyl methacrylate)
using a casting technique. Depending upon the system being studied,
either palladium black or a mixture containing 2-ethyl anthraquinone and
palladium black are incorporated in the polymer membrane. A different
apparatus than was used in the previous systems is used to support the
reaction. It is shown in Figure 3-8 and consists of two glass chambers.
The membrane is sealed between them using an 0-ring joint and clamp.
The reaction is facilitated by passing hydrogen gas over the bottom side
of the membrane and by saturating an aqueous solution on the top side of
the membrane with oxygen. Reaction occurs as the two gases diffuse into
the membrane and come in contact with the catalyst system. The
temperature of reaction is maintained by placing the reactor in an oil
bath at the desired temperature. A slightly positive pressure of
hydrogen is maintained in the lower chamber. Reaction occurs over a
four day period. The resulting hydrogen peroxide is extracted into the
aqueous layer and titrated with potassium permanganate to determine the
extent of reaction.


76
OXYGEN IN
OXYGEN OUT
HYDROGEN IN
MEMBRANE
AQUEOUS SOLUTION
HYDROGEN OUT
O-RING JOINT
Figure 3-7.
Hydrogen peroxide membrane reactor.


77
There are several key variables in this process that have been
investigated. Included among these are temperature dependence of the
process, the effect of added promoters, and the effect of cycling the
membranes. Data for the performed reactions are contained in table 3-6.
The results indicate that the anthraquinone systems are the most active.
Increased temperature also results in a more active system. Reaction
using only palladium black was accomplished with comparable activity to
the anthraquinone system. The best system for direct combination of
hydrogen and oxygen is one which incorporates an acid and halide
promoter in the film and employs higher reaction temperatures. Attempts
to find a more active system using a palladium colloid suspended in a
polymer film failed when the poly(vinyl alcohol vinyl acetate) membrane
used in the reaction dissolved during reaction.
In conclusion, the comparison of all membrane reactions with their
respective homogeneous analogues results in some notable distinctions.
The membrane reactions appear to be substantially less reactive. This
is due largely in part to the relative amount of time that the substrate
spends in contact with the catalyst. A possible way of improving upon
this would be to increase catalyst concentration. A thicker membrane
might also provide for better interaction. Comparatively, a solution
reaction occurs with the substrate continuously diffusing in and out of
solution. This results in an infinite amount of exposure with the
catalyst. In a membrane reaction, the substrate is contained in the
film for a much smaller amount of time, effectively limiting the extent
of reaction. Another observation that would explain the difference in
the reactivities of membrane and solution reactions is the relative


78
Table 3-6.
Hydrogen peroxide formation.
CATALYST
PROMOTER
REACTION
CONDITIONS
1
CYCLES
2
(moles H?i
3
Pd BLACK & NONE
2-ETHYL ANTHRAQUINONE
60C
2.2
2.2
1.1
Pd BLACK & NONE
2-ETHYL ANTHRAQUINONE
95C
11.
12.
6.9
Pd BLACK
NONE
60C
0.9
PD BLACK
H+, Br'
60C
1.1
Pd BLACK
NAFION, H+, Br'
60C
1.7
1.7
0.9
Pd BLACK
NONE
85C
1.6
1.4
Pd BLACK
H+, Br'
85C
1.5
1.8
1.5
Pd BLACK
NAFION, H+, Br'
85C
2.0
1.0
2.0
Reaction conditions: PBM film layered on PS, 20.0 mL aqueous
solution for four day cycles. [H+] = 1 M HC1, [Br'] = 1.3 x 10'3 M
KBr, 3.6 x 10'^ moles Pd black, and/or 1.5 x 104 moles 2-ethyl
anthraquinone.


79
difference in substrate concentrations contained in each reaction
medium. This directly affects the number of catalyst substrate
interactions which occur.
The initial objective of this project has been obtained.
Demonstration of the feasibility and versatility of transition metal
reactor membranes has been achieved with both hydroformylation and
oxidation reactions. The activities of the membranes are low as a
result of the engineering design of our experiment. The use of hollow
fiber membranes may lead to a more productive system. For example, the
best hydroformylation system studied produces 8.1 x 10"^ moles of
O
butanal in 24 hours or 4.06 x 10 g of butanal per minute using a film
with a surface area of 5.0 x 10'^ m^. A typical hollow fiber membrane
3
unit using 100/jm fibers contained in a 0.3 m reactor has a surface area
p
of 500 m Transposing our system to this reactor would produce 4.0 x
p
10 g of butanal per minute. This may be one way of increasing
production capabilities in membrane reactors. Optimization of reaction
conditions has been shown to result in remarkable increases in
reactivity.


CHAPTER IV
HETEROGENEOUS HYDROFORMYLATION OF PROPYLENE USING SUPPORTED
RHODIUM CATALYSTS IN A CONTINUOUS GAS FLOW REACTOR
Introduction
The previous chapter demonstrates the feasibility and versatility
of facilitating chemical reactions within an organic polymer
environment. One remarkable attribute of membrane reactions lies in
their ability to achieve high selectivity for a particular product.
This is evidenced in the hydroformylation of propylene to n-butanal with
a high degree of selectivity. A major drawback that is associated with
these membranes is in their extremely low activity. The work presented
in this chapter involves the development of a gas phase, heterogeneous
catalyst based system resulting in substantially increased activity
while maintaining the selectivity associated with the polymer membrane
reactors.
The hydroformylation of propylene is the reaction chosen to
demonstrate this objective. The ability to use a gaseous substrate, the
possibility of producing either straight or branched chain product, and
the availability of a catalyst which is active under moderate reaction
conditions makes it ideal for study. The reaction is previously
described in chapter 3. A more detailed discussion of the reaction is
presented in this section.
80


81
Hydroformylation is the process whereby an alkene reacts with
carbon monoxide, CO, and hydrogen, W^, to form an aldehyde. The
hydroformylation of propylene results in the formation of both n-butanal
and isobutanal as shown below.
0
xNch
I
CH3CHCH3
The reaction does not proceed in the absence of a catalyst.
Commercially, two transition metals, cobalt and rhodium, are used to
form active catalyst complexes and are usually employed as the metal
carbonyl complexes. First discovered by Otto Roelen in 1938,^ the
process has since grown to immense proportion. In 1980, over eight
billion pounds of aldehydes or their derivatives were produced by the
process, with the formation of butanal from propylene being the primary
reaction scheme.^
Commercially, the straight chain isomer, n-butanal, is more
desireable than the branched chain isomer, isobutanal. This is because
of the greater number of uses and applications for n-butanal.^ As
shown below, n-butanal can be converted through a variety of steps to
n-butanol and 2-ethylhexanol. The latter can be converted into
plasticizers for polyvinylchloride resins.
The hydroformyl ation reaction, or oxo process as it is known
industrially, can be achieved using a variety of conditions. Typical
requirements for a cobalt catalyst system require total pressures of 200
0
CH3CH=CH2
RhH(C0MPPh3)3
I,. CO 1 OTO. 65
^ ch3ch2ch2ch +


82
ch3ch2ch2cho
-h2o
cot.
ch3ch2ch2ch2oh
to 300 atmospheres and temperatures of 120 to 170C.^ Use of rhodium
catalysts result in much less severe reaction conditions. Activity can
65
be observed using room temperature and pressure. Equally as important
is the selectivity. Cobalt carbonyl catalysts produce a straight to
branch ratio up to three to one, while modified rhodium carbonyl
c/\
catalysts produce selectivities as high as thirty to one. The
selectivity obtained is dependent upon a number of factors including the
ligand environment of the metal, the presence of excess ligand in the
system, and the pressure of gaseous reactants used. The relatively high
activity achieved under mild reaction conditions makes rhodium an ideal
catalyst for continuous gas flow reactor demonstration.
Modified rhodium oxo catalysts were introduced into commercial use
118-120
in 1976. One of these, hydridocarbonyltristriphenylphosphine
rhodium(I), RhH(CO)(PPh^Jg, was the catalyst chosen to catalyze the
reaction. First reported in 1968 by Wilkinson and associates,66-71
homogeneous catalyst was shown to be active at 25C and less than 1
atmosphere pressure. It is a precursor to the proposed active catalytic


83
species, RhH(CO) (PPh3)2, and has been demonstrated to be one of the more
active rhodium precursors. It does not react to form inactive metal
clusters like many other rhodium carbonyl complexes.
Selectivity is controlled by a number of factors. The use of
polar solvents as the reaction medium leads to increased reactivity and
produces increased selectivity. Most importantly, the addition of
excess triphenylphosphine results in increased linear selectivity. The
reaction has even been carried out in molten triphenylphosphine.^ A
disadvantage though, is that the rate of hydroformylation decreases with
the addition of excess phosphine. The increase in selectivity has been
attributed to increased steric hinderance while the decreased activity
can be explained by the effect of shifting the equilibrium from a
proposed active catalytic species towards the precursor. This
equilibrium is shown in the equation below.
RhH(CO)(PPh3)3 <==========> RhH(C0)(PPh3)2 + PPh3
The widely accepted mechanism of this reaction is depicted in
figure 4-1. As shown, the reaction can occur by either a dissociative
or associative pathway with the first step being the subsequent
65
dissociation of a triphenylphosphine ligand. Coordination of carbon
monoxide is the next proposed step. Next, olefin coordination occurs.
It is the most critical step. Subsequent addition of the olefin to the
rhodium hydride bond determines whether linear or branched chain
aldehyde is formed. Markonikov addition results in the formation of a
branched alkyl complex, while anti-Markonikov addition results in the


84
L...
H
jRhCO
I
CO
H
-L
L Rh CO
L
CO
H
CO
R
R
CO
f-RCHjCHjCHO
Figure 4-1.
Associative and dissociative hydroformyl at ion
reaction mechanism.


85
formation of a linear alkyl complex. Carbon monoxide migration and
insertion to form the acyl complex is the next proposed mechanistic
step. This is followed by the oxidative addition of hydrogen. The
latter step is thought to be rate determining in the reaction but it
65
remains uncertain. Reductive elimination of aldehyde results in
reformation of the catalytic species.
Hydroformylation using modified rhodium catalysts results produces
a rather complex system. Many Rhodium species have been observed in
these systems including RhH(CO) (PPh^)3> RhH(CO) (PPh^)2> RhHfCO^iPPhg^,
118
and RhHiCO^lPPh^). These complexes exist in equilibrium with each
other and are formed from either triphenylphosphine dissociation or CO
addition. The truly active species has not been determined but may be
any one or combination of these in solution.
The high cost of rhodium has limited its use commercially.
Development of a process which alleviates catalyst recovery problems
associated with conventional homogeneous systems while achieving high
selectivity and activity will result in an economically more viable
reaction process. A considerable effort has been devoted to modifying
homogeneous based rhodium catalysts to form heterogeneous catalysts.
This would offer immediate advantages in catalyst/product separations.
Use of insoluble supported catalysts in liquid phase reactions or vapor
phase reactions over supported catalysts might achieve this desired
objective.
Attempts to form heterogeneous oxo catalysts by attaching them to
supports through their phosphine ligands has not resulted in better
1 OO 1 p C
catalytic systems. Use of these supported catalysts in liquid


86
phase reactions leads to active and selective systems, however, catalyst
leaching occurs. Cleavage of the phosphorous carbon bonds used to
attach the catalysts results in degradation of supported complexes
1Pfi 121
providing a pathway for catalyst leaching from the support.
An effective gas phase system is reported by Arai and
co-workers. The process utilizes silica gel as a support. It is
covered with a polymer formed from styrene and divinyl benzene and then
functionalized with phosphine ligands. Chiorocarbonylrhodium(I) dimer,
[Rh(CO)2d]2, is then supported on its surface. This catalyst is found
to be effective in hydroformylating both ethylene and propylene at 100C
with atmospheric pressures of gaseous reactants. One of the major
drawbacks associated with this system is in the low selectivity obtained
for the production of n-butanal (63%) from propylene. The phosphine
linkage was viewed to be important since direct deposition of
(PPh3)2Rh(CO)Cl and RhCl^ on silica exhibited little activity under
similar conditions. Deposition of (PPh-^RhiCOjCl on alumina and
activated charcoal, however, produces active systems under substantially
1 29
more severe reaction conditions. Again low selectivities for the
linear aldehyde are obtained (56.5 to 65.5%). Gas phase
hydroformylation of ethylene and propylene have also been achieved over
130-13?
zeolite supported rhodium catalysts. Again the selectivity of
these systems is poor (<67% linear aldehyde) and the simultaneous
hydrogenation of propylene and aldehyde is a severe problem.
The objective of the work presented in this chapter is to extend
what has been accomplished with membrane based reactors. This is
achieved by the development of a heterogeneous catalyst based system


87
which produces substantially increased activity while maintaining the
intrinsic benefits associated with the polymer membranes, namely their
selectivity. This is accomplished by deposition of a rhodium catalyst
and excess phosphine ligand on silica gel and its use in a gas phase,
continuous flow reaction. The development of a reactor which is
connected to a gas chromatograph ("on-line GC") results in an accurate
evaluation of the reaction properties. Modification of the catalyst
system by coating with a polar, nonvolatile system results in increased
activity and selectivity.
Experimental
The transition metal catalysts studied in this work are prepared
as previously described in chapter III. Identification and
quantification of reaction samples are conducted using a Perkin Elmer
model 900 gas chromatograph placed in conjunction with a continuous flow
gas reactor. This is more simply described as an "On-line" gas
chromatograph.
Catalyst Preparation
The catalysts employed in this study are prepared by dispersion on
a solid support in the presence of an excess quantity of
triphenylphosphine ligand. A typical description of this procedure is
detailed below. A 250 mL round bottom flask is charged with 0.600g of
silica gel (vacuum dried at 80C), 0.0919g (1.000 x 10~4 moles)
RhH(CO)(PPh^)3, and .262g (1.00 x 10'^ moles) triphenylphosphine.
Twenty five milliliters of chloroform is added to the solid mixture and


88
the solution stirred for approximately five minutes. It is then rotary
evaporated giving a yellow granular product which is vacuum dried
overnight at 45C. Catalysts which are coated with propylene carbonate
are prepared similarly with the propylene carbonate being dissolved in
the chloroform before its addition to the solid catalyst mixture. A
brief description of the preparation of all catalyst systems
investigated is listed below. Each is identified by itss appropriate
abbreviation throughout the remainder of the text.
RhH\SG
The catalyst is prepared by dispersion of 0.230g (2.50 x 10~4
moles) RhH(CO)(PPh^)3 and 0.656g (2.50 x 10^ moles) triphenylphosphine,
PPh-j, on 1.50g of silica gel using the method outlined above.
RhH\SG\PC
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10~4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10~3 moles) triphenylphosphine
and 0.08g of propylene carbonate on 0.600g of silica gel using the
method described above.
RhHXMPPS
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10~4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10'^ moles) triphenylphosphine
on 0.600g of macroporous polystyrene beads using the method outlined
above.
RhH\MPPS\PC
The catalyst is prepared by dispersion of 0.0919g (1.00 x 104
moles) RhH(CO) (PPh^3 and 0.262g (1.00 x 10'^ moles) triphenylphosphine


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FILES


CHEMICAL PROCESSES IN VISCOUS MATERIALS
BY
MARK JAY BARNES
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1989

TO MY FAMILY WHOSE SUPPORT NEVER FALTERED

ACKNOWLEDGEMENTS
The most cherished and remembered things which a person can obtain
in his lifetime are those which require sacrifice and dedication to
achieve. The pursuit of knowledge is certainly no exception to this
definition. If exception be taken with this definition, it is due to
the implication that sacrifice and dedication are contributed only by
the individual. On the contrary, an education would be impossible to
achieve without the sacrifice and dedication of a large number of
people.
First and foremost I wish to express my gratitude to my family.
Their continued support and encouragement have given me the opportunity
to fulfill what was once a dream. My parents, Avery and Marilyn, have
instilled in me a sense of security which can never be taken away. From
them I have learned what happiness is, from where it comes, and how it
can be obtained. To my brothers and sister-in-law, Douglas, Curtis, and
Robin, I owe my love of science. It was they who pointed me in the
right direction and taught me to never be apprehensive of the
unexpected. To my grandparents I am indebted for all their generosity
and support.
I would also like to thank my teachers who have instilled in me a
love for chemistry, Glenn Vogel, Heinz and Judy Koch, Harry Sisler, and
most importantly Russell "Doc" Drago. It is truly an inspiration to
i i i

know a person who loves and enjoys his work as much as he does. I would
also like to thank Ruth Drago for making Florida my home away from home.
I would also like to thank all of my friends. There are too many
to list, but there are those who have influenced me greatly in one way
or another. Included in this list are the past and present residents of
the "Thunderdome": Todd "Spud" Gillespie, Stephen "Julio" Brooks, Mark
"Chin" Hail, Gerald "Citrus Connection" Grünewald, and Donald "Bueller"
Ferris. I would also like to extend my gratitude to past and present
members of the Drago Group, in particular, Maribel Lisk, Robert Taylor,
Larry Chamusco, Edward Getty, Cindy Getty, Shannon Davis, Richard Riley,
and especially Ngai Wong, who has been a good friend and source of
information for many years. Lastly, I would like to express my
gratitude to my girl friend, Kaneez Rizvi. I owe a considerable portion
of my sanity to her for the love and understanding she has given me.

TABLE OF CONTENTS
page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vi
LIST OF FIGURES viii
ABSTRACT x
CHAPTERS
IGENERAL INTRODUCTION 1
IICOBALT(11)-FACILITATED TRANSPORT OF DIOXYGEN IN A
POLYSTYRENE MEMBRANE 4
Introduction 4
Experimental 16
Results and Discussion 21
IIIDEMONSTRATION OF THE FEASIBILITY AND VERSATILITY OF
MEMBRANE REACTORS 43
Introduction 43
Experimental 58
Results and Discussion 62
IVHETEROGENEOUS HYDROFORMYLATION OF PROPYLENE USING SUPPORTED
RHODIUM CATALYSTS IN A CONTINUOUS GAS FLOW REACTOR 80
Introduction 80
Experimental 87
Results and Discussion 91
VSUMMARY 115
APPENDIX
COMPUTER PROGRAM 117
REFERENCES 130
BIOGRAPHICAL SKETCH 137
v

LIST OF TABLES
Tabl e page
2-1. Permeation data for PS/[P]-CoSDPT (16.4%)
membrane 22
2-2. Separation data for a series of polystyrene
blank membranes 27
2-3. Separation data for a series of nickel blank
membranes 28
2-4. Difference in oxygen partial pressure for a
series of PS/[P]-CoSDPT membranes 32
2-5. Difference in oxygen partial pressure for a
series of PS/[P]-CoBr^SDPT membranes 33
2-6. Difference in oxygen partial pressure for a
series of PS/[P]-Co3FSDPT membranes 34
2-7. Difference in oxygen partial pressure for a
series of PS/[SG]-CoSDPT membranes 35
2-8. Comparison of the difference in oxygen partial
pressures obtained with increased cobalt
loading in PS/[P]-CoSDPT 38
3-1. Hydroformylation of propylene with
RhH(CO) (PPh3)3 66
3-2. Oxidation of 1-butene 67
3-3. Butyl sulfide membrane conversion data for
various ruthenium catalyzed oxidations by 0? at
1 atm. and 90°C 71
3-4. Butyl sulfide membrane turnover data 72
3-5. Butyl sulfide solution reaction conversion data
for various ruthenium catalyzed oxidations by
02 at 90°C 74
3-6. Hydrogen peroxide formation 78
v:

4-1. Temperature effect upon propylene
hydroformylation activity using RhH\SG 94
4-2. Selectivity as a function of time in the
hydroformylation of propylene with RhH\SG 96
4-3. Effect of gas flow on the hydroformylation of
propylene with RhH\SG 100
4-4. Effect of gas pressure on the hydroformylation
of propylene with RhH\SG 103
4-5. Effect of gas ratios on the hydroformylation of
propylene with RhH\SG 105
4-6. Catalyst comparison at 80°C 109
4-7. Catalyst comparison at 100°C 112
vi i

LIST OF FIGURES
Figure page
2-1. Molecular orbital diagram.
a) Dioxygen; b) Dioxygen adduct of cobalt(II).. 7
2-2. Polystyrene supported N,N'-bis(salicylidene-
imino)di-n-propylamine cobalt(II), [P]-CoSDPT.. 10
2-3. Schematic representation of the dual mode
sorption concept 13
2-4. [P]-CoSDPT reaction scheme 19
2-5. Schematic diagram of the gas permeation
experimental set up 20
2-6. Plot of the natural log of oxygen partial
pressure differential as a function of time
for a PS/[P]-CoSDPT, (16.4%), membrane 24
2-7. Plot of the natural log of nitrogen partial
pressure differential as a function of time
for a PS/[P]-CoSDPT, (16.4%), membrane 25
2-8. Oxygen partial pressure as a function of time,
a) Experimental curve, b) Calculated
non-facilitated curve, c) Calculated
reference curve (a = 1.00) 30
2-9. Contributions to permeation mechanism 40
2-10. Schematic representation of a metal facilitated
transport mechanism due to site to site
interaction 41
3-1. Read and Dudley mechanism for the oxidation of
terminal alkenes with RhH(CO) (PPf^)-} 49
3-2. Proposed mechanism for the oxidation of
terminal alkenes using a
rhodi um( 111 )/copper( 11) co-catalyst 51
vi i i

3-3.
Alternative mechanism for the oxidation of
terminal alkenes using a
rhodium(III)/copper(II) co-catalyst 52
3-4. Sulfide oxidation catalysts:
a) [Ru(0)2(dmp)2](PF6)2 and
b) [Ru30(prop)6(H20)3r 55
3-5. Anthraquinone autoxidation process 56
3-6. Reactor membrane apparatus 61
3-7. Hydrogen peroxide membrane reactor 76
4-1. Associative and dissociative hydroformyl at ion
reaction mechanism 84
4-2. Gas flow reactor schematic 90
4-3. n-Butanal activity as a function of temperature
in the hydroformylation of propylene with
RhH\SG 95
4-4. Comparison of hydroformylation activity in the
production of n-butanal and isobutanal with
RhH\SG 97
4-5. Effect of gas flow on the n-butanal activity in
the hydroformylation of propylene with RhH\SG.. 99
4-6. Effect of gas pressure on the n-butanal
activity in the hydroformylation of propylene
with RhH\SG 102
4-7. Effect of gas ratios on the n-butanal activity
in the hydroformylation of propylene with
RhH\SG 104
4-8. n-Butanal activity for RhH\SG and Rh(tfa)\SG... 107
4-9. Butanal activity as a function of time in the
hydroformylation of propylene with RhH\SG\PC at
100°C 113

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
CHEMICAL PROCESSES IN VISCOUS MATERIALS
By
Mark Jay Barnes
August 1989
Chairman: Russell S. Drago
Major Department: Chemistry
Polymer membranes, in which transition metal complexes have been
dispersed, have been used to facilitate both oxygen enrichment of air
and traditional homogeneous catalytic reactions. The former is a
demonstration of facilitated transport of oxygen through a glassy
polymer. The latter includes the demonstration of a wide variety of
reactions within the polymer environment.
Selective gas permeation through a polymer membrane has become an
attractive alternative for conventional gas separation processes. The
incorporation of additives that modify permeation properties has been
the focus of this research effort in an attempt to enhance the
separation ability of the polymer membranes. This effort involves the
use of metal complexes to facilitate the transport of gases in a polymer
membrane. Specifically, the main objectives investigated were the
incorporation of supported cobalt (II) schiff base complexes into
polystyrene membranes and the demonstration of metal promoted
x

enhancement of oxygen permeation in the separation of air. Back
calculation using a nickel blank to provide an average separation factor
allows for the determination of metal promoted enrichment using the
nitrogen permeability coefficient as an internal standard. These
results are presented and a transport mechanism discussed.
The use of a polymer environment as the medium for chemical
reactions has resulted in a novel approach to heterogenizing homogeneous
catalytic reactions. The feasibility of this process has been
demonstrated by the hydroformylation of propylene and the oxidation of
terminal alkenes. A specific application of the process involves the
use of ruthenium catalysts dispersed in composite polymer membranes for
the oxidative decomposition of butyl sulfide, a mustard agent simulant.
The formation of hydrogen peroxide using the anthraquinone autoxidation
process is another application which has been achieved. Results from
the above mentioned reactions are presented and discussed.
The development of solid supported rhodium catalysts for
heterogeneous hydroformylation reactions has resulted in the production
of straight chain aldehydes with high selectivity. Use of these
catalysts in a pressure-gas flow reactor is demonstrated and discussed.
XI

CHAPTER I
GENERAL INTRODUCTION
Historically, applications of polymer membrane technology have
been dominated by separation processes. The two biggest contributors to
this field are reverse osmosis desalination processes and industrial gas
separations. Many smaller scale applications which utilize membrane
1 2
technology are currently being investigated. Drug production and
delivery, fermentation, basic chemicals synthesis, hydrogenations and
dehydrogenations represent only a portion of these applications. The
types of membranes employed are as widely varied as their applications.
Ceramic, metallic, glass, inorganic, and polymeric membranes have been
used as process media. Also of interest is the engineering design in
which they are used. Integrated or "hybrid" processes are being
developed which combine a membrane separation unit with an existing
7 8
separation process such as cryogenic separation. ’ Layering or
combining the different membrane types may provide systems which allow
chemical reaction and product-reactant separation within the same unit.
The work presented in this dissertation is associated with
combining membrane technology and transition metal reaction chemistry.
The use of polymers and catalysts in conjunction has previously been
widely investigated in an attempt to heterogenize known homogeneous
Q 1 O
catalysts. For the most part, the polymer is used as a support to
which the catalyst is covalently attached. These insoluble
1

2
functionalized catalysts are then used under "normal" solution chemistry
conditions. Alternatively, membrane reactors are systems in which the
polymer is used as the medium for reaction. The polymer functions, in
essence, as the solvent for the reaction.
The concept of membrane reactors is relatively new. Wolynic and
co-workers first published work in this area which dealt with a
catalytic liquid membrane reactor used for the production of
acetaldehyde from ethylene and oxygen.Since that time most
membrane reactor work has been concentrated in two areas. Membrane
bioreactors have been shown to be effective in enzyme catalysis^’
and porous ceramic and glass membranes have been used as inorganic
o _ c
membrane reactors. In the latter case, hydrogenation and
dehydrogenation reactions are the main processes being attempted.
Catalysis with nation membranes has also been reported.^’19 Nation
possesses a chemically resistant, perfluorinated, polymeric backbone
with highly acidic sulfonic acid groups. Its general structure is shown
below. It has been used as a super acid catalyst, catalyst support,
electrocatalyst, and a gas diffusion membrane.
[(CF2-CF2)n-CF-CF2]x
(0CF2CF)m0CF2CF2S03H
Even though a considerable amount of work has been conducted in
the area of membrane reactors, little of it has actually been achieved

3
with the use of organic polymers. The work presented here is an attempt
at filling this void. Specifically, this study involves three areas of
membrane chemistry. The first process investigates the ability of a
transition metal complex to affect the permeation properties of a
polymeric membrane. The second is concerned with how transition metal
complex reactivities are influenced by dispersion in an organic polymer
"solvent" environment. The last area examined deals with dispersing
transition metal complexes in a non-volatile viscous material which is
coated on an inorganic oxide support for the purpose of creating a
heterogeneous gas phase reaction process.

CHAPTER II
COBALT(11)-FACILITATED TRANSPORT OF DIOXYGEN
IN A POLYSTYRENE MEMBRANE
Introduction
The separation of air into its primary components, oxygen and
nitrogen, is of major industrial significance. Today, two main
commercial processes are used to achieve separation, cryogenic
20-22 po pc
fractional distillation of air and pressure swing adsorption.
Both processes have been employed extensively in the last century for
the production of high purity oxygen and nitrogen.
Many applications, however, do not require high purity oxygen but
can instead use oxygen enriched air. This market includes waste water
treatment facilities, the pulp and paper industry, fermentation
processes and numerous medical applications to name a few. Selective
pc po
gas permeation through a polymer membrane provides an alternative
separation method which is becoming increasingly more important in the
29 30
production of oxygen enriched air. ’
The past ten years have seen the advent of membrane based
separation units. The first commercial venture into the field was
initiated by the Monsanto Corporation. It utilized a polysulfone hollow
pq
fiber membrane system and was called "The Prism Process." Since that
time many types of membranes have been increasingly employed for
separation purposes, and recently, are being used in conjunction with
4

5
31 32
the traditional air separation processes. ’ These hybrid systems
have been shown to be an economically attractive alternative in the
production of pure oxygen and nitrogen. The fact that membrane
separation units are economically competitive with existing processes,
coupled with the unlimited number of applications, has resulted in an
explosion in the amount of research being carried out in this field.
Interest is mainly twofold. Most attention is focused on finding new
applications for membrane separation units and developing new, or
modifying existing, polymers for these appl ications.The use of membranes
for gas separations is based upon the phenomenon that different
permeates will have varying rates of permeation through membranes. One
of the first references to a membrane separation procedure is credited
33
to Thomas Graham, who, in 1864, used a dialyzer to separate a solution
into its components. He became known as the father of gas separations
when he published his famous paper "On the Molecular Mobility of
Gases''^ in 1863, which resulted in the formulation of Graham's Law, and
3C
later published a paper dealing with the separation of gases. Since
that time many others have made considerable contributions in the areas
of membrane chemistry and gas separations, but because of the size and
scope of this work, it will not be mentioned in this chapter.
Alternately, a more detailed insight into the properties which affect
membrane permeation will be presented.
Ideally, a permselective polymer membrane should have good
mechanical strength, high selectivity, and high flux (rate of gas
permeation). However, the later two are inversely related. A polymer
membrane which has a high selectivity will have a relatively slow flux

6
and vice versa. Attempts to either increase the rate of permeation in
highly selective membranes or enhance the selectivity of highly
permeable membranes have been the focal point of most research efforts.
The work presented in this chapter represents an undertaking in the
latter area of modification.
The incorporation of additives to modify permeation properties has
been directed towards improving membranes that are highly permeable and
poorly selective. A recent approach to this concept involved enhancing
the transport of dioxygen by encapsulating a metal complex-containing
solution in a porous polymer membrane resulting in excellent
selectivity. This liquid-membrane, oxygen-enrichment process
utilizes cobalt(II) chelate complexes. The role of the cobalt complex
is to act as a carrier by reversibly binding dioxygen and thus increase
the oxygen permeability of the membrane. In systems such as these, the
most important aspects to be considered are the processes which occur at
the carrier site. Essentially, these processes are attributed to the
reversible binding ability of the cobalt(II) complex and can be
explained by extrapolating our knowledge of similar processes which
occur with cobalt(II) complexes in solution.
The ability of the metal center to bind dioxygen and the factors
which affect the interaction between the two can be complex. As shown
in figure 2-la, molecular oxygen in its ground state is a triplet, 2^
★
molecule with two unpaired electrons residing in the 7r molecular
orbitals. Since it is kinetically unfavorable for one of the electrons
to change spin, dioxygen is typically unreactive towards diamagnetic
compounds. Its ability to bind with transition metal complexes results

Figure 2-1.
Molecular orbital diagram.
a) Dioxygen; b) Dioxygen adduct of cobalt(II).

8
primarily from spin orbital coupling, which lessens the severity of a
spin change. The spin pairing modeldeveloped by Drago and Corden
describes this metal-dioxygen bonding scheme and is shown in figure 2-lb
using a simplified molecular orbital diagram. It involves the pairing
of the unpaired dz electron of cobalt(II) with an unpaired 7r electron
of dioxygen which results in the formation of an end on bonded
cobalt(II)-dioxygen adduct.
The stability of the cobalt-oxygen sigma bond is directly related
to the ligand field strength of the complex. By increasing the ligand
2
field strength around the cobalt metal center, the energy of the dz
orbital used in bond formation is increased. Therefore during dioxygen
adduct formation, more energy is given off resulting in a more stable
cobalt-oxygen sigma bond. This is a critical property since if the bond
formed is too stable, the ability to dissociate the dioxygen adduct is
hindered. If the bond formed is too weak, the complex will have poor
oxygen affinity. Thus a compromise is required to have a suitable
carrier.
In 1938, Tsumaki reported the first synthetic complex capable of
reversibly binding dioxygen, N,N'-bis(salicylidene)ethylenediamine
cobalt(II). This complex, better known as cobalt(II) salen, is shown
below. Since that time, many cobalt(II) schiff base complexes have been
\_y

9
reported which are capable of reversibly binding dioxygen.
Unfortunately, deactivation of the metal complexes has hindered their
development. Deactivation, for the most part, is brought about by
either oxidation of the ligand system or irreversible oxidation of the
metal center. An example of the latter would be the formation of a
/¿-peroxodimer complex. Attempts to achieve a stable oxygen carrier have
been directed using two different approaches. Sterically constrained
metal carrier complexes and supported metal carrier complexes have
received the greatest attention. Often, schiff base complexes which
indicate promise as carriers are the focus of such modification. This
is the case in the work presented in this chapter.
One of the best examples cited which has the ability to bind
dioxygen reversibly is N,N'-bis(salicylideneimino)di-n-propylamine
cobalt(II), CoSDPT (figure 2-2 with P replaced by H), in 1:1 DMSO and
a-butyrolactone solvent encapsulated in a 130 /¿ thick microporous nylon
6,6 membrane.42 At 25°C, an air mixture containing 88% oxygen was
produced in a single pass through this membrane. A schematic diagram of
this system is illustrated below. Although the process appears quite
MEMBRANE

10
Figure 2-2.
R - H , B r , F
Polystyrene supported N,N'-bis(salicylideneimino)di-
n-propylamine cobalt(II), [P]-CoSDPT.

11
remarkable, the removal of the volatile solvent by gas flow has hindered
its commercial development. The work presented in this text illustrates
the ability to reversibly bind and facilitate the transport of dioxygen
through a polymer membrane using this complex supported on polystyrene.
A few reports of facilitated transport of dioxygen by carriers in
membranes have appeared^’^ using unsupported complexes that can be
viewed as being dissolved in the polymer.
The concept of a facilitated transport mechanism has been a
controversial subject in membrane separations. Therefore, a brief
mathematical description of permeation in a polymer membrane is
necessary. According to Fick's Law of diffusion, shown below, the flux,
J = DSAP/1
J, of a penetrant can be determined from its diffusion coefficient, D;
solubility, S; and pressure differential, P, across a membrane of
thickness 1. The permeability of the gas, P, is dependent upon both its
solubility and diffusivity in the respective membrane.
P = DS
Generally, sorption and transport in a glassy polymer such as
polystyrene is best explained by a dual mode model. Using this model,
two simultaneous processes in the membrane are predicted to occur. The
first is associated with dissolution in the dense region of the polymer
and follows Henry's Law where CQ is the concentration, KQ is the Henry's

12
law constant which characterizes sorption of the penetrant, and P is the
pressure of the penetrant. The second process is associated with
distribution in the gaps or "holes" of the polymer and is best explained
by a Langmuir isotherm where CH is the concentration, C^' the Langmuir
CH = Ch'BP / (1 + BP)
sorption capacity, and B the affinity of the penetrant for the gaps in
the polymer. Using these simple equations, the total concentration of
the penetrant can be described as the sum of the two individual
C = CD + CH
concentrations. This can be seen schematically in the concentration
versus pressure graph shown in figure 2-3. The overall solubility
isotherm can similarly be described as the sum of the solubility
expressions of each model. The permeability of the penetrant
S = Kd + Ch'B / (1 + BP)
can now be expressed as the diffusivity and solubility associated with
each individual mode where Dq and represent the diffusivities of the
Henry's mode and Langmuir mode respectively.

13
c
Figure 2-3.
P
P
Schematic representation of the dual mode sorption
concept.

14
P = KdDd + C|_|'BDh / (1 + BP)
The model presented is representative of a nonfaci1itated process
and must therefore be modified to explain the contributions made by a
facilitated transport mode. This can be done by initially applying
Langmuir kinetics to describe the equilibrium obtained when oxygen binds
to solid metal complexes. The resulting expression can then be
rearranged to indicate the fraction of oxygenated sites, X, with
X / (1 - X) = KPq2
X = KPq2 / (1 + KPq2)
respect to the equilibrium constant, K, and dioxygen partial pressure.
The fraction of oxygenated sites should be directly related to the
solubility of dioxygen associated with these sites. Therefore, a new
solubility isotherm may be written to express the total solubility of
dioxygen in a membrane capable of facilitating dioxygen transport.
Similarly, a new expression describing dioxygen permeability according
to the three modes of transport can be formulated where represents
the diffusivity associated with the metal sites.
S = Kq + [Ch'B / (1 + BP)] + [KP / (1 + KP)]
P = KqDq + [Ch'BDh / (1 + BP)] + [KPDm / (1 + KP)]

15
The results presented in this work represent a new approach to
enhancing the permeation properties of polymer membranes and
establishing a novel method and mechanism of transport. The goal of
this research was to demonstrate this novel mode of transport as well as
to develop a process that accurately accounted for the quantities of
dioxygen associated with both facilitated and nonfaci1itated transport.
To achieve this, a metal complex that reversibly binds dioxygen is
covalently attached to polystyrene. Though the pure complexes in the
solid state do not bind dioxygen, they do bind dioxygen in the solid
state when covalently linked to a polymer. The dispersion of the
metal complex on highly crosslinked polystyrene into a polystyrene film
resulted in the selective permeation of dioxygen through the membrane.
This membrane system differs from the liquid membranes in that the metal
complexes are bound to the polymer. Since the cobalt complexes are not
mobile, the mechanism is unlike that proposed for isotropic polymers or
AO
liquid membranes as demonstrated in the Bend Research system.
Recently, this system has been extended to cobalt(II) porphyrin
and Schiff base compl exes In all reports^’^4,46-51 of
facilitated transport in solid polymer membranes, the demonstration of
facilitated transport by metal complex binding of dioxygen is dependent
upon the critical selection of a blank. Incorporation of a material in
a polymer film can function to change the structure of the membrane and
the permeability of gases leading to enrichment by a process other than
facilitated transport. The results of this study are significant for
they provide strong support for a facilitated transfer mechanism using
metal complexes to bind simple gas molecules. A procedure for the

16
evaluation of the experimental permeation data is reported that
eliminates imperfections including solvent entrapment that surely exist
in the test and blank films.
Experimental
Complexes studied were prepared using reagents which were either
purchased or synthesized using the procedures listed below. An overall
reaction scheme is shown in figure 2-4 for the preparation of the
polystyrene supported complexes. Solvents used in this work were
purified by distillation, stored over 4A molecular sieves under a
nitrogen atmosphere, and degassed prior to use when necessary.
Characterization of the complexes was conducted using a Perkin Elmer
Plasma II Emission Spectrometer, and Bruker ER 200D-SRC Electron Spin
Resonance Spectrometer. Elemental analyses were conducted by the
University of Florida Department of Chemistry Microanalysis Service, and
Galbraith Laboratories.
Polystyrene Supported Dipropylenetriamine, ÍP1-DPT
Polystyrene beads (90% chloromethylated, 4% divinyl benzene
crosslinked) were donated by Sybron Corporation. Polystyrene bound
45
dipropylenetriamine was prepared according to the literature.
Experimental analysis: %C = 67.41, %H = 6.64, %N = 7.60. Theoretical
analysis: %C = 72.83, %H = 10.19, %N = 16.98.
Polystyrene Supported Bis(3-(salicylideneaminolpropyl)amine, TP1-SDPT
The polymer bound pentadentate ligand was prepared according to
46
the literature. The 3,5-dibromo and the 3-fluoro substituted

17
sal icy1 aldehyde derivatives were prepared in a similar manner.
Experimental analysis: %C = 75.97, %H = 7.19, %N = 7.84. Theoretical
analysis: %C = 76.45, %H = 7.30, %N = 9.22.
rPl-CoSDPT. -Co BroSDPT and -Co3F$DPT
Cobalt was incorporated into the [P]-SDPT type complexes by
slurrying excess cobalt(II) acetate with the appropriate resins in DMF
under argon at room temperature for two days. The polymer supported
cobalt complexes were filtered, washed with DMF and dried under vacuum
at 80°C. Experimental analysis of [P]-CoSDPT: %Co = 0.15. Theoretical
analysis: %Co = 11.50. Overall analysis indicated greater than 95% of
the chloromethylated polystyrene had been converted to the [P]-SDPT and
that 1.15% of the SDPT ligand contained cobalt. The low loading of
cobalt was ideal for this study because site isolation inhibits
formation of the /j-peroxo dimer. EPR studies showed an intense cobalt-
dioxygen signal which was used to monitor reversible binding of O2.
Silica Gel Supported CoSDPT, -CoBroSDPT and -Co3FSDPT
Silica gel supported dipropylenetriamine was prepared as reported
CO
in the literature. The silica supported Cobalt(II)SDPT complexes were
prepared from [SG]-DPT in an analogous manner to the polystyrene bound
analogues. Experimental analyses were not obtained.
ÍPI-NiSDPT, -NiBroSDPT, and \SGI-NiSDPT
The analogous nickel complexes were prepared in the same manner as
reported for the cobalt complexes. Analyses were not obtained.
Membrane Preparation and Characterization
The membranes employed in this study were prepared using a casting
technique. Polystyrene was dissolved in an appropriate solvent, such as

18
toluene or methylene chloride. The viscous polymer solution was then
poured into a leveled circular form. Evaporation of solvent at room
temperature resulted in the formation of homogeneous polymer membranes.
Membranes containing the supported metal complexes were prepared
in a similar manner by grinding the complex into a fine powder (< 1/x in
diameter), adding it to the polymer solution, and then casting the
solution in a mold. After solvent evaporation had occurred, the
membrane's thickness was determined with a vernier caliper to the
nearest hundredth of a millimeter. The weight percent of the added
complex in the membrane was determined after each permeation experiment
by redissolving the polymer film, isolating and drying the supported
complex and then weighing it.
Permeation Apparatus
Permeation experiments were carried out with an apparatus designed
by Ken Balkus.^ The cell was designed to support the membrane and
prevent rupturing when a pressure gradient was applied to the membrane.
A schematic of the permeation setup is shown in figure 2-5.
Permeation Procedure
The following section describes a typical experimental permeation
procedure. A polymer membrane was secured between the two chambers of
the apparatus, after which the membrane deformed to the shape of the
o-rings used to secure its seal. The lower chamber of the cell was
placed under vacuum for approximately six to twelve hours prior to the
start of the experiment to remove any excess solvent or O2 that may have
been trapped in the film during preparation. The lower chamber was then
closed off under vacuum and an initial pressure measurement taken.

19
NH(CH2CH2CN)2
—■»
CH2-!J(CH2CH2CN)2
BHy THF
H2-M(CH2CH2CH2NH2)2
Figure 2-4
[P]-CoSDPT reaction scheme.

20
Figure 2-5.
Schematic diagram of the gas permeation experimental
set up.

21
Periodically, the lower chamber was monitored manometrically to
determine the extent of gas permeation and quantitatively to determine
its dioxygen ( also referred to as oxygen) content. The latter analysis
was carried out using gas samples taken from the lower chamber with a
100 /il gas tight syringe and analyzed by a Varian 3700 gas chromatograph
equipped with a thermal conductivity detector. The column employed was
an 8 foot, 1/8 inch O.D., stainless steel column containing 5A molecular
sieves heated to 30°C.
Since the gas sample taken was at a reduced pressure, it was
diluted with air while being withdrawn from the sampling port. From the
percent oxygen of the injected sample determined by the GC, the actual
percent oxygen in the lower chamber was calculated using the equation
shown below, where Pg is the pressure of the lower chamber in mmHg, P^
(Pl)(0l) + (PH - pl)(oh) = (PH)(0D)
is atmospheric pressure, 0g is the percent oxygen in the lower chamber,
0^| is the percent oxygen in the atmosphere, and 0g is the percent oxygen
as determined by the GC. Using this method, the standard deviation
between samples was typically on the order of 0.1%.
Results and Discussion
The evaluation of the cobalt containing membranes is based upon a
comparison of experimental permeation data with data obtained from an
appropriate blank. Permeation data for a typical PS/[P]-CoSDPT membrane

22
are shown in table 2-1. The percent oxygen was calculated as previously
described and the percent enrichment is the difference between the
percentage of oxygen in the lower chamber and that of air, which is
assumed to be 21.0%.
Tabl e
2-1.
Permeation
data for PS/[P]-CoSDPT
(16.4%)
membrane.
Time
(hr)
Total
Pressure
(mmHq)
FI ux
(mmHq/hr)
Partial
Oxygen
(mmHq)
Pressure
Nitrogen
(mmHq)
Percent
Oxvqen
Percent
Enrichment
5
36.0
7.20
10.56
25.44
29.3
8.3
18
71.0
3.94
23.77
47.23
33.5
12.5
24
92.0
3.83
29.78
62.22
32.4
11.4
29.5
99.0
3.35
32.97
66.03
33.3
12.3
42
118.0
2.81
40.27
77.73
34.1
13.1
According to Henry's Law, permeation of a gas through a membrane
is a first order kinetic process. This is shown mathematically below,
where P is the permeability coefficient (cm (STP)cm/cm s mmHg), 1 is the
film thickness (cm), A is the film area (cm ), Vce-|-j is the volume of
the lower chamber (cm ), (P^ - P^) is the partial pressure differential
across the membrane (mmHg), R is the gas constant (6.24 x 10^
cm mmHg/molK), and T is the temperature (K). Assuming PH is constant
dP
RTA
P(Ph - P,)
22’414Vcell
dt
1

23
throughout the experiment, the equation can be rearranged and integrated
to give a new equation from which a plot of 1 n(- P|_) versus time
should yield a straight line, indicating a first order process.
1 n(P[_| - PL)
-RTA
22'414Vcell 1
t +
constant
This analysis was carried out using the computer program detailed
in Appendix A. Using this program, the permeability coefficients for
both oxygen and nitrogen can be obtained from the slope of the lines
plotted from their respective partial pressures in table 2-1. Graphs of
these analyses are shown in figures 2-6 and 2-7. Values of 4.38 x 10’
If) o ?
and 1.92 x 10 cm (STP)cm/cm s mmHg are obtained respectively.
However, in the cobalt complex containing films, it is obvious that a
slightly curved line is obtained rather than a linear one. This
indicates that the permeability coefficient of oxygen is varying with
the partial pressure of oxygen in the lower chamber. Therefore, oxygen
permeation through the membrane is deviating from a first order process
due to contributions from facilitated transport.
To better demonstrate and quantify the contributions resulting
from facilitated transport, the cobalt containing films must be compared
to an appropriate blank. Analogous nickel(II) complexes do not bind
oxygen, since they have no unpaired electrons, and are similar in
structure to the cobalt complexes resulting in membranes with similar
morphology and free space volumes. Although free volume is difficult to
reproduce in glassy polymers because of air pockets and filler

In (Ph-Pl)
24
TIME (hrs.)
Figure 2-6. Plot of the natural log of oxygen partial pressure
differential as a function of time for a
PS/[P]-CoSDPT, (16.4%), membrane.

In (Ph-Pl)
25
Figure 2-7. Plot of the natural log of nitrogen partial pressure
differential as a function of time for a
PS/[P]-CoSDPT, (16.4%), membrane.

26
aggregation, the nickel complexes are the best simulation for the
unoxygenated cobalt containing films and, therefore, are ideal blanks.
Analysis of the polystyrene and nickel blanks is best made by observing
the ratio of PQ2 to PN2- This value is known as the separation factor,
a, and describes the effectiveness of a membrane for permselectivity.
The a values for both polystyrene and nickel blank membranes are
reported in tables 2-2 and 2-3 respectively.
Certainly, all films contained minor defects, some more severe
than others. An extensive amount of data was collected for a large
number of films. In several instances pinholes were present in the
original film or leaks developed as the experiment progressed. In order
for a run to be found acceptable, it was required that the first data
point have as an upper limit, a value of flux times length, ( J x 1),
below 7.0 (torr-mm/hr) at the start of the experiment. A second
requirement was that in each experiment the flux must decrease as
(PH - P|_) decreases i.e., as time increases. This criterion was used to
discard data sets in which leaks developed during the experiment. A
series of 11 films of polystyrene selected by these requirements and
with varying thicknesses was studied yielding a mean oxygen permeability
-10 3 2
coefficient of 3.1 x 10 cm (STP) cm/(cm s mmHg) with a standard
deviation of +0.8 x 10~* . This permeability coefficient is
approximately one order of magnitude greater than those previously
53 - 57
reported. This is not surprising since polystyrene is a glassy
polymer and the method of membrane preparation will affect the transport
58 59
properties of the membrane. ’ Systematic errors introduced by the
apparatus or sampling technique may also contribute to the deviation.

27
Table 2-2. Separation data for a series of polystyrene blank
membranes.
1 (mm)
J1
(torr-mm/hr)
Pts.a
a
0.371 ± .073
1.7
3F
2.52 ± .02
0.542 ± .124
2.3
4M
1.37 ± .02
0.50 ± .00
3.4
6F
2.14 ± .02
0.164 ± .05
4.3
4M
1.40 ± .01
0.150 ± .052
1.5
4M
1.72 ± .01
0.250 ± .052
1.2
5M
2.19 ± .04
0.110 ± .028
1.0
7F
2.27 ± .02
0.131 ± .048
1.9
9F
2.34 + .03
0.989 ± .16
5.4
5F
1.97 ± .05
1.567 ± .30
4.3
4F
2.76 ± .20
0.238 ± .051
1.5
3M
1.03 ± .16
Avg. a = 1.97 S.D. = 0.17
a number of data points in the data set. E, M, F designate the
time span of the experiment where E is less than 12 hrs., M is
less than 29 hrs., and F is greater than or equal to 29 hrs.

28
Table 2-3. Separation data for a series of nickel blank
membranes.
rPl-NiSDPT
1st Cycle
J1
WT
%
l(i
mm
)
(torr»mm/hr)
Pts.a
a
20
0.457
+
.119
4.8
4E
1.79
+ .
.01
15
0.681
+
.059
3.1
5M
2.05
+ .
02
10
0.423
+
.103
4.0
5E
1.57
+ .
02
Avg.
a = 1.80
S.D. =
0.17
IEL
-NiBr2SDPT
1
st Cycle
20
0.432
+
.12
3.9
5E
2.26
+ .
03
20
0.700
+
.168
5.2
5M
1.80
+ .
12
15
0.600
+
.160
3.0
6M
1.94
+ .
06
10
0.628
+
.138
4.4
5M
1.79
+ .
08
Avg.
a = 1.95
S.D. =
= 0.13
2nd Cycle
25
0.709
+
.159
3.5
4M
2.12 ± .
02
rSGl-NiSDPT
25
0.694
+
.105
4.5
5M
1.77
+
.05
20
0.666
+
.114
3.0
5M
1.73
+
.01
15
0.730
+
.079
4.7
4M
2.00
+
.04
Avg.
a = 1.83
S.D. =
0.10
1 number
of data
points
in
the data set.
E, M, F
designate
the
.ime
span
of the
experi
ment
where E is less than
12 hrs
M
i s
ess
than
29 hrs.
, and
F i s
greater than
or equal
to 29
hrs.

29
The permeabilities were also determined from a gas mixture rather than a
single component gas penetrating through the membrane. The few studies
reported with permeations of gas mixtures through glassy polymers show
deviations in permeabilities of pure penetrants versus those of the
mixture.Although deviations from the literature values exist, the
important point to be considered is that all films were similarly made
and evaluated so that consistent data could be obtained and compared.
Using PN2 as an internal standard ensures that the cobalt complex-
containing membranes can be compared with their respective blanks and
the difference in oxygen partial pressures can be attributed to metal
promoted enhanced oxygen permeability and not to film preparation or
defects. To illustrate the enrichment that is obtained by facilitated
transfer, the partial pressure of oxygen in the lower chamber has been
plotted as a function of time for PS/[P]-CoSDPT (16.4% functionalized
ligand with 0.15% cobalt) membrane (figure 2-8). The change in nitrogen
partial pressure with time for this film is used as an internal standard
to calibrate the permeation experiment. The average a value from the
PS/[P]-NiSDPT blanks is used to calculate the oxygen partial pressure
corresponding to this nitrogen pressure for an identical membrane in
which facilitated transport does not occur and a first order kinetic
process is observed. Since the cobalt complex does not bind nitrogen
and facilitate its transport, this affords an ideal blank. This
calculated pressure of oxygen is representative of all diffusion
mechanisms other than facilitated transport and is also plotted in
figure 2-8. The difference between the curves represents the enrichment
obtained by a cobalt(II) facilitated transport mechanism. Again this

OXYGEN PARTIAL PRESSURE (mm
30
cn
Figure 2-8. Oxygen partial pressure as a function of time.
a) Experimental curve, b) Calculated non-facilitated
curve, c) Calculated reference curve (a = 1.00).

31
analysis was conducted using the computer program listed in appendix A.
Figure 2-8 also contains a reference curve indicating the oxygen partial
pressure which would be present if no permselectivity were achieved,
i.e. a = 1.00.
By analyzing the data using the blank nickel a values and nitrogen
permeability coefficients from the cobalt containing membranes,
systematic errors in measuring the enrichment of oxygen (such as
membrane thickness and imperfections) are cancelled out. This is
verified experimentally with the nickel blanks themselves, where a is
independent of film thickness. It was also observed in the nickel data,
that percent loading and variation in substituents on the phenyl ring
did not influence the a values within the experimental standard
deviation of + 0.2. The reaction chamber can be evacuated after 25
hours and the experiment cycled a second time with no change in a.
Table 2-4 contains the differences in partial pressures of oxygen
between the cobalt facilitated and back-calculated non-facilitated
curves (as plotted in figure 2-8) for a series of cobalt complex
containing membranes. The differences were determined graphically at
three different reaction times: when the back-calculated
D
non-facilitated partial pressure of oxygen, Pg^ , was 15, 20, and 25
torr. The polymer bound CoSDPT complex shows an enrichment of oxygen
over the non-faci1itated process. The increasing oxygen partial
pressure at the three different reaction times can be explained by the
variance in its permeation coefficient. Early in the experiment, the
oxygen permeation coefficient is largest leading to an increase in the
difference in Pg^. Later in the experiment, the increased Pg^ value in

32
Table 2-4. Difference in oxygen partial pressure for a series of
PS/[P]-CoSDPT membranes.
TP1-CoSDPT
1st Cycle
Difference
in PQ2
(torr)
J1
P B
^02
P B
^02
P B
y02
WT%
1 (mm)
(torr*mm/hr)
15
20
25
44
0.261 ± .144
2.4
3.7
N. A.
N.A.
18.6
0.357 ± .065
2.6
1.0
2.5
2.6
16.4
0.687 ± .124
4.9
2.3
4.1
4.9
Avg. P02 =
2.3
3.3
3.8
S.D. =
1.0
1.1
1.6
2nd Cycle
17.2
0.677 ± .044
5.1
4.2
5.0
5.9
16.4
0.687 ± .124
2.5
2.8
3.6
4.2
Avg. PQ2 =
3.5
4.3
O
LT)
S.D. =
1.0
1.0
1.2
3rd Cycle
16.4
0.687 + .124
2.9
2.6
3.2
3.6
4th Cycle
0.687 ± .124 4.4 -2.4 -3.5 -3.9
16.4

33
Table 2-5.
Difference in oxygen partial pressure
PS/[P]-CoBr2SDPT membranes.
for a
series of
TPl-CoBroSDPT
1st Cycle
J1
Difference
P02
p1nBP02
K02
(torg)
P02
WT%
1 (mm)
(torr-mm/hr)
15
20
25
7.4
0.528 ± .072
3.7
2.9
3.9
4.0
6.76
0.671 ± .047
6.7
2.6
3.5
4.4
Avg. PQ2 =
2.8
3.7
4.2
S.D. =
0.2
0.3
0.3
2nd Cycle
20.20
0.640 ± .051
5.8
-5.8
-4.5
-5.6
12.62
0.747 ± .074
3.7
-4.0
N.A.
N.A.
Avg. PQ2 =
-4.9
-4.5
-5.6
S.D.
1.3

34
Table 2-6.
WT%
24.6
16.47
6.42
6.30
24.6
6.30
Difference in oxygen partial pressure for a series of
PS/[P]-Co3FSDPT membranes.
r PI-Co3FSDPT
1st Cycle
J1
1(mm) (torr*mm/hr)
0.359
+
.050
2.3
0.506
+
.075
4.4
0.625
+
.085
5.9
0.541
+
.051
3.8
Avg
• P02 =
S.D. =
2nd Cvcl
0.359
+
.050
1.4
0.541
+
.051
2.4
Avg. PQ2 =
S.D. =
Difference
in P02
(torr)
P 8
*02
P 8
*02
P 8
*02
15
20
25
6.0
7.1
7.9
1.0
0.6
0.0
3.0
4.0
4.4
5.4
5.0
5.0
3.8
4.2
4.3
1.3
1.6
1.9
-2.1
N.A.
N.A
0.5
1.0
1.3
-0.8
1.0
1.3
1.8

35
Table 2-7. Difference in oxygen partial pressure for a series of
PS/[SG]-CoSDPT membranes.
Í SGI-CoSDPT
1st Cycle
WT%
1 (mm)
J1
(torr*mm/hr)
Difference in Pg^ (torr)
p B p B p B
r02 02 02
15 20 25
14,
.9
0.
.533
+
.097
5.6
1.0
2,
.1
2,
.5
10,
.0
0,
.807
+
.70
6.4
2.8
3,
.0
3,
.2
6,
.56
0,
.571
+
.082
4.8
1.6
1,
.5
0,
.9
4,
.6
0.
.614
+
.077
6.1
2.6
3.
.1
3,
.0
2
0.
.492
+
.028
4.9
1.3
2.
J5
2,
.6
Avg.
P02 =
1.9
2,
.5
2.
.4
S.D. =
0.4
0,
.3
0.
.4
2nd
Cvcl e
16.
.5
0.
.647
+
.051
4.2
4.0
N.
.A.
N.
.A.
14.
.9
0.
.533
+
.097
3.2
2.5
3.
.2
2.
.5
10.
.0
0.
.807
+
.70
5.6
2.0
2.
.2
2.
,5
Avg.
P02 =
2.8
2.
.7
2.
.5
S.D. =
0.7
0.
.7
0.
,0
Lower Surface Studies
16.
1
0.
384
+
.037
4.6
0.7
0.
,0
-0.
5
1.
87
0.
358
+
.062
2.7
-1.0
-1.
6
-1.
5
Avg.
P02 =
-0.2
-0.
8
-1.
0
S.D. =
1.2
1.
1
0.
7

36
the lower chamber approaches the value of the complex and the
facilitated transport of oxygen decreases. Eventually the cobalt
complex is fully oxygenated and does not facilitate oxygen transport.
At this point in time, no subsequent enrichment occurs, i.e. the
experimental PQ2 curve and blank back-calculated curves become parallel
(figure 2-8). This is observed in all cases with the different cobalt
complexes.
Second and third cycle experiments with PS/[P]-CoSDPT membranes
produced similar enrichments in comparison with the original experiment.
The fourth cycle showed a loss of enrichment presumably because of
formation of a ¿¿-peroxo complex or oxidation of the cobalt(II) complex.
While cycling experiments were not conducted on the nickel blanks with
much regularity, those that were conducted resulted in similar a values
and indicate no serious loss in separation ability. To confirm that the
observed enrichment of oxygen was due in part to the reversible binding
of oxygen and not just its desorption from the complexes already formed
during preparation of the membranes, the maximum amount of oxygen that
could possibly be bound to the cobalt centers was calculated to be
considerably less than that observed in the permeation reactions.
Facilitated transport is also demonstrated for polymer bound
CoB^SDPT and Co3FSDPT with slightly higher enrichment values
respectively (tables 2-5 and 2-6). However, in these cases the second
cycle no longer showed any enhancement, again presumably because of
formation of a /¿-peroxo complex or oxidation of the cobalt(II) complex.
When CoSDPT was covalently attached to silica gel (0.5 millimoles/g) and
added to a polystyrene membrane, a smaller degree of oxygen enrichment

37
was obtained (table 2-7). Second cycles of these membranes resulted in
similar enrichments.
Attempts to achieve higher loadings of cobalt in the
functionalized polymer were moderately successful. Data reported in
tables 2-4 through 2-7 are from functionalized complexes which contain
approximately 0.30% cobalt. Using more strenuous reaction conditions
(elevated temperature and longer reaction time), loadings of 0.70% and
5.1% cobalt in P-CoSDPT were obtained. Permeation experiments and
cycling of the membranes were carried out as reported. Comparison data
are reported in table 2-8. The results indicate that with a moderate
increase in loading (0.70%), an initial increase in enrichment is
obtained; however, subsequent cycles are somewhat less, indicating
deactivation of the metal complex due primarily to increased loading.
It is not unexpected then that a loading of 5.1% had a small amount of
enrichment since approximately one out of every two ligand sites was
occupied. Expectedly, this should lead to a greater chance of metal-
metal interaction and increased formation of /¿-peroxodimers.
The incorporation of phenol (4% by weight) into the 5.1% cobalt
loaded membrane resulted in lowering the oxygen enrichment for the film
(Pq2B 15 = -1.7, Pq2B 20 = -2.3, and Pq2B 25 = -2.7 torr). It was
thought that the addition of a hydrogen bonding complex such as phenol
might stabilize the complex from deactivation. However, it appears that
it prevents reversible oxygen binding and distorts the membrane's
morphology.
The use of a more rubbery polymer, poly(butyl methacrylate), in
place of polystyrene did not result in increased facilitated transport

38
Table 2-8. Comparison of the difference in oxygen partial
pressures obtained with increased cobalt loading in
PS/[P]-CoSDPT.
Difference in Pg^ (torr)
Cobalt
Loadinq
Cvcl e
P°2B
15
Pn 8
po2
20
Pn B
P°2
25
0.30%
1
2.3
3.3
3.8
2
3.5
4.3
5.0
3
2.6
3.2
3.6
4
-2.4
-3.5
-3.9
0.70%
1
3.6
4.5
5.7
2
2.0
2.0
2.8
3
2.0
2.2
2.3
5.1%
1
0.8
1.4
N.A,
2
2.4
2.5
2.9

39
enrichment. Instead, it was observed that the experimental oxygen
partial pressure was essentially the same or slightly lower, (oxygen
enrichment at 15 = -1.0, Pg ® 20 = -0.5, and Pg ® 25 = -0.25 torr),
than the back-calculated non-faci1itated partial pressure. This is
explained by the fact that a blank poly(butyl methacrylate) membrane
without any additives has a high permselectivity (a = 2.2). Any
enrichment obtained with the addition of [P]-CoSDPT is overshadowed by
the increased permeability of oxygen. It is possible that this may
result in fully oxygenating the cobalt complexes at very low oxygen
pressures. This effectively blocks a facilitated transport mechanism.
In this case the complexes act as fillers and alter the permeability of
the membrane accordingly. Essentially, the rubbery polymer's diffusion
mechanism dominates that of the facilitated transport.
The mechanism of oxygen transport involved in the PS/[P]-CoSDPT
membranes described above is unlike that in liquid membranes. For
oxygen permeation using supported metal complexes in solid polymer
membranes, at least five individual processes are involved. These are
shown in figure 2-9. They include within the non-faci1itated process:
solubility of the gas, diffusion of the gas, and desorption of it from
the polymer. The facilitated path also involves oxygen binding to the
metal complex, oxygen transfer to cobalt sites through the polymer, and
deoxygenation of the metal complex. On the high pressure side, the
attainment of equilibrium for oxygen solubility at the polymer interface
is an exothermic process, as is oxygen binding to the metal center.
These are not viewed as rate determining in the transport process. The
importance of the metal center in the diffusion process is much more

40
Figure 2-9.
Contributions to permeation mechanism.

41
Figure 2-10. Schematic representation of a metal facilitated
transport mechanism due to site to site interaction.

42
complex. It is proposed that the cobalt complexes transport oxygen via
a site to site transfer (figure 2-10). The oxygen bound to cobalt is in
equilibrium with oxygen that is soluble in the polymer maintaining a
reservoir of free oxygen through the film. Cobalt-oxygen complexes on
the low pressure side dissociate oxygen into the gas phase and replace
it by binding oxygen from a neighboring reservoir. This necessitates a
dispersion of the oxygen carriers throughout the membrane as opposed to
having them only on the lower surface. The latter configuration showed
no oxygen enrichment (table 2-7--Lower Surface Studies).
In conclusion, a procedure was developed for ascertaining
facilitated transfer of oxygen that uses the permeation of nitrogen in
the sample membrane as an internal standard. Using this, it has been
demonstrated that supported cobalt complexes incorporated into a
polystyrene membrane enhance the permeation of oxygen. Having
accomplished these objectives, extension of the process using higher
cobalt(II) loadings and rubbery polymers has failed to produce a more
attractive system.
The mechanism of facilitated transport in this system differs from
that in liquid membranes where diffusion of the entire complex carries
oxygen across the membrane. A site to site transfer is proposed here
and this mechanism requires that some of the cobalt be deoxygenated in
the membrane. The P^ value for CoSDPT in solution is reported*^ to be
6.715 x 10^ mmHg at 295 °K. A more stable adduct forms in the
polymer, and its P^ value determines the partial pressure of oxygen
that can be attained on the lower pressure side before metal facilitated
enhancement ceases.

CHAPTER III
DEMONSTRATION OF THE FEASIBILITY AND VERSATILITY
OF MEMBRANE REACTORS
Introduction
The previous chapter discussed some of the recent technological
and commercial developments which have occurred in membrane separation
processes over the past decade. The achieved results have subsequently
spawned a new area of membrane development and application. Membranes
are no longer being used only for separations. Increasingly, they are
being extended to biochemical process applications, petrochemical
1 2
operations, and inorganic membrane reactors. ’
Similarly, the work presented in this chapter has been sparked by
the demonstration of transition metal complexes supported in liquid and
polymer membranes for gas separations^'^’^"^. The concept of
permselective transport of gases by such systems has led to the use of
similar membranes, or films, to catalyze reactions of gaseous
substrates. A process such as this might lead to a facile separation of
products from the catalyst. Additionally the selective removal of the
products can shift an equilibrium system.
Even though much research is being conducted within this rapidly
expanding area, the application of polymeric membrane reactors to pre¬
existing commercial homogeneous processes has been widely neglected.
The objective of this research was twofold. The first was to
43

44
demonstrate the feasibility of a polymeric membrane reactor using well
characterized catalytic reactions. The second was to apply the
knowledge gained in obtaining the first goal to more reactions which
utilize the advantages of a membrane reactor. The hydroformyl at ion of
propylene and the oxidation of 1-butene using transition metal compounds
supported in polystyrene, poly(butyl methacrylate), and composite
polystyrene/silicone gum rubber membranes were studied for demonstration
purposes. The oxidation of mustard agent simulants and the formation of
hydrogen peroxide were studied for application purposes.
The use of insoluble, polymer bound transition metal complexes to
9-12
catalyze homogeneous reactions has been reported. A polymeric
membrane reactor, however, utilizes a polymer medium for the reaction
environment. This novel method of reaction has not been explored and
thus investigation of its feasibility, illustration of its versatility,
and elucidation of the factors which influence reactivity are warranted.
The concept of using membranes for reaction stems from attempts to
combine multiple processing steps and thus achieve economically more
attractive systems. The ability to conduct a reaction within a membrane
along with the membrane's inherent ability for separation might
eliminate several purification steps which might otherwise be necessary.
To achieve this goal, layering or combining different membrane types may
provide systems which allow chemical reaction and product-reactant
separation within the same process unit. Hollow fiber membranes may
offer another attractive pathway for improving these processes. These
membranes consist of bundles of hollow fibers (10-1000 iim in diameter)

45
O
and provide extremely high surface area per unit volume,(e.g. 500 m in
3
a 0.3 m reactor).
An important aspect to be considered when investigating the
feasibility of membrane reactors is how a reaction at the transition
metal center is affected by the surrounding polymer environment. As in
any discipline, the most useful information is obtained by comparing
experimental systems and results with well characterized processes. In
this case, using analogous solution chemistry as a basis for comparison
gives an accurate determination of the properties associated with
reaction in a membrane. Therefore, a brief description of the reactions
employed will be presented. A more thorough description of
hydroformylation follows in chapter 4.
Hydroformylation is the term applied to the process whereby an
alkene reacts with carbon monoxide and hydrogen to form an aldehyde.
This is shown schematically below. The reaction does not proceed in the
absence of catalysts. Typically the catalysts or catalytic precursors
employed are metal carbonyls, with cobalt and rhodium being the most
widely used. The formation of butanal from propylene is the primary
reaction of industrial significance.
0
II
ch3ch2ch2ch
ch3ch = ch2
RhH(CO)(PPh3)3
H2,
>
+
0
\\
CH-
CH
I
CHCH
3
co i Pin. 65°C

46
Commercially, the straight chain isomer, n-butanal, is more
desireable than the branch chain isomer, isobutanal. This is mainly
because of the greater number of uses and applications for n-butanal.^
The hydroformylation reaction, or oxo process as it is known
industrially, is carried out under a variety of conditions. Typical
requirements when using a cobalt catalyst are total pressures of 200 to
300 atmospheres and temperatures of 120 to 170°C.^ Use of a rhodium
catalyst results in much less severe reaction conditions. Rhodium
65
catalysts are active at room temperature and pressure. Equally as
important is the selectivity of products produced. Cobalt carbonyl
catalysts will produce a straight to branch ratio up to three to one,
while modified rhodium carbonyl catalysts can produce selectivities as
high as thirty to one. The relatively high activity achieved under
mild reaction conditions makes rhodium an ideal catalyst for membrane
reactor demonstration.
Hydridocarbonyltristriphenylphosphine rhodium(I), RhH(CO) (PPh^,
was the complex chosen to catalyze the reaction in a polymer membrane.
First reported in 1968 by Wilkinson and co-workers,^"^ this
homogeneous solution catalyst was shown to be active at 25°C and less
than 1 atmosphere pressure. It is a precursor to the proposed active
catalytic species, RhH(CO) (PPh^, and has been shown to be one of the
more active precursors. It is an ideal catalyst for demonstration
purposes.
The second system chosen to demonstrate the reactor membrane
process was that of an oxidation reaction. The word oxidation can be
used to describe many things. Equally as diverse as the applications

47
and definitions are the products and mechanisms by which oxidation
reactions occur. The aspect of this work is limited to a small portion
of the area of oxidations and therefore the scope of material presented
will be focused only upon pertinent information. There are, however,
72-75
many reviews and references on this broad subject which are
available.
Specifically, the oxidation of terminal alkenes to their
respective methyl ketones, as shown below, was studied. This reaction
was ideal since it offered a different type of reaction scheme from that
of hydroformylation, yet was possible to achieve under mild conditions -
- a necessity for laboratory purposes. It also is a process which has
been widely studied and well characterized and thus affords an excellent
example for demonstration purposes.
CH3CH2CH = CH2
CRTRLYST
08 1 Bin. 40°C
>
0
ch3ch2cch
3
The oxidation work presented in this chapter is based upon two
different catalyst systems which have received considerable attention
over the past twenty years. One of the first examples of selective,
non-radical alkene oxidations using molecular oxygen was demonstrated by
Dudley and Read in 1972. It involved a stoichiometric oxidation of a
terminal alkene in the presence of RhH(CO)(PPh^)^ or RhCl(PPh3)3 and
produced a moderately high selectivity for ketone formation relative to
aldehyde. Subsequent work indicated that an equivalent quantity of

48
triphenylphosphine oxide was produced.^ The system was made catalytic
with the incorporation of excess triphenylphosphine ligand. The
selectivity of the system indicates that the reaction does not proceed
by a free radical pathway. The mechanism proposed for this process is
shown in figure 3-1. It essentially involves coordination of olefin,
formation of a peroxo species, nucleophilic attack of the peroxo ligand
on the coordinated olefin to produce a five-membered peroxymetal1ocycle
followed by reductive elimination of the peroxymetal1ocycle intermediate
and its subsequent decomposition to the observed products.
Another catalytic system which was found to produce selectivities
in excess of 98% for methyl ketone formation was reported by Mimoun and
79
co-workers in 1978. It involves the use of a 2:1 ratio of
copper(11)/rhodium(111) co-catalyst. The system is unique. Not only
does it produce a high selectivity to methyl ketone, but also it
involves the incorporation of both atoms of dioxygen in ketone product
while exhibiting a zero order dependence for dioxygen. At 40°C, greater
than 100 turnovers in four hours were achieved. It was demonstrated
that the incorporation of a small quantity of isopropyl alcohol
increases the activity of the reaction and results in an initial
formation of acetone as a byproduct. Typically the catalyst precursors
used were RhClj'X^O and CutNOj^^.SH-jO. However many others were also
employed.
80-82
Subsequent work on this system by Drago and co-workers has
shown that in the absence of a copper(II) co-catalyst, only one oxygen
atom is incorporated into the ketone and that acetone and water are
continuously produced. It was also demonstrated, that in the absence of

49
PPh i O
+
MeCOC Hj R
♦ PPh,
/ 1
0} CvCHjR
rch2
0 CH
0 C H j
+ X
PPh3
Figure 3-1.
78
Read and Dudley mechanism for the oxidation of
terminal alkenes with RhH(CO)(PPh^)3-

50
oxygen, either hydrogen peroxide or tertiary butyl hydroperoxide could
be used as the oxidant. This was shown in both the systems with and
82
without copper(II) co-catalyst. Proposed mechanisms based upon these
observations are shown in figures 3-2 and 3-3.
The previously discussed reactions were utilized for demonstration
purposes. Based upon the strategies and successes achieved, more
advantageous systems were studied. Because of the high cost of
producing and using membranes, an advantage must be gained over existing
traditional technology in order to employ membranes in these reaction
processes. Two reactions which might provide these advantages were
tested. The first of these, the oxidation of alkyl sulfides to
sulfoxides and sulfones with oxygen is shown below. The development of
reactor membranes for this purpose is of particular importance. Their
use as self decontamination systems is being actively investigated by
the United States Army Chemical Research Development and Engineering
Center. Alkyl sulfides are simulants for mustard gas agents and new
routes to their decomposition are being investigated. Reactor membranes
which can oxidatively decompose alkyl sulfides are being studied for
their use as a polymer "self-decontaminating film" on tanks and other
weaponry.
(CH3CH2CH2CH2)2S
CPTRLYST
>
0
II
C CH3CH2CH2CH2)2S
II
(CH,CH2CH,CH2)2S
0
2 am. Oj
90°C

51
RhCI
â– rtf
Rh -O-C-H
ch3chr'oh
= C HR
Figure 3-2.
Proposed mechanism82 for the oxidation of terminal
alkenes using a rhodium(111)/copper(11) co-catalyst.

52
Rh CU
l/J-'CH3CHR'OH
H+A f R#
u
Rh -O-C-H
CH-
H
2Cu
vK
k
, Rh
CH3CRb
2Cu
III
H*
2Cu"
CH3CRO Rh' r HÓOH
^\/^ + 2Cu 2Cu" Rh-O-O-H
R ,/"* Op + 2H
Rh-O-C-H
ch3
h3cro^
H
ch2=chr
Cu
R
R-C-CH3
O.
Rh O
l\ ^
h-c-c-h
I I
H R
R
RhrO-O-C-H
V 1
ch2=chr ch3
Rh-O-O-C-H
ch3
CH p=CHR
Kn-u-
A
Figure 3-3.
82
Alternative mechanism for the oxidation of terminal
alkenes using a rhodium(111)/copper(11) co-catalyst.

53
The selective oxidation of sulfides to sulfoxides using transition
metal catalysts has been the object of an extensive quantity of
oo oc
research. Most of this reported work utilizes alkyl
07 OQ QQ QO
hydroperoxides or hydrogen peroxide as the oxidant and results
in the formation of sulfones as a byproduct. The use of O2 or air with
these transition metal catalysts, in most cases, results in similar
product formation. Ledlie and co-workers used RuClj^xh^O to
97
catalyze the oxidation of butyl sulfide. Later, Riley utilized
ruthenium(II) dimethyl sulfoxide catalysts in similar systems and
proposed two possible mechanisms whereby a ruthenium(11)/ruthenium(IV)
cycle operated.®8-10 These are shown in the equations la and b, and 2.
"Ru(11)" + 02 <--=
=--> "Ru(IV)"
+ o22'
(la)
SR2 + H2C)2 + ROH <===
=—> S(0)R2 +
H20 + ROH
(lb)
"Ru(IV)-SR2" + h2o <--=
=—> "Ru( II)"
+ S(0)R2 + 2H+
(2)
The demonstration of ruthenium-oxo complexes in the catalysis of a
variety of organic substrate oxidations^’^ indicated that such
catalysts might be suitable sulfide oxidation catalysts. Subsequently,
Drago and co-workers have shown both cis-dioxo bis(2,9-dimethyl-1,10-
phenanthrol ine) - rutheni um(VI )hexafl uorophosphate, [Ru(0)2 (dmp) 2] (Pfr6)2’
and the trimer trisaquo-oxo-hexapropianato-trisruthenium(III)
propionate, [Ru^prop^^O^] (prop), to be capable of oxidizing butyl
sulfide to butyl sulfoxide^'^ in acetonitrile under relatively mild

54
reaction conditions of 100°C and 2 atmospheres of oxygen. The catalysts
are shown in figure 3-4a and b respectively.
The second application of membrane reactors is focused on the
formation of hydrogen peroxide. The commercial production of hydrogen
1 08
peroxide is accomplished by the anthraquinone autoxidation process or
by direct combination of hydrogen and oxygen. Presently, there is a
rapidly expanding market for hydrogen peroxide. It was estimated that
365 million pounds of were used in 1987 for many different
applications. The largest of these included chemical production, pulp
and paper processes, and environmental purposes. It is estimated that
in 1992 590 million pounds will be utilized per year.^ In order to
keep up with such a rapidly expanding need, many companies are being
forced to expand and modernize their existing plants or to develop new
methods for production.
The anthraquinone autoxidation process was first commercially
operated in Germany during World War II. While many new processes have
been developed, all retain the basic features of the Riedl-Pfleiderer
108
process shown in figure 3-5. The process involves catalytically
reducing an anthraquinone to its corresponding anthraquinol which is
then oxidized in air to reform the anthraquinone and produce hydrogen
peroxide. The process has remained essentially the same for almost
fifty years. Little improvement has been achieved in the numerous
separation and purification steps which are required to maintain an
active system.
The hydrogenation portion of the reaction requires a chemically
stable, water insoluble, nontoxic solvent with a high flash point

55
b)
Figure 3-4.
(pp6)2
Sulfide oxidation catalysts: a) [RuCO^idmp^] (p^6)2
and b) [Ru20(prop)g(H20)3]+.

56
+ H202
Figure 3-5.
Anthraquinone autoxidation process.

57
and low volatility. Typically, a 50:50 mixture of benzene and - Cg
secondary alcohols is used. One of the major problems associated with
this system involves maintaining a soluble working material. Reduction
is carried out using slightly elevated partial pressures of hydrogen at
temperatures under 100°C and conversion is limited to 50% to minimize
anthraquinone-deactivating secondary reactions. Catalysts which have
been utilized for this process step include supported Raney nickel and
pal 1 adi um. ^
The oxidation of the resulting anthrahydroquinol is easily
accomplished without the aid of a catalyst. The rate is dependent upon
the pressure of oxygen and temperature of the reaction. The most
critical portion of this step is in the removal of the reducing catalyst
and the subsequent phase boundary surface area between the organic
solvent and water used for extraction. Regeneration of the working
solution is required to remove all inactive anthraquinone derivatives
formed as well as any aqueous solution retained in the system.
A second method used for hydrogen peroxide production could be
considered to be in its infancy by comparison with the anthraquinone
process. Only within the past ten years has the ability to directly
combine hydrogen and oxygen to produce hydrogen peroxide become
109
available. While little has been reported of its mechanistic detail,
the procedure involved is rather straightforward. The reaction is run
in an aqueous medium using palladium on adsorbent carbon as a
hydrogenation catalyst with superatmospheric pressures (200 to 4000
psig) of hydrogen and oxygen. The reaction is conducted under mild
temperatures (0 to 50°C) and produces an aqueous solution which is

58
approximately 20% by weight. The use of an all-aqueous reaction
medium provides a safer reaction process since it does not produce
mixtures of H2O2 and an organic component. Application of these
processes to membrane reactors may similarly produce a system which
reduces the number of process steps required to maintain an active
system while operating under safer reaction conditions.
The primary goal of this project was to demonstrate the ability to
achieve reaction within a polymer environment and, based upon the
achieved success, apply the process to reaction systems which would be
advantageous for one reason or another to carry out within a membrane.
The work presented supports this objective. The process developed is an
extension of pre-existing catalyst technology and is not an attempt at
discovering new catalysts.
Experimental
The complexes studied and/or used in this work were prepared from
reagents which were either purchased or previously synthesized. The
following procedures can be used to prepare these compounds. The
solvents used were purified by storage over 4A molecular sieves under an
atmosphere of nitrogen. Characterization of the complexes was conducted
using a Nicolet 5DXB FTIR Spectrometer. Identification and
quantification of reaction samples were conducted using a Varian Model
3700 gas chromatograph, a Hewlett-Packard 5890A gas chromatograph in
connection with a Nicolet 5DXB FTIR Spectrometer and a Varian Model 3400
gas chromatograph in connection with a Finnigan Mat Model 700 Ion Trap

59
Detector. Elemental analyses were conducted by the University of
Florida Department of Chemistry Microanalysis Service.
Hvdridocarbonvltris(triphenylphosphine)rhodium( I), RhH(CO) (PPh^
Hydridocarbonyltris(triphenyl phosphine)rhodium(I), RhH(CO)(PPh^)3,
was prepared according to the literature.111 Experimental analysis:
%C = 71.8, %H = 5.12, %N = 0.00. Theoretical analysis: %C = 71.9,
7oW = 5.05, %N = 0.00. Melting point 120 - 122°C (lit. 121 -122°C). Ir
analysis (nujol mull): Rh-H: 2041 and 785 cm"1 (lit. 2040 and 786 cm"1),
C=0: 1918 cm"1 (lit. 1923 cm'1).
Tri fl uoroacetatotri s (tri phenyl phosphine) rhodium! I), RhlOoCCF-,) (PPh^K
Trifluoroacetatotris(triphenylphosphine)rhodium(I),
Rh(O2CC)(PPh^)3, was obtained from Dr. Cindy Getty and Steve
112 113
Showalter. It can be prepared ’ from RF^^CCFj)^ according to a
method similar to that reported by Drago and Telser.11^
Pioxo-bis(2.9-dimethyl -1,10-phenanthrol inelruthenium(VI) hexafluoro-
phosphate, ÍRu(0)o(dmp)ol(PF^lo
[Ru^^dmp^] (PFg^ was obtained from Dr. Cindy Bailey. It can
be prepared with moderate difficulty from the oxidation of
[Ruidmp^F^O^]^ with ceric ammonium nitrate, (NH^CeiNO^g.1^11 ’ ^
Trisaquohexapropionatotrisrutheniumnil) propionate.
IRu30 (prop) 6XH20131,( prop).
The ruthenium trimer [RujCKpropJg^O^] (prop) was obtained from
Dr. Shannon Davis. It can be prepared from RuCl^xF^O.1 ^
Membrane Preparation
The membranes employed in this study were prepared using a casting
technique. The appropriate polymer was dissolved in a suitable solvent,

60
most often toluene or methylene chloride. The transition metal complex
to be used for a specific reaction was then dissolved in the same
solvent and added to the viscous polymer solution. The resulting
solution was then transferred to an aluminum foil form. Evaporation of
the solvent at room temperature resulted in the formation of uniform
polymer membranes with an average thickness between 0.5 and 1.0 mm.
These were used without further treatment.
Permeation Apparatus
The apparatus used for the membrane reactions, (shown in
figure 3-6), was designed to provide support of the membrane under
experimental reaction conditions. The film is supported both on the low
and high pressure sides by stainless steel metal frits (5/¿ pore size).
Temperature of the reaction is controlled by a Variac and thermal tape
in conjunction with a temperature controller.
Permeation Procedure
A typical permeation experiment is described in the following
paragraph. The membrane to be used is secured between the two chambers
of the reactor using o-rings and the two parts screwed together to
ensure a proper seal. Both chambers are evacuated for approximately 1
hour to remove any excess solvent trapped in the membrane. The lower
and upper chambers are then closed off under vacuum and the upper
chamber filled with one atmosphere of the reactants. The gases permeate
through the membrane during which time reaction occurs. The products
and unreacted substrates then desorb from the film into the evacuated
chamber. Periodically, both chambers are monitored to determine the
extent of reaction. This is done using FID gas chromatography using a

61
5 micron pore size
Figure 3-6.
Reactor membrane apparatus.

62
2.5m stainless steel column packed with either porapak Q or
diethyleneglycol adipate. GC-FTIR, and GC-MS were also run to confirm
all of the product identities.
Results and Discussion
Hydroformvlation of propylene
The hydroformylation of propylene was the first reaction attempted
in order to demonstrate the reactor membrane process. The reaction was
carried out at 65°C using a 1:1:1 gas mixture of the reactants hydrogen,
carbon monoxide, and propylene at a total pressure of 1 atmosphere with
a polystyrene membrane which contained 2.14 x 10’^ moles of
RhH(CO)(PPh2)3. The pressures in the two chambers equilibrated over a
period of three days. Gas samples were taken periodically, however with
a decreasing pressure gradient, it is impossible to report the data on
an activity curve as would normally be done with a catalytic run.
Alternatively, the amount of product produced within a given period of
time is reported. In this case, 4.7 x 10’^ moles of butanal and
6.6 x IQ'10 moles of isobutanal was produced in 72 hours. While it is
true that this is an extremely small quantity of product and represents
a very small amount of conversion, it is, never-the-1ess important since
it is the first demonstration of reaction within a polymer environment.
There are many factorss which might account for the low
conversion. First, it must be considered that the reactants are gases
and therefore their concentrations in the membrane are appreciably less
than those of an analogous solution. The interaction of substrate and

63
catalyst is reduced because of this lower concentration of reactants.
It is entirely possible that within the polymer, there is little
catalyst substrate interaction occurring as a result of the reactants
permeating through the film relatively rapidly. This is heightened by
the slow diffusion of reactants within the film and the immobility of
the catalyst. It is likely that a large fraction of the reactants pass
through the film via pores and channels without ever coming into contact
with the catalyst. Coupled with this problem is the fact that three
different reactants must make contact with the catalyst for reaction to
occur.
Considering this, a possible way to improve upon the extent of
reaction would be to alter the diffusion and solubility characteristics
of the gases in the polymer. To accomplish this, a different polymer
was chosen for the reaction medium. Poly(butyl methacrylate), PBM, was
the polymer chosen to demonstrate how the diffusion and solubility
characteristics of the polymer could influence the reaction
characteristics. Pure PBM has a glass transition temperature (Tg) of
27°C whereas the corresponding value for polystyrene is 100°C. PBM is a
rubbery polymer under reaction conditions and its diffusion and
solubility properties are considerable different than of polystyrene,
PS, a glassy polymer under the same reaction conditions.
Using reaction conditions identical with the previously mentioned
_ C
reaction, in conjunction with 3.9 x 10 moles of catalyst contained in
-8
the PBM film, 1.1 x 10 moles of butanal was produced with only trace
quantities of isobutanal present. This is a remarkable observation
since it demonstrates just how great an effect the polymer medium can

64
have on the reaction. This result can be likened to running a solution
reaction in which two entirely different solvents are utilized. Perhaps
the most important observation is not in the increased activity, but
rather in the drastic improvement in selectivity that is achieved.
The use of a different polymer shows that the extent of reaction
can be altered by changing the diffusion and solubility properties of
the polymer. It was thought that a greater extent of reaction might be
obtained through optimization of the reaction conditions. This can be
accomplished through two means. The first involves the addition of
excess ligand. The second pertains to increasing the reaction
-
temperature and pressure. This is carried out using 2.4 x 10 moles of
RhH(CO)(PPh^)3 in conjunction with five times as much triphenyl phosphine
in a PBM film at 100°C. A pressure of two atmospheres of synthesis gas
(H2 and CO), in a 1:1 ratio, is placed on both sides of the membrane and
left for a period of two days. At the start of the reaction, 2.0 mL of
propylene was injected into the upper chamber creating a small pressure
differential (50 mmHg). This experimental setup ensures complete
saturation of the membrane with synthesis gas and the partial pressure
of propylene is used to facilitate its permeation through the membrane.
Within twenty four hours, 2.2 x 10~^ moles of butanal are produced with
trace amounts of isobutanal also observed.
The best results are achieved using a system that contains
Rh(Ü2CCF2)(PPh3)3 in PBM with a fivefold excess of ligand under the same
reaction conditions reported previously. It produces 8.1 x 10’^ moles
of butanal and trace amounts of isobutanal. This catalyst had
112
previously been studied and shown to be efficient for the

65
hydroformyl ation of liquid substrates in solution. In this reported
case, a five molar excess of triphenylphosphine in neat 1-hexene
produced 225 turnovers and a 4.3 to 1 ratio of straight to branch chain
aldehyde. Comparison of the polymer and solution reaction mediums
reveals that they have similar dielectric constants. A summary of the
membrane reactions is shown below in table 3-1.
Oxidation of 1-butene
The second system studied for demonstration purposes resulted from
a serendipitous discovery. When air accidently leaked into the initial
hydroformylation system described above, the rapid production of acetone
from propylene was observed. This product formation appeared to occur at
a much faster rate than that of the hydroformylation products. This
discovery led to attempting the oxidation of terminal alkenes to their
respective methyl ketones for the demonstration of reactor membranes.
Again the first membrane studied is a PS film that contains
. 5
3.9 x 10 moles of RhH(CO) (PPh^K. Reaction conditions employed were
slightly milder than those of the hydroformylation systems. Temperature
is maintained at 40°C and a 1 atmosphere mixture of and 1-butene is
charged into the upper chamber. After three days, 7.9 x 10 moles of
2-butanone is produced selectively. Data for this reaction and others
similar in nature are reported in table 3-2. The first thing observed
with this demonstration reaction is that under milder conditions, a
substantially larger quantity of product is produced relative to the
similar hydroformylation system. This indicates, as expected, that
different types of reactions are influenced to varying extents by the
surrounding environment.

66
Table 3-1. Hydroformyl ation of propylene with RhH(CO)(PPh^)3•
Membrane
Moles
Catalvst
Mol es
Butanal
Turnovers3
Butanal
Moles
Isobutanal
Turnovers3
Isobutanal
PSb
2.14xl04
O
r â–  <
1
O
T—1
X
1—
2.2xl0'6
O
1
O
r—1
X
tO
3.1 x 10'6
PBMb
3.9 xlO"5
l.lxlO'8
2.8xl0'4
trace
—
PBMC
2.4 xlO’6
2.2x10*7
9.2xl0'2
trace
—
PBMd
2.4 xlO'6
8. lxlO’7
3.4x10'1
trace
a turnover is moles of product/mole of catalyst.
b reaction conditions are 65°C, 1 atm. H2, CO, and propylene
(1:1:1 mix) in the upper chamber, and reaction time is three days.
c membrane contains 1.2x10~^ moles triphenylphosphine at 100°C.
Both chambers contain 1 atm. of H2, CO (1:1 mix). Upper chamber
contains an additional 2.0 mL of propylene (1 atm. pressure).
Reaction time is one day.
d Rh(O2CCF2)(PPh^)3 catalyst in place of RhH(CO)(PPh^)3 under
identical conditions to note c. Reaction time is one day.

67
Table 3-2. Oxidation of 1-butene.
Membrane
Catalvst
Conditions3
Mol es
2-butanone
( x 10y)
Turnovers
2-butanone
( x 1041
PS
RhH(CO)(PPh3)3
7.9
2.0
PS
RhH(CO)(PPh3)3
2nd cycle
14.
3.6
PBM
RhH(CO)(PPh3)3
12.
3.1
PBM
RhH(CO)(PPh3)3
2nd cycle
47.
12.
PBM
RhH(CO)(PPh3)3
60°C
24.
6.2
SGR/PS
Rh(111 )/Cu(11)b
200.
25.
PBM
Rh (III )/Cu(11)b
60°C
160.
20.
PBM
RhH(CO)(PPh3)3
1-hexene
240.
62.
a standard reaction conditions: 3.9x10"^ moles catalyst at 40°C
with 1 atm. O2 and 1-butene (1:1 mix). Reaction time is three
days.
b 8.0x10’^ moles RhCl^xh^O and 1.6xl0'4 moles Cu(N03)2»2.5H20.

68
The same quantity of catalyst as was used in the previous reaction
was supported in a PBM film. Under similar reaction conditions, an
increase in the amount of product was observed. In this case,
g
1.4 x 10 moles of 2-butanone was produced. Cycling experiments were
conducted by reevacuating each system and refilling the upper chambers
with reactants. Essentially all membranes are saturated with reactants
at the start of the second cycle. This results in almost a twofold
increase in the production of 2-butanone for the polystyrene system and
nearly a fourfold increase with poly(butyl methacrylate). Again this is
best explained by the theory that saturation of the membranes with
reactants has occurred resulting in increased catalyst-substrate
interaction. Improved reactivity is the end result of this increased
interaction. Raising the reaction temperature to 60°C while using the
PBM/RhH(CO)(PPh^)3 membrane also improves reactivity in the butene
system. This is expected for a temperature dependent reaction.
Another reaction using the liquid substrate 1-hexene was conducted
to verify that higher substrate concentration within the membrane would
indeed result in increased reactivity. Five drops of the substrate was
placed on the film and the reaction run with the same quantity of
catalyst and reaction conditions. In three days, 2.40 x 10~'7 moles of
2-hexanone are produced selectively. This lends support to the idea
that the reactivity of the membrane can be increased dramatically under
more solution-like reaction conditions.
Based upon the observed results, a mechanistically different
reaction was attempted. It involved the use of a Rh(III)/Cu(II) co¬
catalyst system in the oxidation of terminal alkenes. A silicone gum

69
-5 -4
rubber polymer containing 8.0 x 10 moles of RhCl3*xH20 and 1.6 x 10
moles of Cu(N03)2»2.5H20 along with a approximately 1.0 ml of
isopropanol was layered on a polystyrene blank membrane. This resulted
in the production of 2.0 x 10’^ moles of 2-butanone in 72 hours. The
same catalyst system contained in a PBM film at 60°C was not quite as
reactive (1.60 x 10"^ moles in 72 hours). These observations show that
mechanistically different reactions such as this can be very active.
This supports the conclusion that the reaction type itself plays a large
part in determining the extent of reaction within the polymer framework.
Oxidation of butyl sulfide
Based upon the successes achieved in the above reactions,
attention next turned towards processes in which membrane use may be
more economically attractive. The catalytic oxidation of the simulant
butyl sulfide is studied with (1) Ru(Cl)2(Pph^)3, (2)
[Ru(0)2(dmp)2](PF6)2, and (3) [Ru30(prop)6(H20)3](prop) in
polystyrene/silicone gum rubber composite membranes. Composite catalyst
membranes are obtained by evaporating a catalyst/silicone gum
rubber/toluene solution onto a preformed blank polystyrene film. The
ruthenium membrane oxidations of butyl sulfide are carried out by
coating the upper side (the side exposed to the higher pressure) of the
films with a small amount of the liquid substrate. The top chamber of
the reactor is then filled with 30 psi 02 and the bottom chamber is
closed off under vacuum. Temperature of the reaction is maintained at
90°C. The pressures within the two chambers equilibrate over a period
of two days. The gas which collects in the bottom chamber is determined
to contain large percentages of butyl sulfoxide, butyraldehyde, and

70
propionaldehyde, along with a small quantity of unreacted butyl sulfide.
Trace quantities of 1-butene and 1,2-epoxybutane are also observed using
GC-MS.
In all membrane reactions, the total amount of products formed
appears to be substantially smaller in comparison with solution data. A
better method of analysis in this particular case would be to compare
the percentage conversion of butyl sulfide. In analyzing these membrane
reactions, the percent conversion is based upon the amount of butyl
sulfide and products which have passed through the membrane and not on
the original amount exposed to the film. This is the most relevant mode
of analysis since the employment of these materials as self
decontaminating films focuses only on the gases which permeate the film
and their relative amounts.
Table 3-3 lists the mole percent conversion for each of the
composite membrane catalysts systems. It should be noted that a
modified reactor design employing a smaller film with less catalyst is
used in the phenanthroline derivative system. In light of this, a
better judge of the membrane activities is made by comparing turnovers
of the respective catalyst membranes. A turnover is defined as the
number of moles of product produced per mole of catalyst. This gives an
accurate representation of the reaction assuming that an excess amount
of substrate was exposed to each film. Turnover data is presented in
table 3-4 and indicates that the ruthenium trimer is the best overall
catalyst employed in the membranes. Evidence which supports the th ry
that a large quantity of substrate may never come in contact with the

71
Table 3-3. Butyl sulfide membrane conversion data for various
ruthenium catalyzed oxidations by 0? at 1 atm. and
90°C.
Mole Percent
Reaction Butyl Butyl
Time (hrs) Sul fide Sulfoxide Butanal Propanal
Total
Conversion
Ru(Cl)2(PPh3)3
0
24
2.8
11.3
40.0
45.9
97.2
48
1.9
15.5
40.0
42.6
98.1
0
24
[Ru30(prop)6(H20)3](prop)
10.8
1.4
2.0
85.8
89.2
42
3.6
0.2
0.3
95.9
96.4
n
[Ru(02)2
(dmp)2](PF6)2
V
24
85.6
1.2
13.2
--
14.4
48
78.0
2.6
19.4
trace
22.0

72
Table 3-4. Butyl sulfide membrane turnover data.
Turnovers
CSJ
o
' 1
X
Catalvst
Butyl
Sulfoxide
Butanal
ProDanal
Total
Ru(Cl)2(Pph3)3
0.27
0.97
1.11
2.35
[Ru30(prop)6(H20)3](prop)
1.00
1.49
63.70
66.19
[Ru(0)2(dmp)2](PF6)2
0.40
4.68
—
5.08
Turnover data are reported at a reaction time of 24 hours based on
data in table 3-3.

73
catalyst in the membrane is obtained by comparing tables 3-3 and 3-4.
It is apparent that a larger conversion percentage can be obtained by
increasing the catalyst loading in the membrane and thus increasing the
extent of interaction between substrate and catalyst.
Comparison of the membrane data can be made to their solution
analogues*06 as well. Reported mole percent conversions of butyl
sulfide for the three ruthenium catalysts in solution under similar
reaction conditions is presented in table 3-5. The relatively high
percentage of conversion compared to solution studies indicates that
reactor membranes may prove to be useful as self decontamination
systems. The data obtained is very encouraging and indicates that the
catalyst is active when incorporated into a polymer network. Though the
activity of the membranes is lower than the solution systems, based on
the amount converted per unit time, the high conversion of material
passing through film is a desired result.
Formation of hydrogen peroxide
The production of hydrogen peroxide has been accomplished by the
anthraquinone autoxidation process and by direct combination of hydrogen
and oxygen. The application of these two systems to membrane reactors
is yet another process which has shown membrane reactors to be a
versatile process. One part of this research incorporates the basic
reaction scheme outlined in the introduction. As noted earlier, a major
drawback associated with the anthraquinone autoxidation process is
maintaining a soluble system. Several reaction and separation steps are
needed to maintain an active process. This work represents a novel

74
Table 3-5.
Butyl sulfide solution reaction conversion data for
various ruthenium catalyzed oxidations by 0? at
90°C.
Mole Percent
Reaction
Time (hrs)
Butyl
Sul fide
Butyl
Sulfoxide Butanal
Total
ProDanal Conversion
Ru(Cl)^(PPh3)3
0
100
- -
0
12
49.7
50.3
50.3
36
40.9
59.1
59.1
[Ru30(prop)6(H20)3](prop)
0
97.4
2.6
2.6
12
77.2
22.8
22.8
37
59.7
40.7 0.6
41.3
[Ru(02)2(dmp)2](PF6)2
0
99.3
0.7
0.7
12
72.1
25.9 2.0
27.9
36
69.1
28.1 2.8
30.9
Source
of data is
reference 106.

75
approach aimed at minimizing the number of required process steps while
maintaining the solubility and stability of the working material in both
its oxidized and reduced states. This would result in a more
economically attractive system. The reaction is conducted by
incorporating the catalytic system into a rubbery polymer membrane, PBM,
which is used as the medium for reaction. The second system under
investigation, the direct combination of oxygen and hydrogen, is
performed by incorporating a palladium catalyst into a PBM membrane and
using it as the reaction medium.
Flat reactor membranes are formed from poly(butyl methacrylate)
using a casting technique. Depending upon the system being studied,
either palladium black or a mixture containing 2-ethyl anthraquinone and
palladium black are incorporated in the polymer membrane. A different
apparatus than was used in the previous systems is used to support the
reaction. It is shown in Figure 3-8 and consists of two glass chambers.
The membrane is sealed between them using an 0-ring joint and clamp.
The reaction is facilitated by passing hydrogen gas over the bottom side
of the membrane and by saturating an aqueous solution on the top side of
the membrane with oxygen. Reaction occurs as the two gases diffuse into
the membrane and come in contact with the catalyst system. The
temperature of reaction is maintained by placing the reactor in an oil
bath at the desired temperature. A slightly positive pressure of
hydrogen is maintained in the lower chamber. Reaction occurs over a
four day period. The resulting hydrogen peroxide is extracted into the
aqueous layer and titrated with potassium permanganate to determine the
extent of reaction.

76
OXYGEN IN
OXYGEN OUT
HYDROGEN IN
MEMBRANE
AQUEOUS SOLUTION
HYDROGEN OUT
O-RING JOINT
Figure 3-7.
Hydrogen peroxide membrane reactor.

77
There are several key variables in this process that have been
investigated. Included among these are temperature dependence of the
process, the effect of added promoters, and the effect of cycling the
membranes. Data for the performed reactions are contained in table 3-6.
The results indicate that the anthraquinone systems are the most active.
Increased temperature also results in a more active system. Reaction
using only palladium black was accomplished with comparable activity to
the anthraquinone system. The best system for direct combination of
hydrogen and oxygen is one which incorporates an acid and halide
promoter in the film and employs higher reaction temperatures. Attempts
to find a more active system using a palladium colloid suspended in a
polymer film failed when the poly(vinyl alcohol vinyl acetate) membrane
used in the reaction dissolved during reaction.
In conclusion, the comparison of all membrane reactions with their
respective homogeneous analogues results in some notable distinctions.
The membrane reactions appear to be substantially less reactive. This
is due largely in part to the relative amount of time that the substrate
spends in contact with the catalyst. A possible way of improving upon
this would be to increase catalyst concentration. A thicker membrane
might also provide for better interaction. Comparatively, a solution
reaction occurs with the substrate continuously diffusing in and out of
solution. This results in an infinite amount of exposure with the
catalyst. In a membrane reaction, the substrate is contained in the
film for a much smaller amount of time, effectively limiting the extent
of reaction. Another observation that would explain the difference in
the reactivities of membrane and solution reactions is the relative

78
Table 3-6. Hydrogen peroxide formation.
CATALYST
PROMOTER
REACTION
CONDITIONS
1
CYCLES
2
(moles H?0? x 10b)
3 4
Pd BLACK &
NONE
60°C
2.2
2.2
1.1 1.2
2-ETHYL ANTHRAQUINONE
Pd BLACK &
NONE
95°C
11.
12.
6.9
2-ETHYL ANTHRAQUINONE
Pd BLACK
NONE
60°C
0.9
PD BLACK
H+, Br'
60°C
1.1
Pd BLACK
NAFION, H+, Br'
60°C
1.7
1.7
0.9
Pd BLACK
NONE
85°C
1.6
1.4
Pd BLACK
H+, Br'
85°C
1.5
1.8
1.5
Pd BLACK
NAFION, H+, Br'
85°C
2.0
1.0
2.0 1.2
Reaction conditions: PBM film layered on PS, 20.0 mL aqueous
solution for four day cycles. [H+] = 1 M HC1, [Br'] = 1.3 x 10'3 M
KBr, 3.6 x 10’^ moles Pd black, and/or 1.5 x 10‘4 moles 2-ethyl
anthraquinone.

79
difference in substrate concentrations contained in each reaction
medium. This directly affects the number of catalyst substrate
interactions which occur.
The initial objective of this project has been obtained.
Demonstration of the feasibility and versatility of transition metal
reactor membranes has been achieved with both hydroformylation and
oxidation reactions. The activities of the membranes are low as a
result of the engineering design of our experiment. The use of hollow
fiber membranes may lead to a more productive system. For example, the
best hydroformylation system studied produces 8.1 x 10"^ moles of
O
butanal in 24 hours or 4.06 x 10 g of butanal per minute using a film
with a surface area of 5.0 x 10'^ m^. A typical hollow fiber membrane
3
unit using 100/jm fibers contained in a 0.3 m reactor has a surface area
p
of 500 m . Transposing our system to this reactor would produce 4.0 x
p
10 g of butanal per minute. This may be one way of increasing
production capabilities in membrane reactors. Optimization of reaction
conditions has been shown to result in remarkable increases in
reactivity.

CHAPTER IV
HETEROGENEOUS HYDROFORMYLATION OF PROPYLENE USING SUPPORTED
RHODIUM CATALYSTS IN A CONTINUOUS GAS FLOW REACTOR
Introduction
The previous chapter demonstrates the feasibility and versatility
of facilitating chemical reactions within an organic polymer
environment. One remarkable attribute of membrane reactions lies in
their ability to achieve high selectivity for a particular product.
This is evidenced in the hydroformylation of propylene to n-butanal with
a high degree of selectivity. A major drawback that is associated with
these membranes is in their extremely low activity. The work presented
in this chapter involves the development of a gas phase, heterogeneous
catalyst based system resulting in substantially increased activity
while maintaining the selectivity associated with the polymer membrane
reactors.
The hydroformylation of propylene is the reaction chosen to
demonstrate this objective. The ability to use a gaseous substrate, the
possibility of producing either straight or branched chain product, and
the availability of a catalyst which is active under moderate reaction
conditions makes it ideal for study. The reaction is previously
described in chapter 3. A more detailed discussion of the reaction is
presented in this section.
80

81
Hydroformyl ation is the process whereby an alkene reacts with
carbon monoxide, CO, and hydrogen, W^, to form an aldehyde. The
hydroformylation of propylene results in the formation of both n-butanal
and isobutanal as shown below.
0
xNch
I
CH3CHCH3
The reaction does not proceed in the absence of a catalyst.
Commercially, two transition metals, cobalt and rhodium, are used to
form active catalyst complexes and are usually employed as the metal
carbonyl complexes. First discovered by Otto Roelen in 1938,^ the
process has since grown to immense proportion. In 1980, over eight
billion pounds of aldehydes or their derivatives were produced by the
process, with the formation of butanal from propylene being the primary
reaction scheme.^
Commercially, the straight chain isomer, n-butanal, is more
desireable than the branched chain isomer, isobutanal. This is because
of the greater number of uses and applications for n-butanal.^ As
shown below, n-butanal can be converted through a variety of steps to
n-butanol and 2-ethylhexanol. The latter can be converted into
plasticizers for polyvinylchloride resins.
The hydroformyl ation reaction, or oxo process as it is known
industrially, can be achieved using a variety of conditions. Typical
requirements for a cobalt catalyst system require total pressures of 200
0
CH3CH=CH2
RhH I,. CO 1 OTO. 65
^ ch3ch2ch2ch +

82
ch3ch2ch2cho
-h2o
cot.
ch3ch2ch2ch2oh
to 300 atmospheres and temperatures of 120 to 170°C.^ Use of rhodium
catalysts result in much less severe reaction conditions. Activity can
65
be observed using room temperature and pressure. Equally as important
is the selectivity. Cobalt carbonyl catalysts produce a straight to
branch ratio up to three to one, while modified rhodium carbonyl
c/\
catalysts produce selectivities as high as thirty to one. The
selectivity obtained is dependent upon a number of factors including the
ligand environment of the metal, the presence of excess ligand in the
system, and the pressure of gaseous reactants used. The relatively high
activity achieved under mild reaction conditions makes rhodium an ideal
catalyst for continuous gas flow reactor demonstration.
Modified rhodium oxo catalysts were introduced into commercial use
118-120
in 1976. One of these, hydridocarbonyltristriphenylphosphine
rhodium(I), RhH(CO)(PPh^Jg, was the catalyst chosen to catalyze the
reaction. First reported in 1968 by Wilkinson and associates,66-71
homogeneous catalyst was shown to be active at 25°C and less than 1
atmosphere pressure. It is a precursor to the proposed active catalytic

83
species, RhH(CO) (PPh3)2, and has been demonstrated to be one of the more
active rhodium precursors. It does not react to form inactive metal
clusters like many other rhodium carbonyl complexes.
Selectivity is controlled by a number of factors. The use of
polar solvents as the reaction medium leads to increased reactivity and
produces increased selectivity. Most importantly, the addition of
excess triphenylphosphine results in increased linear selectivity. The
reaction has even been carried out in molten triphenylphosphine.^ A
disadvantage though, is that the rate of hydroformylation decreases with
the addition of excess phosphine. The increase in selectivity has been
attributed to increased steric hinderance while the decreased activity
can be explained by the effect of shifting the equilibrium from a
proposed active catalytic species towards the precursor. This
equilibrium is shown in the equation below.
RhH(CO)(PPh3)3 <==========> RhH(C0)(PPh3)2 + PPh3
The widely accepted mechanism of this reaction is depicted in
figure 4-1. As shown, the reaction can occur by either a dissociative
or associative pathway with the first step being the subsequent
65
dissociation of a triphenylphosphine ligand. Coordination of carbon
monoxide is the next proposed step. Next, olefin coordination occurs.
It is the most critical step. Subsequent addition of the olefin to the
rhodium hydride bond determines whether linear or branched chain
aldehyde is formed. Markonikov addition results in the formation of a
branched alkyl complex, while anti-Markonikov addition results in the

84
L...
H
jRh—CO
I
CO
H
-L
L Rh CO
♦L
CO
H
CO
R
R
CO
f-RCHjCHjCHO
Figure 4-1.
Associative and dissociative hydroformylation
reaction mechanism.

85
formation of a linear alkyl complex. Carbon monoxide migration and
insertion to form the acyl complex is the next proposed mechanistic
step. This is followed by the oxidative addition of hydrogen. The
latter step is thought to be rate determining in the reaction but it
65
remains uncertain. Reductive elimination of aldehyde results in
reformation of the catalytic species.
Hydroformylation using modified rhodium catalysts results produces
a rather complex system. Many Rhodium species have been observed in
these systems including RhH(CO) (PPh^)3> RhH(CO) (PPh^)2> RhHfCO^iPPhg^»
118
and RhH(C0)2(PPh2)- These complexes exist in equilibrium with each
other and are formed from either triphenylphosphine dissociation or CO
addition. The truly active species has not been determined but may be
any one or combination of these in solution.
The high cost of rhodium has limited its use commercially.
Development of a process which alleviates catalyst recovery problems
associated with conventional homogeneous systems while achieving high
selectivity and activity will result in an economically more viable
reaction process. A considerable effort has been devoted to modifying
homogeneous based rhodium catalysts to form heterogeneous catalysts.
This would offer immediate advantages in catalyst/product separations.
Use of insoluble supported catalysts in liquid phase reactions or vapor
phase reactions over supported catalysts might achieve this desired
objective.
Attempts to form heterogeneous oxo catalysts by attaching them to
supports through their phosphine ligands has not resulted in better
1 OO 1 p C
catalytic systems. Use of these supported catalysts in liquid

86
phase reactions leads to active and selective systems, however, catalyst
leaching occurs. Cleavage of the phosphorous carbon bonds used to
attach the catalysts results in degradation of supported complexes
1Pfi 171
providing a pathway for catalyst leaching from the support. ’
An effective gas phase system is reported by Arai and
co-workers. The process utilizes silica gel as a support. It is
covered with a polymer formed from styrene and divinyl benzene and then
functionalized with phosphine ligands. Chiorocarbonylrhodium(I) dimer,
[Rh(CO)2d]2, is then supported on its surface. This catalyst is found
to be effective in hydroformylating both ethylene and propylene at 100°C
with atmospheric pressures of gaseous reactants. One of the major
drawbacks associated with this system is in the low selectivity obtained
for the production of n-butanal (63%) from propylene. The phosphine
linkage was viewed to be important since direct deposition of
(PPh3)2Rh(CO)Cl and RhCl^ on silica exhibited little activity under
similar conditions. Deposition of (PPh-^RhiCOjCl on alumina and
activated charcoal, however, produces active systems under substantially
1 29
more severe reaction conditions. Again low selectivities for the
linear aldehyde are obtained (56.5 to 65.5%). Gas phase
hydroformylation of ethylene and propylene have also been achieved over
130-13?
zeolite supported rhodium catalysts. Again the selectivity of
these systems is poor (<67% linear aldehyde) and the simultaneous
hydrogenation of propylene and aldehyde is a severe problem.
The objective of the work presented in this chapter is to extend
what has been accomplished with membrane based reactors. This is
achieved by the development of a heterogeneous catalyst based system

87
which produces substantially increased activity while maintaining the
intrinsic benefits associated with the polymer membranes, namely their
selectivity. This is accomplished by deposition of a rhodium catalyst
and excess phosphine ligand on silica gel and its use in a gas phase,
continuous flow reaction. The development of a reactor which is
connected to a gas chromatograph ("on-line GC") results in an accurate
evaluation of the reaction properties. Modification of the catalyst
system by coating with a polar, nonvolatile system results in increased
activity and selectivity.
Experimental
The transition metal catalysts studied in this work are prepared
as previously described in chapter III. Identification and
quantification of reaction samples are conducted using a Perkin Elmer
model 900 gas chromatograph placed in conjunction with a continuous flow
gas reactor. This is more simply described as an "On-line" gas
chromatograph.
Catalyst Preparation
The catalysts employed in this study are prepared by dispersion on
a solid support in the presence of an excess quantity of
triphenylphosphine ligand. A typical description of this procedure is
detailed below. A 250 mL round bottom flask is charged with 0.600g of
silica gel (vacuum dried at 80°C), 0.0919g (1.000 x 10~4 moles)
RhH(CO)(PPh^)3, and .262g (1.00 x 10'^ moles) triphenylphosphine.
Twenty five milliliters of chloroform is added to the solid mixture and

88
the solution stirred for approximately five minutes. It is then rotary
evaporated giving a yellow granular product which is vacuum dried
overnight at 45°C. Catalysts which are coated with propylene carbonate
are prepared similarly with the propylene carbonate being dissolved in
the chloroform before its addition to the solid catalyst mixture. A
brief description of the preparation of all catalyst systems
investigated is listed below. Each is identified by itss appropriate
abbreviation throughout the remainder of the text.
RhH\SG
The catalyst is prepared by dispersion of 0.230g (2.50 x 10~4
moles) RhH(CO)(PPh^)3 and 0.656g (2.50 x 10’^ moles) triphenylphosphine,
PPh-j, on 1.50g of silica gel using the method outlined above.
RhH\SG\PC
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10"4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10'^ moles) triphenylphosphine
and 0.08g of propylene carbonate on 0.600g of silica gel using the
method described above.
RhHXMPPS
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10~4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10'^ moles) triphenylphosphine
on 0.600g of macroporous polystyrene beads using the method outlined
above.
RhH\MPPS\PC
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10’4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10-^ moles) triphenylphosphine

89
and 0.08g of propylene carbonate on 0.600g of silica gel using the
method described above.
RhHXNafion
The catalyst is prepared by dispersion of 0.0919g (1.00 x 10'4
moles) RhH(CO)(PPh^)3 and 0.262g (1.00 x 10’^ moles) triphenylphosphine
on 0.600g of ground nafion using the method outlined above.
Rh(tfa)\SG
The catalyst is prepared by dispersion of 0.253g (2.50 x 10~4
moles) Rh(tfa)(PPh^)3 and 0.656g (2.50 x 10’^ moles) triphenylphosphine
on 1.50g of silica gel using the method outlined above.
Rh(tfa)\SG\PC
The catalyst is prepared by coating 0.92g of the previously
prepared Rh(tfa)\SG with 0.08g of propylene carbonate. This is
accomplished by rotary evaporation as described above in the catalyst
preparation section. This provides the exact quantities of reagents
used in the preparation of the other catalysts.
Reaction Procedure
The reaction is conducted in a stainless steel tube connected in
line with a GC as noted above. A schematic diagram of this setup is
shown in figure 4-2. The tube is 1/8" chromatography tubing, 45cm in
length with approximately a 25cm catalyst bed height. It is packed with
0.500g of the catalyst. A preblended lecture bottle of CO, and
propylene is used to deliver the gases to the reactor. The flow and
internal pressure of the gases are controlled by valves positioned
before and after the reactor tube. Reaction temperature is controlled
by an oil bath. The extent of reaction is determined using a sample

90
Figure 4-2.
Gas flow reactor schematic.

91
loop which allows a 0.80 mL sample to be sent through a chromatographic
column (diethylene glycol adipate, 60°C) in the GC equipped with a FID
detector. The gas flow rate through the reactor tube is measured by a
bubble flow meter at the end of the system.
Results and Discussion
The development and demonstration of this project is critically
dependent upon the ability to achieve reaction quickly with moderate
activity. The use of a catalyst under gas flow conditions necessitates
this property. Many catalyst systems were initially studied in a closed
reactor to determine if their activity was adequate for use in the flow
reactor. Through these preliminary catalyst evaluations, it was
determined that two catalysts were adequate for flow purposes. These
are RhH(CO)(PPhjjj and Rh(tfa)(PPh^)3• It was also determined that the
mixture of support, catalyst, and excess ligand in the quantities
described previously offered considerable reactivity over lower rhodium
concentration mixtures.
Initial studies in the flow reactor presented many observations
leading to the development of a more active reaction process. Included
among the improvements made from these observations are slower flow
rates, lower reaction temperatures, and most importantly pre-mixing of
the gaseous substrates. In the later case, the activity obtained
increased by five orders of magnitude! In hindsight, it indicates that
with three individual substrate lines coming together, one of the gases,
which has a slightly greater partial pressure than the other two, is

92
shutting off the other two gas flows. Therefore only one reactant is
effectively coming in contact with the catalyst.
After the reaction had been demonstrated to occur at a
considerable rate, the physical properties that affect reaction in the
flow system are investigated to afford an optimized reaction process.
The properties studied include temperature, pressure, gas flow rate, and
substrate ratio. The catalyst RhH\SG is used to investigate these
factors. Analysis of the gas stream after reaction is made by
calculating the activity of a particular product. The activity, as
defined in the equation below, is the number of moles of product
produced in a given amount of time. Throughout the remainder of this
section, all reported activity data, unless otherwise noted, will
represent the activity achieved after production of n-butanal has
maximized and leveled out.
Activity = ( moles/0.8 mL)(flow rate in mL/min)
The first of these properties studied is the influence of
temperature upon reaction. The reaction is carried out at four
temperatures to see the affect on both the selectivity and activity. At
50°C, little reactivity is observed. The selectivity of the reaction is
difficult to determine due to the small amount of product which is
produced. At a slightly elevated temperature, 65°C, the reaction
proceeds at an increased rate. It is apparent from the analysis of the
data that the quantity of n-butanal and isobutanal produced grows
rapidly and after a period of time reaches a maximum and levels out.

93
The selectivity is determined to be 81.1% for the production of
n-butanal relative to isobutanal. At a temperature of 80°C the reaction
is observed to occur at a substantially greater rate than observed at
65°C; however the selectivity decreases slightly to 80.5%. At a
temperature of 95°C, the reaction becomes erratic. Three different
attempts to achieve reaction at this temperature produced three
different sets of activity data. It appears from this information that
even under slower flow rates, reaction is difficult to achieve at this
temperature. The collected data indicates a substantial decrease in
activity accompanied by a decrease in selectivity to 74%. In all cases,
the amount of propylene converted to the linear and branched chain
aldehydes is small (<1.4%), but with increasing temperature, it is shown
to increase. The results of these experiments are summarized in table
4-1 and are shown graphically in figure 4-3. The activity data reported
represents the activity obtained after the rate of production levels
off. Typically, this is approximately thirty minutes.
After conducting the temperature dependence studies upon the
reaction, it is apparent that a pattern develops in each system. The
rate at which isobutanal is produced occurs at an increased rate
relative to that of n-butanal as shown in figure 4-4. It reaches a
maximum at an earlier time than the linear isomer and then levels off.
Therefore the selectivity increases throughout the reaction with the
maximum selectivity occurring after the production of n-butanal has
maximized and leveled off. Data are shown in table 4-2.
The second property of the process to be investigated is the
effect that the rate of gas flow has upon the reaction properties.

94
Table 4-1. Temperature effect upon propylene hydroformylation
activity using RhH\SG.
Temperature
(°C)
Activity
n-Butanal
(moles/min)
xl06a
Isobutanal
(moles/min)
Selectivity
(%)
Total
Conversion
(%)
50
0.58
N.A.
<0.05
65
3.61
0.84
81.1%
0.35
80
11.4
2.76
80.5%
0.87
100b
7.01
2.48
73.9%
1.35
a Reactor
conditions: 0.
50g RhH\SG.
Pressure is 13
psi using a
(1:1:1) H2, CO, and CHjCtbCH^ gas mixture. Rate of gas flow for
various temperatures is 25 mL/min (50°C), 26 mL/min (65°C), 33
mL/min (80°C), 20 mL/min (100°C). Reaction time for various
temperatures is 20 min. (50°C), 25 min. (65°C), 20 min. (80°C),
15 min. (95°C).
b catalyst becomes less active and produces varying amounts of
products.

Activity x 10 (moles/min)
95
Figure 4-3. n-Butanal activity as a function of temperature
in the hydroformylation of propylene with
RhH\SG.

96
Table 4-2.
Reaction
Time
(min)
Selectivity as a function of time in the
hydroformylation of propylene with RhH\SG.
Activity xl06a
n-Butanal Isobutanal Selectivity
(moles/min) (moles/min) (%)
Total
Conversion
(%)
5
2.40
1.13
68.0
0.37
10
10.7
3.18
77.0
1.16
15
14.3
3.83
79.0
1.48
20
15.9
4.12
79.5
1.56
25
15.9
4.07
79.6
1.54
a Reactor
conditions: 0.50g RhH\SG.
Temperature is 80°C
Pressure
is 13 psi using a
(1:1:1) H2
, CO, and CH?CH=CH?
, gas
mixture.
Rate of gas flow
is 12.5 mL
/mi n.

Activity x 10 (moles/min
97
Figure 4-4.
Comparison of hydroformylation activity in the
production of n-butanal and isobutanal with RhH\SG.

98
Again the catalyst system chosen to catalyze the reaction is RhH\SG.
Based upon the reaction data, the maximum selectivity obtained occurs
with the fastest flow rate. This advantage is offset by the fact that
the smallest conversion of propylene also occurs with the fastest flow
rate. An important observation from the flow rate data is that over the
range of 7.7 mL/min to >30 mL/min, the activity that results reaches
approximately the same magnitude. This is remarkable and indicates that
under the slower flow rates, saturation of the catalyst environment with
gaseous reactants is probably occurring, leading to improved reactivity.
At the higher flow rates, a smaller fraction of the catalysts are
interacting with the substrate. This, however, is offset by the
increased quantities of reactants which are flowing through the reactor
leading to similar activities as those reported for the slower flow
rates.
The main difference observed using different flow rates is in the
rate at which the maximum activity is obtained. This is shown
graphically in figure 4-5. It is obvious that at extremely slow flow
rates (2.0 mL/min), the greatest conversion occurs with the poorest
selectivity. The activity obtained from the slower system is also
substantially less than those of the higher flow rates. Given long
enough reaction times, however, the activity should approach those of
the faster flow rates. Data from the flow rate studies are presented in
table 4-3.
The effect of increased pressure on the reaction under a
continuous gas flow process is investigated. Once again, RhH\SG is the

Activity x 10 (moles/min
99
Figure 4-5.
Effect of gas flow on the n-butanal activity in
the hydroformylation of propylene with RhH\SG.

100
Table 4-3. Effect of gas flow on the hydroformylation of
propylene with RhH\SG.
Flow rate
(mL/min)
Activity
n-Butanal
(moles/min)
xl06a
Isobutanal
(moles/min)
Selectivity
(%)
Total
Conversi
(%)
2.0
2.26
0.85
72.1
3.97
7.7
6.24
1.91
76.6
2.08
12.5
6.63
1.92
77.5
1.34
30.0
6.45
1.86
77.6
0.53
a Reactor conditions: 0.50g RhH\SG. Pressure is 13 psi using a
(1:1:1) F^, CO, and CHjCFbCF^ gas mixture. Temperature is 80°C.
Reaction time for various flow rates is 60 min. (2.0 mL/min), 30
min. (7.7 mL/min), 25 min. (12.5 mL/min), and 20 min.
(30.0 mL/min).

101
catalyst system used for determining the affect of increased pressures.
Reactions are conducted with 10, 20, and 45 psi pressure within the
reactor tube. As expected, the most active system results from the
highest gas pressure as shown graphically in figure 4-6. The increased
activity is accompanied by an increase in the percent conversion of
propylene and decreased selectivity. Data are reported in table 4-4.
The effect of the ratio of substrate gases utilized is also
investigated. Ratios of 1:1:1, 3:1:1, and 1:3:1 hydrogen, carbon
monoxide, and propylene are used for this purpose in conjunction with
the RhH\SG catalyst. Slightly different flow rates in each reaction
were used, however this should not affect the equilibrium activity
obtained in any of the reactions. The total activity achieved in each
case is small but indicates that an equivalent ratio of each gas (1:1:1)
leads to the greatest activity (figure 4-7). The use of the higher
quantity of hydrogen results in the most selective system. Data based
on these results are shown in table 4-5.
Additional information is obtained from the above reactions. All
optimization experiments described were achieved with the same catalyst,
RhH\SG. After subjecting the catalyst to all these reported conditions,
a gradual loss of activity is observed. It is important to note that
all reactions used to investigate each reaction property were run
consecutively with as nearly identical conditions as possible. This
allows for accurate comparison of the individual reactions. However,
comparison of an individual reaction from one investigative reaction
series with that from another may result in slightly different

Activity x 10 (moles/min
102
Figure 4-6.
Effect of gas pressure on the n-butanal activity in
the hydroformylation of propylene with RhH\SG.

103
Table 4-4. Effect of gas pressure on the hydroformylation of
propylene with RhH\SG.
Activity xl06a
Reactor
Pressure
(DS i )
n-Butanal
(moles/min)
Isobutanal
(moles/min)
Selectivity
(%)
Total
Conversion
(%)
10
3.06
0.90
77.3
0.49
20
5.07
1.46
77.6
0.72
45
9.19
3.18
74.3
1.29
a Reactor conditions: 0.50g RhH\SG. Pressure is 13 psi using a
(1:1:1) H2» CO, and CH-jCH=CH2 gas mixture. Temperature is 80°C.
Rate of gas flow relative to various pressures is 16.0 mL/min (10
psi), 17.5 mL/min (20 psi), 19.5 mL/min (45 psi). Reaction time
for various pressures is 25 min. (10 psi), 25 min. (20 psi), 25
min. (45 psi).

g
Activity x 10 (moles/min)
104
Figure 4-7.
Effect of gas ratios on the n-butanal activity in
the hydroformylation of propylene with RhH\SG.

105
Table 4-5. Effect of gas ratios on the hydroformylation of
propylene with RhH\SG.
H^COrC.H,-
Cn . . 00
Ratio
1:1:1
3:1:1
1:3:1
Activity xl06a
n-Butanal Isobutanal
(moles/min) (moles/min)
1.92 0.46
1.48 0.33
0.73 0.17
Selectivity
80.7
81.8
81.1
Total
Conversion
m
0.13
0.12
0.09
a Reactor conditions: 0.50g RhH\SG. Pressure is 13 psi using a
(1:1:1) Hj, CO, and CH^CLbCl^ gas mixture. Temperature is 80°C.
Rate of gas flow for various gas mix ratios is 35.0 mL/min
(1:1:1), 50.0 mL/min (3:1:1), 38.0 mL/min (1:3:1). Reaction time
for various ratios is 25 min. (1:1:1), 25 min. (3:1:1), 25
min. (1:3:1).

106
activities or conversions. Based upon this observed gradual decrease in
activity, all remaining experiments and catalyst evaluations are
conducted with fresh (unused) catalysts.
The above studies allowed for the determination of the most
optimum conditions of reaction. The most ideal reaction temperature is
determined to be 80°C. The flow rate is not as critical since almost
all give similar activities; however, flow rates of 7.5 to 20 mL give
the best percent conversion of propylene. A pressure of 15 to 20 psi
allows for moderate activity while maintaining a reasonable selectivity.
Use of a 1:1:1 ratio of F^:CO:propyl ene is determined to be the best for
reactivity purposes. These reaction conditions are utilized in the
following studies for the development of more active and selective
catalysts.
Fresh RhH\SG catalyst was reran in the flow system using the
determined optimum conditions. An equilibrated steady state activity of
15.9 x 10~6 moles/min is obtained for the production of n-butanal. A
selectivity of 79.6% is also achieved. The analogous Rh(tfa)(PPh^)3
catalyst system, Rh(tfa)\SG, produces a greater selectivity (81.4%), but
also results in considerably lower activity (1.93 x 10'^ moles/min)
under identical conditions. This is shown graphically in figure 4-8.
The extremely high selectivity achieved in using polymer membranes
(as shown in chapter 3) indicates that the polymer environment plays a
large role in affecting the reaction properties. To test this theory,
use of a similar environments in the flow reactor was tested. Reactions
were ran at a temperature of 80°C using the previously determined
optimum reaction conditions. The only reaction condition which

Activity x 106 (moles/min)
Figure 4-8.
n-Butanal activity for RhH\SG and Rh(tfa)\SG.

108
deviated from the optimum conditions was flow rate. In reactions where
the catalyst activities were observed to be very low under moderate flow
rates, the reactions were reran over longer periods of time using slower
flow rates.
RhH(CO)(PPh^)3 on macroporous polystyrene, RhH\MPPS, was
investigated. The results achieved are dramatic. The activity of the
system is extremely small (0.33 x 10"® for the production of n-butanal),
however the selectivity observed is greater than 90%. Attempts to
disperse RhH(CO)(PPh^)3 on ground-up poly(butyl methacrylate) results in
the formation of a yellow solid which cannot be isolated for reaction
purposes. Another polymer support investigated is Nation.1^,19 use 0f
this catalyst based system results in very little activity with high
selectivity. The production of n-butanal occurs with an activity of
0.19 x 10"® moles/min and >90% selectivity. Data for these systems are
contained in table 4-6.
The reduced activity of the polymer supported systems is not
unexpected. The filling of the reactor tube with a silica gel based
catalyst results in a more densely packed volume. This results in
increased substrate/catalyst interaction. Filling the reactor tube with
the polymer based catalyst results in a more loosely packed volume in
which pores and channels exist. This leads to decreased interaction
between catalyst and substrate and decreased activity. The increased
selectivity is noteworthy. It supports the theory that the polymer
environment in both membrane and gas flow reactions alter the reaction
properties. One property which the polymer may contribute is

109
Table 4-6.
Catalyst comparison at 80°C.
Activity xl06a
Total
n-Butanal
Catalyst (moles/min)
Isobutanal
(moles/min)
Selectivity
(%)
Conversion
(%)
RhH\SG
15.9
4.07
79.6
1.54
RhH\SG\PC
3.08
0.05
98.4
0.79
Rh(tfa)\SG
1.93
0.44
81.4
0.42
Rh(tfa)\SG\PC
0.02
0.00
0.01
RhH\MPPS
0.33
0.00
>90
0.16
RhH\MPPS\PC
0.35
0.00
>90
0.22
RhH\Nafion
0.19
0.00
>90
0.05
a Reactor
conditions:
0.50g catalyst.
Pressure is
13 psi using
(1:1:1) H2> CO, CHjCFhCH^ gas mixture. Temperature is 80°C. Flow
rate for various reaction times is RhH\SG is 26.0 mL/min (25
min.) RhH\SG\PC is 8.0 mL/min (35 min.), Rh(tfa)\SG is 11.5 mL/min
(30 min.), Rh(tfa)SG\PC is 4.5 mL/min (20 min.), RhH\MPPS is
4.0 mL/min (30 min.), RhH\MPPS\PC is 3.4 mL/min (25 min.),
RhH\Nafion is 7.3 mL/min (25 min.).

110
in its ability to act as a "sponge" in the reaction by soaking up the
gaseous substrates and allowing reaction to occur.
This theory is further tested by attempting to mimic the polymer
systems by coating the RhH\SG catalyst with an 8.0% loading of propylene
carbonate. Propylene carbonate is a very polar solvent which has a
large dielectric constant, E = 69, and a high boiling point, 242°C. It
is nonvolatile under normal reaction conditions and no solvent
evaporation is observed. The resulting propylene carbonate coated
catalyst, RhH\SG\PC, results in reduced activity for n-butanal
production ( 3.08 x 10’® moles/min). The selectivity of the reaction,
however, is observed to increase dramatically to 98.4%. This
experimental result verifies the pronounced influence of the environment
on this reaction.
Based upon this knowledge, Rh(tfa)\SG\PC was investigated. Using
the previous reaction conditions, a reduced n-butanal activity
(0.02 x 10"6 moles/min) is obtained. The selectivity again is increased
but cannot be determined accurately. The formation of isobutanal is
observed in such a small quantity that an accurate determination of the
number of moles produced is not possible. Use of RhH\MPPS\PC yields
similar results. Data from these reactions are listed in table 4-6.
The "sponge effect" which may be affecting reaction in the
propylene carbonate added systems has also been investigated. This
concept is tested by changing the reaction temperature. A higher
reaction temperature, 100°C, has been shown to produce a decrease in the
activity of the systems without the solvent coating. RhH\SG produces an
activity of 7.01 x 10’® moles/min in the formation of n-butanal and a

Ill
selectivity of 73.9%. In comparison, at 80°C the same system produces a
n-butanal activity of 15.9 x 10"® moles/min with a selectivity of 79.6%.
Presumably, this occurs due to a minimized contact time between catalyst
and substrates. The use of propylene carbonate may provide increased
contact time between the catalyst and substrate by acting as a sponge.
The use of RhH\MPPS\PC at 100°C results in increased activity
(0.79 x 10"® moles/min) relative to its analogous 80°C experiment
(0.33 x 10"® moles/min) without propylene carbonate. Accompanying the
increased activity is increased selectivity. No isobutyraldehyde is
observed in the system. If it is present, there is too little of an
amount to detect. The most dramatic results are achieved in the
RhH\SG\PC. Again for reference purposes, RhH\SG has an activity of
C
7.01 x 10" moles/min in the formation of n-butanal and a selectivity of
73.9%. RhH\SG\PC produces an incredible increase in activity and
selectivity. The production of n-butanal is obtained with an activity
C.
of 36.4 x 10 moles/min and a remarkable 95.7% selectivity. Data are
summarized in table 4-7 and presented graphically in figure 4-9. The
activity generated in this system produces about 45 turnovers of n-
butanal in one hour with a space velocity of 1370 hr"*. Equally as
important is the observation that greater than 4% of the propylene is
converted to n-butanal. This is achieved in one pass through the
reactor tube. On a commercial scale, the reaction engineering could be
altered to produce much higher conversions.
In conclusion, it has been demonstrated that the production of
n-butanal and isobutanal can be achieved in a gas flow reactor using
supported rhodium catalysts. It has also been shown that increased

112
Table 4-7. Catalyst comparison at 100°C.
Catalvst
Activity
n-Butanal
(moles/min)
xl06a
Isobutanal
(moles/min)
Selectivity
(%)
Total
Conversion
(%)
Rh(tfa)\SG
1.39
0.47
74.8
0.39
RhH\MPPS\PC
0.79
0.00
>90
0.17
RhH\SG
7.01
2.48
73.9
1.35
RhH\SG\PC
36.4
1.64
95.7
4.1
a Reactor conditions: 0.50g catalyst. Pressure is 13 psi using a
(1:1:1) H2, CO, and CH2CH=CH2 gas mixture. Temperature is lOO^C.
Flow rate for various reaction times is Rh(tfa)\SG is 9.4 mL/min
(30 min.), RhH\MPPS\PC is 9.5 mL/min (25 min.), RhH\SG is
11.0 mL/min (15 min.), RhH\SG\PC is 18.0 mL/min (60 min.).

Activity x 10 (moles/min
113
Figure 4-9.
Butanal activity as a function of time in the Q
hydroformylation of propylene with RhH\SG\PC at 100 C.

114
selectivity occurs with polymer supported catalysts relative to silica
gel supported catalysts. The use of a nonvolatile polar solvent for
coating purposes results in a substantially increased selectivity and
provides substrate saturation of the catalyst environment. This results
in increased activity even using the less favorable conditions (higher
temperatures) of the uncoated systems. This verifies the pronounced
influence that the polymer has in the previously demonstrated membrane
reactions (chapter 3).

CHAPTER V
SUMMARY
This research focuses on combining transition metal reaction
chemistry and membrane technology. Specifically, this work involves
three regions of this hybrid area. The first is concerned with the
ability of a transition metal complex to affect the permeation
properties of a polymer membrane. Investigation into this area has
resulted in the development of a procedure for accomplishing facilitated
transport of oxygen. The permeability coefficient for nitrogen in the
sample membrane is used as an internal standard and is used to determine
the quantity of oxygen which permeates via a facilitated transport
mechanism. This study has demonstrated that supported cobalt complexes
incorporated into a polystyrene membrane enhance the permeation of
oxygen.
The second area of research investigates the use of a polymer
environment as the medium for chemical reaction. The concept of
membranes utilized for reaction purposes continues to be of industrial
significance. This stems from their ability to serve a dual purpose by
achieving reaction and then functioning as a separation unit. The
feasibility of this process is realized by the facilitation of both
hydroformylation and oxidation reactions in polystyrene, poly(butyl
methacrylate), and silicone gum rubber media. Versatility of membrane
reactors is evidenced by alkyl sulfide oxidations and hydrogen peroxide
115

116
formation in similar polymer membranes. The selectivity obtained in the
hydroformylation of propylene to n-butanal is encouraging. The activity
of these systems is low, but improved engineering in conjunction with
optimization of reaction conditions should provide increased activity.
Lastly, the extension of membrane reactors to a continuous flow,
gas phase hydroformylation reaction process has been achieved with
remarkable success. This process utilizes the membrane reactor concept
by coating the catalyst system with viscous materials or films. The use
of a heterogeneous catalyst based system yields substantially increased
activity while maintaining the high degree of selectivity associated
with polymer membrane reactors. This is accomplished with solid
supported rhodium catalysts which are coated with a viscous material,
propylene carbonate. These catalysts are capable of producing linear
aldehyde selectivities of greater than twenty-two to one. Use of these
catalyst systems produces forty-five turnovers in one hour. Development
of this process is continuing to be investigated for improved reaction
properties.

APPENDIX A
COMPUTER PROGRAM FOR OXYGEN ENRICHMENT ANALYSIS
The following program was co-written with Ngai Wong. It allows
for the determination of both oxygen and nitrogen permeability
coefficients using either inputed partial pressures or measured total
pressure and oxygen percentages. The program will calculate the
separation factor of a membrane as well as determine the enrichment from
the membrane that occurs by a facilitated transport mechanism.
117

118
OEF FNUCASES(X$)
LENGTH=LEN(X|)
IF LENGTH=0 THEN FNUCASE|=””:EXIT DEF
FOR 1=1 TO LENGTH
CH=ASC(MID$(X$ .1.1))
IF CH>96 ANO CH<127 THEN
MID$(X$,I,1)=CHR$(CH-32)
END IF
NEXT I
FNUCASE$=X$
END DEF
DEF FNNUM$(X)
X$ = STR$(X)
LENGTH = L EN(X$)
IF LEFTS(X$,1) <> THEN LENGTH = LENGTH - 1
FNNUMS = RIGHT$(X$.LENGTH)
END DEF
DEFINT I
DIM SHARED RT(15),02A(15),PB(15),02BD(15),FLUX(15),P02(15),PN2(15)
DIM SHARED LNP02(15),LNPN2(15),02S(15),02R(15),LP02B(15),POB(15)
DIM SHARED ENR(15),XIN(3,15),YIN(3,15),IX(3,15),IY(3.15),RES(3,15)
DIM SHARED ILO(3).IHI(3),NP(3)
10 PRINT " IS THE 02 ENRICHMENT DATA IN A DATA FILE? Y/N "
999 ANS$=FNUCASE$(INKEYS)
IF ANS$="" GOTO 999
IF ANS$="N" GOTO 20
IF ANS$="Y” GOTO 30
GOTO 10
20 PR I NT:PR I NT "Is your data in partial pressures? Y/N"
998 ANSI = FNUCASEK INKEYS)
IF ANS$="" GOTO 998
IF ANSI = "Y" GOTO 25
IF ANSI <> "N" GOTO 20
INPUT " HOW MANY DATA POINTS? MAX=15 ";N:PRINT
PRINT " FOR RETENTION TIME = 0, ENTER 0 FOR 02S AND 1 FOR PB”:PRINT
PRINT " ENTER RUN TIME, RT; 02 IN AIR, 02A; 02 AFTER SEP., 02S"
PRINT " PRESS IN BOT CHAMBER, PB":PRINT
FOR I = 1 TO N
PRINT " RT, 02A, 02S, AND PB FOR POINT "I
INPUT RT(I),02A{I),02S(I),PB(I)
NEXT I
40 PRINT " DATA ENTERED IS RT, 02A, 02S, AND PB FOR "N" POINTS"
50 PRINT
FOR I = 1 TO N
PRINT I")",RT(I),02A(I),02S(I),PB(I)
NEXT I
60 PRINT " A - ADD A POINT”
PRINT " C - CHANGE A POINT"
PRINT " D - DELETE A POINT"
PRINT " N - DO NOTHING"
997 ANS|=FNUCASE|(INKEYI)
IF ANS|="" GOTO 997
IF ANS|="N" GOTO 70
IF ANS|="A" GOTO 80
IF ANS|="C" GOTO 90
IF ANS|="D" GOTO 100
GOTO 60
80 IF N<15 GOTO 110
PRINT " MAX NUMBER OF POINTS EXCEEDED! GOTO 50
110 N=N+1
PRINT " ENTER RT, 02A.02S, AND PB FOR NEW POINT"
INPUT RT(N),02A(N),02S(N),PB(N)
GOTO 50
90 INPUT " WHAT POINT DO YOU WISH TO CHANGE";J
IF J>N GOTO 50
IF J<1 GOTO 50
PRINT " WHAT ARE THE NEW VALUES OF RT, 02A, 02S, PB FOR POINT "J
INPUT RT(J),02A(J),02S(J),PB(J)
GOTO 50

119
100 INPUT " WHAT POINT DO YOU WISH TO DELETE”;J
IF J>N GOTO 50
IF J<1 GOTO 50
N=N-1
FOR I = J TO N
RT(I)=RT(1+1):02A(I)=02A(I+1):02S(I)=02S(I+1):PB(I)=PB(I+1):NEXT I
GOTO 50
25 INPUT " HOW MANY DATA POINTS? MAX=15 N:PRINT
PRINT " FOR RETENTION TIME = 0, ENTER 0 FOR P02 AND PN2":PRINT
PRINT " ENTER RUN TIME, RT; 02 IN AIR, 02A; PART. PRESS. OF 02, P02;"
PRINT " PARTIAL PRESSURE OF N2, PN2":PRINT
FORMS = "PARTIAL"
FOR I = 1 TO N
PRINT " RT, 02A, P02, AND PN2 FOR POINT "I
INPUT RT(I),02A(I),P02(I),PN2(I)
NEXT I
41 PRINT " DATA ENTERED IS RT, 02A, P02, AND PN2 FOR "N" POINTS"
51 PRINT
FOR I = 1 TO N
PRINT I")",RT(I),02A(I),P02(I),PN2(I)
NEXT I
61 PRINT " A - ADD A POINT"
PRINT " C - CHANGE A POINT"
PRINT " D - DELETE A POINT"
PRINT " N - DO NOTHING"
996 ANS$=FNUCASE$(INKEYS)
IF ANSS="" GOTO 996
IF ANS$="N" GOTO 70
IF ANSS="A" GOTO 81
IF ANSS="C" GOTO 91
IF ANSS="D" GOTO 101
GOTO 61
81 IF N<15 GOTO 111
PRINT " MAX NUMBER OF POINTS EXCEEDED! GOTO 51
111 N=N+1
PRINT " ENTER RT, 02A, P02, AND PN2 FOR NEW POINT"
INPUT RT(N),02A(N),P02(N),PN2(N)
GOTO 51
91 INPUT " WHAT POINT DO YOU WISH TO CHANGE";J
IF J>N GOTO 51
IF J<1 GOTO 51
PRINT " WHAT ARE THE NEW VALUES OF RT, 02A, P02, PN2 FOR POINT "J
INPUT RT(J),02A(J),P02(J),PN2(J)
GOTO 51
101 INPUT " WHAT POINT DO YOU WISH TO DELETE";J
IF J>N GOTO 51
IF J<1 GOTO 51
N=N-1
FOR I = J TO N
RT(I)=RT(1+1):02A(I)=02A(1+1):P02(I)=P02(1+1):PN2(I)=PN2(1+1):NEXT I
GOTO 51
70 GOSUB 300
FOR I = 1 TO N
IF RT(I)=0 THEN P02(I) = 0.22
IF RT(I)=0 THEN PN2(I) = 0.78
IF FORMS = "PARTIAL" GOTO 121
IF RT(I)=0 THEN 02BD(I)=02A(I)
IF RT(I)=0 GOTO 120
02BD(I)= (760*02S(I)-(760-PB(I))*02A(I))/PB(I)
120 02R(I)=02BD(I)-02A(I)
IF RT(I)=0 THEN FLUX(I)=0 ELSE FLUX(I)=PB(I)/RT(I)
P02(I)=02BD(I)*PB(I)/100
PN2(I)=PB(I)-P02(I)
121 LNP02(I)=LOG(((760’02A(I))/100)-P02 (I))
LNPN2(I)=LOG(((760*(100-02A(I)))/100)-PN2(I))
NEXT I
IF FORMS = "PARTIAL" GOTO 145
PRINT " CALCULATED DATA - 02BD = 02 BEFORE DILUTION"
PRINT " 02R = 02 ENRICHMENT"

PRINT " FLUX = 02 FLUX"
PRINT " P02 = PARTIAL PRESSURE OF 02"
PRINT " PN2 = PARTIAL PRESSURE OF N2"
PRINT " HIT ANY KEY TO CONTINUE "
995 AA$=INKEYS
IF AA$="" GOTO 995
CLS:PRINT " CALCULATED DATA AS FOLLOWS RT, 02BD, 02R, AND FLUX":PRINT
FOR 1=1 TO N
PRINT I")",RT(I),02BD(I),02R(I),FLUX(I)
NEXT I
PRINT "HIT ANY KEY TO CONTINUE"
994 ANS$=INKEYS
IF ANS$="" GOTO 994
PRINT " DO YOU WANT A HARDCOPY OF THIS? Y/N"
880 ANS$=FNUCASE$(INKEYS)
IF ANS$ = "" GOTO 880
IF ANSS <> "Y" GOTO 140
OPEN "LPT1:" FOR OUTPUT AS #1
PRINT #1, " CALCULATED DATA AS FOLLOWS RT, 02BD, 02R, AND FLUX":PRINT #1,
FOR I = 1 TO N
PRINT #1, I")",RT(I),02BD(I),02R(I),FLUX(I)
NEXT I
PRINT #1,”"
CLOSE #1
CLS:GOTO 140
130 PRINT
140 PRINT " CALCULATED DATA AS FOLLOWS RT, PB, P02, AND PN2":PRINT
FOR I = 1 TO N
PRINT I")",RT(I),PB(I),P02(I),PN2(I)
NEXT I
PRINT:PRINT "HIT ANY KEY TO CONTINUE”
993 ANS$=INKEYS
IF ANSS=”" GOTO 993
PRINT "DO YOU WANT A HARDCOPY OF THIS? Y/N"
879 ANSS=FNUCASES(INKEYS)
IF ANS$='"' GOTO 879
IF ANS$<>”Y" GOTO 145
OPEN "LPT1:" FOR OUTPUT AS #1
PRINT #1," CALCULATED DATA AS FOLLOWS RT, PB, P02. AND PN2":PRINT #1,""
FOR I = 1 TO N
PRINT #1,I")",RT(I),PB(I),P02(I),PN2(I)
NEXT I
PRINT #1,""
CLOSE #1
145 FOR I = 1 TO N
XIN(1,1) = RT (I)
NEXT I
NSET = 1
FOR I = 1 TO 2
FOR J = 1 TO N
IF I = 1 THEN YIN(1,J) = LNP02(J) ELSE YIN(1,J) = LNPN2(J)
NEXT J
CALL LEAST(N,M,B,SDM,SDB.RES.RESVAR.SE,NSET)
IF I = 1 THEN 02S10P=M ELSE N2SL0P=M
IF I = 1 THEN BINTC = B
IF I = 2 GOTO 165
PR I NT:PR I NT "Slope of Ln 02 vs reaction time is "02SL0P
GOTO 166
165 PR I NT:PR I NT "Slope of Ln N2 vs reaction time is "N2SL0P
166 PRINT "Intercept for this plot is "B
PRINT "Standard deviation of slope is "SDM
PRINT "Standard deviation of intercept is "SDB
PRINT "Residual variance is "RESVAR
PRINT "Standard estimated error is "SE
PRINT:PRINT
992 ANS$=INKEYS
IF ANS$="” GOTO 992
PRINT "DO YOU WANT A HARDCOPY OF THIS? Y/N"
878 ANS$=FNUCASE$(INKEYJ)

121
IF ANS$="" GOTO 878
IF ANS$<> "Y" GOTO 877
OPEN "LPT1:" FOR OUTPUT AS #1
IF I = 2 GOTO 876
PRINT #1,"Slope of Ln 02 vs reaction time is "O2SL0P
GOTO 875
876 PRINT #1,"Slope of Ln N2 vs reaction time is "N2SL0P
875 PRINT #1,"Intercept for this plot is "B
PRINT #1,"Standard deviation of slope is "SOM
PRINT #1,"Standard deviation of intercept is "SOB
PRINT #1,"Residual variance is "RESVAR
PRINT #1,"Standard estimated error is ”SE
PRINT #1,""
CLOSE #1
877 PR I NT:PR I NT "The following plot routinues will use points."
PRINT "Please specify symbols for points."
991 ANS$=INKEY$
IF ANS$="" GOTO 991
CALL SETUP (TITLES,XLA$,YLA$, MAJX .MINX, YMAJ, YMIN, POI N$)
CALL CONVERTÍPXL,PXH,PYL,PYH,NSET,N)
CLS
CALL GMODE
CALL CLRSCR
CALL LAB(TITLE$,XLA$,YLA$)
CALL AXIS(MAJX,MINX.YMAJ,YMIN)
CALL STRAIGHT(PXL,PXH,M,B,PYL,PYH)
CALL DOT(POIN$,NSET,N)
CALL SCALE(PXL.PXH,MAJX,PYL,PYH,YMAJ)
990 ANS$=INKEY$
IF ANS$="" GOTO 990
CALL TMODE
NEXT I
170 PRINT " DO YOU WISH TO CALCULATE ALPHA? Y/N "
989 ANS$=FNUCASE$(INKEYS)
IF ANS$="" GOTO 989
IF ANS$="N" GOTO 180
IF ANS$="Y" GOTO 190
GOTO 170
190 INPUT " WHAT IS THE FILM THICKNESS"; THIC
INPUT " WHAT IS THE FILM AREA"; AREA
INPUT " WHAT IS THE TEMPERATURE";TEMP
INPUT " WHAT IS THE CELL VOLUME”;VOL
GOTO 200
210 PC02=-02SL0P*22414*V0L*THIC/(TEMP*AREA*3600*6.24E5)
PCN2=-N2SL0P*22414*V0L*THIC/(TEMP*AREA*3600*6.24E5)
ALPHA=PC02/PCN2
CLS; PRINT ” THE FILM THICKNESS IS "THIC
PRINT " THE FILM AREA IS "AREA
PRINT " THE TEMPERATURE IS "TEMP
PRINT " THE CELL VOLUME IS "VOL
PRINT:PRINT " THE PERMEABILITY COEFF FOR 02 IS "PC02
PRINT " THE PERMEABILITY COEFF FOR N2 IS "PCN2
PRINT " THE SEPERATION FACTOR IS "ALPHA
PRINT:PRINT:PRINT:PRINT " HIT ANY KEY TO CONTINUE "
988 AA$=INKEY$
IF AA$="" GOTO 988
PRINT "00 YOU WANT A HARDCOPY OF THIS? Y/N"
874 ANS$=FNUCASE$(INKEY$)
IF ANS$="" GOTO 874
IF ANS$<>"Y" GOTO 180
OPEN "LPT1:" FOR OUTPUT AS #1
PRINT #1," THE FILM THICKNESS IS "THIC
PRINT #1, " THE FILM AREA IS "AREA
PRINT #1," THE TEMPERATURE IS "TEMP
PRINT #1,""-.PRINT #1," THE PERMEABILITY CEFF FOR 02 IS "PC02
PRINT #1," THE PERMEABILITY COEFF FOR N2 IS "PCN2
PRINT #1," THE SEPARATION FACTOR IS "ALPHA
PRINT #1,””
CLOSE #1

122
GOTO 180
200 PRINT:PRINT " THE FILM THICKNESS IS "THIC
PRINT " THE FILM AREA IS "AREA
PRINT " THE TEMPERATURE IS "TEMP
PRINT " THE CELL VOLUME IS "VOL
220 PRINT:PRINT " DO YOU WANT TO CHANGE ANYTHING? Y/N "
987 ANSS=FNUCASE$(INKEYS)
IF ANS$="" GOTO 987
IF ANS$="N" GOTO 210
IF ANS$="Y" GOTO 230
GOTO 220
230 PRINT " WHAT WOULD YOU LIKE TO CHANGE? L, A, T, OR V "
986 ANS$=FNUCASE$(INKEYS)
IF ANS$="" GOTO 986
IF ANS$="L" GOTO 240
IF ANS$="A" GOTO 250
IF ANS$="T" GOTO 260
IF ANS$="V" GOTO 270
GOTO 200
240 INPUT " WHAT IS THE FILM THICKNESS";THIC
GOTO 200
250 INPUT " WHAT IS THE FILM AREA";AREA
GOTO 200
260 INPUT " WHAT IS THE TEMPERATURE";TEMP
GOTO 200
270 INPUT " WHAT IS THE CELL VOLUME";VOL
GOTO 200
290 END
180 PRINT:PR I NT " DO YOU WANT TO RUN THIS DATA AGAIN? Y/N "
985 ANS$=FNUCASE$(INKEYS)
IF ANSS="" GOTO 985
IF ANSS="N" GOTO 330
IF ANSS="Y" GOTO 40
GOTO 180
30 PRINT:INPUT " WHAT IS THE FILENAME OF THE DATA? (FILENAME.EXT) ";A$
OPEN AS FOR INPUT AS #5
INPUT #5, N
INPUT #5, FORMS
FOR I = 1 TO N
IF FORMS <> "PARTIAL" THEN INPUT #5.RT(I),02A(I),02S(I),PB(I)
IF FORMS = "PARTIAL" THEN INPUT #5,RT(I),02A(I),P02(I),PN2(I)
NEXT I
CLOSE #5
IF FORMS = "PARTIAL" THEN GOTO 41 ELSE GOTO 40
300 PRINT:PR I NT " DO YOU WISH TO SAVE THIS DATA? Y/N "
984 ANS$=FNUCASE$(INKEYS)
IF ANSS="" GOTO 984
IF ANSS="N" GOTO 310
IF ANSS="Y" GOTO 320
GOTO 300
320 PRINT:INPUT ” FILENAME YOU WISH TO SAVE DATA UNDER (FILENAME.EXT)";AS
OPEN AS FOR OUTPUT AS #4
PRINT #4, N
PRINT #4, FORMS
FOR I = 1 TO N
IF FORMS <> "PARTIAL" THEN PRINT #4,RT(I),02A(I),02S( I),PB( I)
IF FORMS = "PARTIAL” THEN PRINT #4,RT(I),02A(I),P02(I),PN2(I)
NEXT I
CLOSE #4
PRINT:PRINT " DATA HAS BEEN SAVED IN FILE : "AS:PRINT
310 RETURN
330 PR I NT:PRI NT "Do you want to calculate the reference data? Y/N"
983 ANSS = FNUCASES(INKEYS)
IF ANS$="" GOTO 983
IF ANSS = "N" GOTO 301
IF ANSS <> "Y" GOTO 330
PRINT:INPUT "What value of reference ALPHA do you want";ALPHA2
PC02B = ALPHA2 * PCN2
BSLOP = -1 * PC02B * TEMP * AREA * 10022.4 / (VOL * THIC / 10)

123
FOR I = 1 TO N
LP02B(I) = BSLOP * RT(I) + BINTC
POB(I) = 02A(I) * 7.60 - EXP(LP02B(I))
IF RT(I)=0 THEN POB(I)=.22
ENR(I) = P02(I) - POB(I)
NEXT I
PRINT:PR I NT "Permeability of 02 blank is "PC02B
PRINT "Blank slope is "BSLOP
PRINT:PRINT "Run time P02 POB Enrich":PRINT
FOR I = 1 TO N
PRINT RT(I),P02(I),POB(I),ENR(I)
NEXT I
PR I NT:PR I NT "Hit any key to continue."
982 ANSS = INKEYS
IF ANS$="” GOTO 982
PRINT "DO YOU WANT A HARDCOPY OF THIS? Y/N"
873 ANS$=FNUCASE$(INKEY$)
IF ANS$=”" GOTO 873
IF ANS$<>"Y" GOTO 872
OPEN "LPT1:" FOR OUTPUT AS #1
PRINT #1," Permeability of 02 blank is "PC02B
PRINT #1," Blank sloe is "BSLOP
PRINT #1,"":PRINT #l,"Run time P02 POB Enrich":PRINT #1,""
FOR I -1 TO N
PRINT #1.RT(I),P02(I),POB(I),ENR(I)
NEXT I
PRINT #1.""
CLOSE #1
872 PRINT:PRINT "Run time Ln P02B":PRINT
FOR I = 1 TO N
PRINT RT(I),LP02B{I)
NEXT I
PR I NT:PR I NT "Hit any key to continue."
981 ANS$ = INKEYJ
IF ANS$="" GOTO 981
PRINT "DO YOU WANT A HARDCOPY OF THIS? Y/N"
871 ANS$=FNUCASES(INKEYS)
IF ANS$="" GOTO 871
IF ANSS<>"Y" GOTO 340
OPEN "LPT1:" FOR OUTPUT AS #1
PRINT #1," Run time Ln P02B":PRINT #1,""
FOR I = 1 TO n
PRINT #1, RT(I).LP02B(I)
NEXT I
PRINT #1,""
CLOSE #1
340 PR I NT:PR I NT "Do you want to see a plot? Y/N"
980 ANSS = FNUCASE$(INKEYS)
IF ANSS="" GOTO 980
IF ANSS = "N" GOTO 301
IF ANSS <> "Y" GOTO 340
FOR I = 1 TO N
XIN(l.I) = RT(I)
YIN(1,1) = P02(I)
XIN(2,1) = RT(I)
YIN(2,1) = POB(I)
NEXT I
NSET = 2
PR I NT:PR I NT "The following plot routinues will use points."
PRINT "Please specify symbols for points."
979 ANS$=INKEY$
IF ANSS="" GOTO 979
CALL SETUP (TITLES,XLAS,YLAS,MAJX,MI NX,YMAJ.YMIN.P0IN$)
CALL CONVERTÍPXL,PXH,PYL,PYH,NSET,N)
CLS
CALL GMODE
CALL CLRSCR
CALL AXIS(MAJX.MINX,YMAJ,YMIN)
CALL DOT(POIN$,NSET,N)

124
CALL SCALE(PXL,PXH,MAJX,PYL,PYH,YMAJ)
CALL LAB(TITLE$,XLA$,YLA$)
978 ANS$=INKEY$
IF ANS$="" GOTO 978
CALL TMODE
301 PR I NT:PR I NT "Do you want to quit? Y/N"
977 ANS$=FNUCASE$(INKEYJ)
IF ANS$="” GOTO 977
IF ANS$="Y" GOTO 290
IF ANS$="N" GOTO 10
GOTO 301
REM
REM SUBPROGRAM FOR LEAST SQUARE FITS
REM
SUB LEAST(N,M,B.SDM,SDB.RES,RESVAR,SE,NSET) STATIC
SX=0
SY=0
SXY=0
SXQ=0
SYQ=0
UZ=0
SUQ=0
SRES2=0
SZQ=0
FOR 1=1 TO N
SX=SX+XIN(NSET, I)
SY=SY+YIN(NSET,I)
SXQ=SXQ+XIN(NSET,I)*XIN(NSET,I)
SYQ=SYQ+YIN(NSET,I)*YIN(NSET,I)
SXY=SXY+XIN(NSET,I)*YIN(NSET,I)
NEXT I
D=N*(SXQ)-(SX*SX)
M={(N*SXY)-(SX*SY))/D
B=((SXQ*SY)-(SX*SXY))/D
REM COMPUTE CORRELATION COEFFICIENT, C
XA=SX/N
YA=SY/N
FOR 1=1 TO N
U=XIN(NSET,I)-XA
Z=YIN(NSET,I)-YA
uz=uz+u*z
SUQ=SUQ+U*U
SZQ=SZQ+Z*Z
NEXT I
E=SUQ*SZQ
F=SQR(E)
C=UZ/F
REM COMPUTE STD. DEV. FOR SLOPE (SDM) AND FOR INTERCEPT (SDB)
VARY=(SZQ-(M*M*SUQ))/(N-2)
VARB=(VARY*SXQ)/(N*SUQ)
VARM=VARY/SUQ
SDB=SQR(ABS(VARB))
SDM=SQR(ABS(VARM))
REM FIND RESIDUALS [Y-YCALC] AND SUM SQUARES
FOR 1=1 TO N
RES(NSET,I)=YIN(NSET,I)-M*XIN(NSET, I )+B
SRES2=SRES2+RES(NSET, I)*RES(NSET, I)
NEXT I
REM CALCULATE RESIDUAL VARIANCE AND STANDARD ERROR OF ESTIMATE
IF N= 2 THEN RESVAR = 1 ELSE RESVAR=SRES2/(N-2)
SE=SQR(RESVAR)
END SUB
REM
REM SUBPROGRAM SETUP IS USED TO INPUT LABELS, TICK MARKS, AND POINT SYMBOLS
REM
SUB SETUP(TITLES,XLA$,YLA$,TXL,TXS,TYL,TYS,POIN$) STATIC
INPUT "What title would you like";TITLE$
INPUT "What label would you like on the X axis";XLA$
INPUT "What label would you like on the Y axis";YLA$

is 25 characters.
11 LONG = LEN(YLA$)
IF LONG < 25 GOTO 15
PR I NT:PR I NT "Label for Y axis is too long. Max. length
PR INT:PR I NT "Enter new label for Y axis."
INPUT YLA$
GOTO 11
15 TXL = 10
TXS = 10
TYL = 10
TYS = 10
PR I NT:PR I NT "Default number of major ticks on X axis is "TXL
PRINT "Default number of minor ticks on X axis is "TXS
PR I NT:PR I NT "Default number of major ticks on Y axis is "TYL
PRINT "Default number of minor ticks on Y axis is "TYS
PR I NT:PR INT "Major ticks are labeled on the axis and minors ticks are not
PRINT "Major ticks min. is 3 and max. is 10."
PRINT "Minor ticks min. is 0 and max. is 10."
26 PR I NT:PR I NT "Do you wish to change these values? Y/N"
976 ANS$=FNUCASE$(INKEYS)
IF ANS$='"’ GOTO 976
IF ANS$ = "N" GOTO 42
IF ANS$ <> "Y" GOTO 26
19
PRINT:
INPUT
"How many major
ticks
on
the
X
axis";TXL
IF TXL
> 10
OR TXL < 3 GOTO
19
21
PRINT:
INPUT
"How many minor
ticks
on
the
X
axis";TXS
IF TXS
> 10
GOTO 21
IF TXS
< 0 THEN TXS = 0
22
PRINT:
INPUT
"How many major
ticks
on
the
Y
axis";TYL
IF TYL
> 10
OR TYL < 3 GOTO
22
23
PRINT:
INPUT
"How many minor
ticks
on
the
Y
axis";TYS
IF TYS
> 10
GOTO 23
IF TYS < 0 THEN TYS = 0
42 PR I NT:PR I NT "The plot routinues are setup to handle three sets of
data”
PRINT "The default symbol for plotting points will be circles."
PRINT "You may choose any symbol from the keyboard to represent"
PRINT "your point in the plot."
PR I NT:PR I NT "Do you want to choose your own symbols? Y/N"
975 ANSÍ = FNUCASEÍ(INKEYÍ)
IF ANSÍ="" GOTO 975
P0INÍ = ”000”
IF ANSÍ = "N" GOTO 31
IF ANSÍ <> "Y" GOTO 42
FOR I = 1 TO 3
PR I NT:PR I NT "What symbol would you like for data set number "I
974 ANSÍ = INKEYÍ
IF ANSÍ="" GOTO 974
MIDÍ(P0INÍ .1.1) = ANSÍ
NEXT I
31 END SUB
REM
REM SUBPROGRAM CONVERT IS FOR THE CONVERSION OF REAL X AND Y COORDINATES
REM TO SCREEN X AND Y COORDINATES WITH VARIABLE LIMITS IN WINDOW
REM
SUB CONVERTÍPXL,PXH,PYL,PYH,NLINE,N) STATIC
XLO = XIN(l.l)
XHI = XIN(l.l)
YLO = YIN(l.l)
YHI = YIN(l.N)
FOR I = 1 TO NLINE
FOR J = 1 TO N
IF XLO > XIN(I.J) THEN XLO = XIN(I.J)
IF XHI < XIN(I.J) THEN XHI = XIN(I.J)
IF YLO > YIN (I, J) THEN YLO = YIN(I.J)
IF YHI < YIN(I.J) THEN YHI = YIN(I.J)
NEXT J
NEXT I
32 PRINT:PRINT "Default X min is "XL0:PRINT "Default X max is "XHI
PRINT:PRINT "Default Y min is "YLO:PRINT "Default Y max is "YHI

126
PR I NT:PR I NT "Do you wish to plot the default
973 ANS$ = FNUCASES(INKEYS)
IF ANS$="" GOTO 973
IF ANSÍ = "Y" GOTO 27
IF ANSI <> "N" GOTO 32
PRINT:INPUT "Plot w
PRINT:INPUT "Plot w
PRINT:INPUT "Plot w
PRINT:INPUT "Plot what value of
FOR I = 1 TO NLINE
FOR J = 1 TO N
IF PXL < XIN(I.J) GOTO 62
NEXT J
62 ILO(I) = J - 1
IF ILO(I) < 1 THEN ILO(I)
FOR J = 1 TO N
value
of
X
min”
; PXL
value
of
X
max"
; PXH
value
of
Y
min"
; PYL
value
of
Y
max"
; PYH
= 1
IF PXH
NEXT J
82 IHI(I)
IF IHI
NEXT I
LO = PYL
> XIN(I,J) GOTO 82
= N + 1 - J
I) > N THEN IHI{I) = N
limits? Y/N"
HI = PYH
FOR J = 1 TO NLINE
FOR I = ILO(J) TO IHI(J)
IF LO > YIN(J.I) THEN LO = YIN(J.I)
IF HI < YIN(J,I) THEN HI = YIN(J.I)
NEXT I
NEXT J
IF PYL =< LO GOTO 102
103 PR I NT:PR I NT "Lower limit is too high, min value is "LO
INPUT "What is the new value of Y min";PYL
IF PYL > LO GOTO 103
102 IF PYH => HI GOTO 43
131 PR I NT:PR I NT "Upper limit is too low, max value is "HI
INPUT "What is the new value of Y max";PYH
IF PYH < HI GOTO 131
GOTO 43
27 PXL = XLO
PXH = XHI
PYL = YLO
PYH = YHI
FOR J = 1 TO NLINE
ILO(J) = 1
IHI(J) = N
NP(J) = N
NEXT J
43 FOR J = 1 TO NLINE
NP(J) = IHI(J) - ILO(J) + 1
FOR I = ILO(J) TO IHI(J)
II = I - ILO(J) + 1
IX(J,II) = ((XIN(J.I) - PXL) * 600/(PXH - PXL)) + 84
IY(J,II) = 315 - ((YIN(J.I) - PYL) * 300/(PYH - PYL))
NEXT I
NEXT J
END SUB
REM
REM SUBPROGRAM AXIS IS TO DRAW THE X AND Y AXIS AND THE TICK MARK
REM DIVISIONS FOR SCALE
REM
SUB AX IS(TXL,TXS.TYL,TYS) STATIC
REM
REM Draws the X and Y axis
REM
IXA = 84
IYA = 15
CALL MOVE(IXA,IYA)
IYA = 315
CALL DLINE(IXA,IYA)

127
I XA = 684
CALL DLINE(IXA,¡VA)
REM
REM Draws tic marks on the Y axis
REM
IXA = 84
IXA1 = 87
IF TYS = 0 GOTO 1001
IN = 300 / (TYS * TYL)
FOR 1=1 TO TYS * TYL
IYA = 15 + IN * (I-1)
CALL MOVE(IXA,IYA)
CALL DLINE(IXA1, IYA)
NEXT I
1001 IXA = 89
INN = 300 / TYL
FOR I = 1 TO TYL
IYA = 15 + INN * (I - 1)
CALL MOVE(IXA1,IYA)
CALL DLINE(IXA,IYA)
NEXT I
REM
REM Draws tic marks on the X axis
REM
IYA = 315
IYA1 = 312
IF TXS = 0 GOTO 1002
IN = 600 / (TXL * TXS)
FOR 1=1 TO TXL * TXS
IXA = 84 + IN * (I-1)
CALL MOVE(IXA,IYA)
CALL DLINE(IXA,IYA1)
NEXT I
1002 IYA = 310
INN = 600 / TXL
FOR 1=1 TO TXL
IXA = 84 + INN * (I-1)
CALL MOVE(IXA,IYA1)
CALL DLINE(IXA.IYA)
NEXT I
END SUB
REM
REM SUBPROGRAM LAB IS TO LABEL THE TITLE, X AXIS, AND Y AXIS
REM
SUB LAB(TITLE$,XLA$,YLABEL$) STATIC
IXA = 110
IYA = 13
CALL TEXTB(IXA,IYA,TITLES)
ILEN = LEN(YLABELS)
IXA = 24
IYA = 144 - ILEN * 5.5
ILN = 1
FOR I = 1 TO ILEN
YLAS = MID$(YLABELS,I,ILN)
IYA = IYA + 11
CALL TEXTB(IXA,IYA,YLA$)
NEXT I
ILEN = LEN(XLAS)
IYA = 340
IXA = 384 - ILEN * 4.5
CALL TEXTB(IXA,IYA,XLAS)
END SUB
REM
REM SUBPROGRAM SCALE IS TO LABEL EACH AXIS WITH THE SCALE
REM
SUB SCALE(PXL,PXH,XMAX,PYL,PYH,YMAX) STATIC
NVX = (PXH - PXL)/XMAX
NVY = (PYH - PYL)/YMAX
IN = 300 / YMAX

128
INN = 600 / XMAX
FOR 1=1 TO XMAX
Xl$ = FNNUM$(PXL + (I - 1) * NVX)
LONG = LEN(XL$)
IXA = 84 - LONG * 4.5 + INN * (I - 1)
IYA = 328
CALL TEXTBfIXA,IYA,XL$)
NEXT I
FOR I = 1 TO YMAX
XL$ = FNNUM$(PYH - (I - 1) * NVY)
LONG = LEN(XL$)
IYA = 20 + IN * (I - 1)
IXA = 83 - 9 * LONG
CALL TEXTB(IXA,IYA,XL$)
NEXT I
END SUB
REM
REM SUBPROGRAM CURVE IS USED TO DRAW A CURVE FROM THE DATA
REM
SUB CURVE(N,NL) STATIC
CALL MOVE(IX(NL,1),IY(NL, 1))
FOR I = 2 TO NP(NL)
CALL DLINE(IX(NL.I),IY(NL, I))
NEXT I
END SUB
REM
REM SUBPROGRAM STRAIGHT IS USED TO DRAW A STRAIGHT LINE FROM SLOPE
REM AND INTERCEPT CALCULATIONS
REM
SUB STRAIGHT(XMIN,XMAX,M.B.YMIN,YMAX) STATIC
Y = XMIN * M + B
ZY = 300 / (YMAX - YMIN)
ZX = 600 / (XMAX - XMIN)
IXMI = 84
IXMA = 684
IYMI = 315 - (Y - YMIN) * ZY
Y = XMAX * M + B
IYMA = 315 - (Y - YMIN) * ZY
IF IYMI > 15 GOTO 1100
IYMI = 15
X = (YMAX - B)/M
IXMI = 84 + (X - XMIN) * ZX
1100 IF IYMI < 315 GOTO 1110
IYMI = 315
X = (YMAX - B)/M
IXMI = 84 + (X - XMIN) * ZX
1110 IF IYMA > 15 GOTO 1120
IYMA = 15
X = (YMIN - B) / M
IXMA = 84 + (X - XMIN) * ZX
1120 IF IYMA < 315 GOTO 1130
IYMA = 315
X = (YMIN - B) / M
IXA = 84 + (X - MIN) * ZX
1130 CALL MOVE(IXMI,IYMI)
CALL DLINE(IXMA,IYMA)
END SUB
REM
REM SUBPROGRAM POINT IS USED TO PLOT A POINT WITH A SYMBOL
REM
SUB DOT(POIN$,NSET,N) STATIC
ILN = 2
FOR I = 1 TO NSET
PT$=MID$(POIN$,1,1)
IF PT$ = "0" GOTO 12
FOR J = 1 TO NP( I)
IPX = IX(I,J) - 4
IPY = IY(I,J) + 5
CALL TEXTB(IPX,IPY,PT$)

129
NEXT J
GOTO 29
12 FOR J = 1 TO NP(I)
CALL CIRCÍIX(I.J).IY(I.J).1LN)
NEXT J
29 NEXT I
END SUB

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BIOGRAPHICAL SKETCH
Mark J. Barnes was born in Towanda, Pennsylvania, on July 20,
1962. He graduated with honors from Towanda High School in June 1980
and attended Ithaca College in Ithaca, New York, that fall. The next
year he was elected into the Oracle Society, a freshman honor society,
and later became a member of both the honor societies of Phi Kappa Phi
and Sigma Xi, the Scientific Research Society. At Ithaca College, he
conducted research in the area of synthetic organic chemistry under the
supervision of Dr. Heinz F. Koch. He presented papers based on this
work at both the Eastern College's Science Conference and the Middle
Atlantic Regional Meeting of the American Chemical Society. He
graduated with honors from Ithaca College in May 1984.
In August 1984, he entered the University of Florida as a graduate
student and joined the research group of Dr. Russell S. Drago. While at
Florida, he presented papers at the Florida Conference on Catalysis,
Florida Advanced Materials Conference, the 1987 Middle Atlantic Regional
Meeting of the American Chemical Society, the 1987 Southeast Regional
Meeting of the American Chemical Society, and the 1987 National Meeting
of the American Chemical Society in New Orleans.
The author has published one paper in the Journal of the American
Chemical Society and is currently preparing two others for publication.
Upon receiving the degree of Doctor of Philosophy, he plans to begin his
career with Savannah River Laboratories in Aiken, South Carolina.
137

I certify that I
conforms to acceptable
adequate, in scope and
Doctor of Philosophy.
I certify that I
conforms to acceptable
adequate, in scope and
Doctor of Philosophy.
I certify that I
conforms to acceptable
adequate, in scope and
Doctor of Philosophy.
I certify that I
conforms to acceptable
adequate, in scope and
Doctor of Philosophy.
have read this study and that in my opinion it
standards of scholarly presentation and is fully
quality, as a dissertation for the degree of
Russell S. Drago
Graduate Research Professor
of Chemistry
have read this study and that in my opinion it
standards of scholarly presentation and is fully
quality, as a dissertation for the degree of
David E. Richardson
Associate Professor of
Chemistry
have read this study and that in my opinion it
standards of scholarly presentation and is fully
quality, as a dissertation for the degree of
tía'
:ingu
Emeritus
S^sler
¡shed Service
of Chemistry
Professor
have read this study and that in my opinion it
standards of scholarly presentation and is fully
quality, as a dissertation for the degree of
William M. Jones
Professor of Chemistry-

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of
adequate, in scope and quality, as
Doctor of Philosophy.
scholarly presentation and is fully
a dissertation..£ar the^tegree of
John R. Ambrose
Associate Professor of
Materials Science and
Engineering
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and
to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
August 1989
Dean, Graduate School

UNIVERSITY OF FLORIDA
3 1262 08554 2776



UNIVERSITY OF FLORIDA
3 1262 08554 2776



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