THE GRADUATE SCHOOL
University of Florida
REPORT ON THESIS OR DISSERTATION AND/OR FINAL EXAMINATION
TO THE DEAN OF THE GRADUATE SCHOOL:
Mr. Wesley Laowr Miller has submitted,
in partial fulfillment of the requirements for the degree of DOctor Of PhiloUopW
in the College of
Arts and ScincOe a thesis entitled
Preparation of Stereospecifto Polymers Through A Cyclio Polymrisation Mechanis
This thesis has been examined by all members of the candidate's special supervisory committee and has been
approved MiBO i (delete one). The committee has examined the candidate in accordance with the regulations gov-
erning the Final Examination and has adjudged his performance satisfactory u (delete one). Exceptions
or qualifications are noted as follows:
SUPER ~RY COMMITTEE: Date October 28. 1960
SG. B. Butler Ch istry
SJ. Pal .- Pau DH
[t-r ,.,l oh .- i i / ,
DIRECTIONS: Two copies of this form are signed by all members of the special supervisory committee and by the Dean
of the College or his representative, and one copy thus signed is sent to the Dean of the Graduate School.
Dr-in o.f mt frudii uat ch .,.l
PREPARATION OF STEREOSPECIFIC
POLYMERS THROUGH A CYCLIC
W. LAMAR MILLER
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
In the undertaking of a task such as the recording of information
gained over a long period of time on any given subject, it would not be
possible for the author to say how he acquired any given body of
knowledge. If such be the case, then it must be admitted that this
work is not entirely the work of an individual but rather is the work
of many people. It is only possible to record what many have taught
to an individual student.
Since it is impossible for the author to acknowledge his thanks
to all of these people, then he must be limited to those who aided
directly in the completion of this work.
The author would like to express his deep gratitude to his
research director, Dr. George B. Butler, for his patience, encouragement,
and capable direction of this work. The author is also indebted to
Drs. W. S. Brey, Jr. and I. G. Clark, III, for many enlightening
discussions and help at times when it was most needed. The author also
wishes to thank his supervisory committee for many valuable suggestions
and encouragement. To Mrs. Marie Eckart for typing the manuscript goes
a special expression of thanks.
The author is also indebted to the Chemstrand Corporation for
their support of this work by providing The Chemstrand Fellowship for
Research in High Polymers during the year 1959-1960.
TABLE OF CONTENTS
ACKNIOWLEDGMENTS . #. .
LIST OF TABLES . #. .
LIST OF ILLUSTRATIONS . . .
I. INTRODUCTION. * *
II. PREPARATION AND CHARACTERIZATION OF N,N-DIALLYLAMIDES .
A. Nomenclature o *
Materials a & .
Physical Measurements . .
Preparations * *
1. N,N-Diallylformamide *-
2. N,N-Diallylacetamide .
3. N, i-Diallyl-trifluoroaoetamide
4. N, -Diallylpropionamide *
5. N,N-Diallylheptanamide. *
6. N,N-Diallylnonanamidde *
* S r
7. N,NMDiallyl-N-trioyanovinylamine. *
III. POLYMERIZATION STUDIES ON DIALLYLAMIDES *
A. Materials a . .
B. Polymerization Procedure o *
C. Homopolymerization Attempts * *
D. Telomerization Reactions *o .* *
TABLE OF CONTENTS (continued)
1. Addition of Ethyl Bromoaeetate to
Diallylacetamide and Diallylpropionamide 19
a. Diallylacetamide .. 19
be Diallylpropionamide 20
2. Addition of Bromotrichloronrthane to
Diallylacetamide and Diallylpropionamide 20
a. Diallylaoetamide 20
b. Diallylpropionamide 20
3. Attempted Separation of Adducts 21
IV. INFRARED INVESTIGATION OF THE DIALLYLAMIDES AND
RELATED COMPOUNDS * 23
V. STUDIES ON POLY-(METHACRIIC ANHDRIDE) 29
A. Materials * 31
B. Polymerization Procedure 32
C. 1fdrolysis to Poly-(Methacrylio Anhydride) 33
1. General Method of Hydrolysis 33
2. Basic JIdrolysis * 36
3. Mild Hydrolysis a 36
D. Esterifioation of Polf-(Methacryli Acid) 37
E. X-Ra Diffraction Studies ...... 39
F. Nuclear Magnetic Resonance Studies 40
1. Preparation of NMR Samples. 44
2. Measurements e a a e 45
TABLE OF CONTENTS (continued)
G. Interpretation of Results .- 45
VI. SIMMARY ................ ... ... 51
BIBLIOGRAPHY........ .*.... 53
BIOGRAPHICAL NOTES *. ..... ..... 56
LIST OF TABLES
I. PROPERTIES OF THE COMPOUNDS PREPARED 10
II. ANALYSIS OF THE COMPOUNDS PREPARED .. 12
III. ATTEMPTED POLYMERIZATION OF DIALLYLAMIDES 17
IV. ABSORPTION FREQUENCY OF IN-PLANE-DEFORMATION VIBRATION
OF TERMINAL METHYLENE GROUP. . 26
V. RESULTS OF METHACRILIC ANHYDRIDE POLYMERIZATIONS .. 34
VI. HYDROLYSIS OF POLY-(METHACRYLIC ANHYDRIDE) TO
POLY-(METHACRLIC ACID) .. .. 35
VII. CONVERSION OF POLY-(METHACRYLIC ACID) TO
POLY-(METHEL METHAC. LATE) BY REACTION WITH
DIAZOMETHANE *. ... .. 38
VIII. FRACTIONS OF POLY-(METHYL NETHACRYLATE) IN THE THREE
STEREO CONFIGURATIONS AS DETERMINED BY N4R .. 6
LIST OF ILLUSTRATIONS
1. The probabilities of occurrence of isotactie,
Pi, heterotaotic, Ph, and syndiotactio, Po,
sequences of monomer units as a function of a,
the probability of isotactic placement of
monomer units during propagation *. 43
2. The probabilities of occurrence of isotastio,
heterotactic and syndiotaatic sequences of
monomer units as a function of a, the probability
of isotactio placement of monomer units during
propagation. The fraction of isotactio is
placed on the isotactic line to determine the
value Of a. 0 0 # a 0 0 6 0 0 47
3. Plot of log of the percentage of isotactio
fraction in the poly-(methyl methaerylate)
samples versus the temperature of polymerisation 49
Previous work in both these and other laboratories has
conclusively demonstrated that many non-conjugated diene systems may
be polymerised to linear, soluble polymers containing a recurring cyclic
unit. Reports2'3 from these laboratories have outlined a mechanism
for these systems and offered evidence to prove the presence of the
recurring cyclic units in the polymers.
The original work on this type of polymer system was the free
radical polymerisation of dially1 quaternary ammonium salts. The
intramolecular-dntermolecular chain propagation mechanism has since
been extended to cover diene systems initiated by free radical
initiators,1-10 cationic,18 and anionic16'18 initiators, and Ziegler-type
initiating systems.711,12'13'18 The monomers have been extended to
cover systems such as 1,5 and 1,7 dienes of many structural types as
well as higher a,a'-olefin systems.1,13
The main objectives in this investigation were as follows
1) To investigate monomer systems which may give evidence to explain
why these diene systems undergo the cyclic polymerization mechanism.
2) To investigate one polymerization system to determine whether any
stereo-control is exerted via this mechanism. 3) To determine what
effect the stereo-control will have on the configuration of the polymers
produced via this mechanism.
PREPARATION AND CHARACTERIZATION OF NN-DIALLYLAMIDES
Since work in these laboratories has shown that diallyldimethyl-
ammonium bromide and related quaternary ammonium salts could be
polymerized quite readily while diallylamine did not polymerise under
similar free radical conditions, it was decided to investigate the
relation between monomer structure and polymerisability.
Other workers in these laboratories synthesized and polymerized
diallylalkylphosphine oxides,6 diallyldialklphosphonium bromides, and
diallyldialkyl silanes,7 but these compounds are dissimilar from the
series under consideration in that they contain no central nitrogen atom.
With the exception of diallylformamide19 and diallylaoetamide,20
no reference is made to the diallyl amides in the literature. No data
were given in the single references to diallylformamide and diallyl-
acetamide to their preparation and properties. The preparations in
this work follow the general methods outlined by Hickinbottom.2
The inclusion of diallyltricyanovinylamine in this section
seemed reasonable since the effect of the substituents on the central
nitrogen atom followed the same course as that of the amides.
All nomenclature in this work will follow that used by
Fobmic acid and propionic anhydride were practical grade,
purchased from Matheson, Coleman and Bell; thionyl chloride, quinoline,
and heptanoic acid were purchased from Fisher Scientific Company.
Nonanoic acid was practical grade, purchased from Rohm and Haas Company;
acetic anhydride was purchased from Union Carbide Chemicals Company.
Diallylamine was provided by the Shell Chemical Company, and tetracyano-
ethylene was graciously provided by Dr VA. Engelhardt, Central
Research Department, Experimental Station, E. I. du Pont de Nemours
and Company, Incorporated. Ethyl trifluoroacetate was furnished by
W. S. Durrell, Department of Chemistry, University of Florida.
C. Physical Measurements
The crude reaction mixtures from the preparation of the amides
were fractionally distilled to give 55-65% yields of a reasonably pure
material. Prior to determination of the physical constants, the aides
were all redistilled and a narrow cut consisting of about the middle
one-third of the products taken for the determination of the physical
constants. A gas chromatographic analysis indicated the presence of
a single component in each sample used for the measurement of the
physical properties. The gas chromatographic analyses were made on
an Aerograph Gas Chromatographic Instrument using helium as the
carrier gas and a five foot Aerograph 150-A-1 column (silicone on fire
Distillation pressures were read on a Zimmerli gauge; temperatures
are 0C. and are uncorrected.
The refractive indexes were measured by means of a Bausch and
Lomb Abbe 3L refractometer fitted with an achromatic compensating prism.
Densities were determined on approximately five milliliter
samples, and all weighing were made on an analytical balance.
The heats of vaporisation were calculated from at least four
different temperatures and pressures using the Clausius-Clapeyron
equation. These should be considered as approximate values only.
The elemental analyses were performed by Galbraith Laboratories,
1. N,N-Diallylformanide, (CH2=CICH2)2
Formic acid (25 g., 0.54 mole) was added dropwise with stirring
to diallylamine (50 g., 0.52 mole) and the reaction was allowed to stir
for one hour. The mixture was then heated to remove excess reactants
and the water formed during the reaction. The temperature was maintained
at 150 for one hour and the residue distilled off at reduced pressure.
The crude product was redistilled and a careful fractionation gave a
clear, water-white liquid (48.9 g., 65.2%), b.p. 81.50 at 9.0 mu.,
88.20 at 12.4 mm., 93.00 at 15.8 m., 96.5 at 19.0 a.; n2*5 1.4693
d215 0.9326. MRD 37.395, calod. 37,413; AMH 13,200 1,000 cal. mole"
deg.-1; retention time, 4.12 minutes at 196, helium flow rate, 20 ml./min.
Anal. Calod. for C7HLNO: %C, 67.17; %S, 8.861 %5, 11.19.
Found: %C, 67.34; %H, 9.03; %N, 11.04.
2. N,qDiallylacetamide, (CH2=CHCH2)2NCCH.
Diallylamine (49 g,, 0.5 mole) was added dropwise with stirring
to acetic anhydride (51 g., 0.5 mole); the mixture was then refluxed
gently for twenty-four hours. Unreacted materials and acetic acid were
removed by distillation at atmospheric pressure, and the remaining crude
product was distilled at reduced pressures. Fractionation gave a clear,
water-white liquid (60.0 g., 85.7%), b.p. 950 at 12.7 mm., 980 at 14.6
mm., 100" at 16.3 m., 101.40 at 17.3 m., 103.2" at 19.0 ma.;
1 1.4693; d21 0.9341. 1 41.516, oalod. 42.031; AR 13,500 1,500
cal. mole-1 deg.-1; retention time, 4.96 minutes at 200, helium flow
rate, 20 ml./ain.
Anal. Called. for C8H13NO: %C, 69.03; -%, 9.41; %N, 10.07.
Found: %C, 68.85; %H, 9.64; %N, 10.21.
3. N,N-Diallyl-trifluoroacetamide, (CH2=C1H2)2NCCF
Diallylamine (50 g., 0.52 mole) was added dropwise to ethyl
trifluoroacetate (75 g., 0.53 mole). The reaction mixture was protected
by a Drierite tube and allowed to stand at room temperature for one
week. The reaction mixture was fractionally distilled to yield a clear,
water-white liquid (80.0 g., 80.5%), with a pungent, nauseating odor,
b.p. 71.30 at 15.3 mm., 76.35 at 20 mn., 81.1* at 25 am*, 84.3 at
30 m; n0.5 1.4130; d205 1.138. I 42.342, calad. 42.031;
AH 12,800 1,500 eal. ole- deg. retention time, 2.65 minutes at
1950, helium flow rate, 20 ml./min.
Anal. Called. for Cg8H1NOF : %C, 49.749 ; %i, 5.22; %N, 7.25.
Found: c., 50.01; %H, 5.21; %N, 7.03.
4. N,N-Diallylpropionamide, (CH2=CHC2)21ICCH2CH
Diallylanine (44 g., 0.045 mole) was added dropwise with stirring
to propionic anhydride (59 g., 0.45 mole) over a one hour period. The
mixture was heated to reflux and maintained at reflux for sixteen hours
with stirring. On careful fractionation, the reaction mixture yielded
a clear, water-white liquid (50.2 g., 80%), diallylpropionamide,
b.p. 1U10-11 at 20 mm. Refractionation gave b.p. 86.00 at 5.6 m.,
96.00 at 9.5 m., 102.00 at 12.6 m., 110 at 19 am.; nD 1.4685;
d24 0.9203. m 46.326, called. 46.649; AH 13,600 300 cal. ole1
deg.-1; retention time, 6.30 minutes at 2000, helium rate, 20 l. /min.
Anal. Called. for C9HJO: %C, 70.55; %H, 9.87; lN, 9.14.
Found: %c, 70.61; H, 9.89; %I, 9.32.
5. N,-DiMallylheptanamide, (C2=CH2CH2)2NCC6H13
Heptanoyl chloride (30 g., 0.20 mole), prepared by the method
outlined by Shirley22 by reaction of thionyl chloride and heptanoic
acid, was added dropwise with stirring to diallylamine (40 g., 0.41
mole) in benzene (100 ml.) over a one hour period. After addition was
complete, the reaction mixture was heated to reflux and stirred for an
additional four hours. The solid, amine hydrochloride, was removed by
filtration, washed with 30 ml. of benzene, and discarded. The filtrates
were combined; the benzene removed under reduced pressure; and the
remaining orude product fractionally distilled to yield a clear, water-
white liquid (29.3 g., 70%), diallylheptanamide, b.p. 143-144.5" at
9.6 mr. Refractionation gave b.p. 140 at 10 ma., 145 at 12.4 ma.,
1500 at 15.6 m., 154 at 18.4 m.; 22 1.4672; 210.8977; B 64.706,
+ -1 -1
called. 65.121; AH 15,300 500 cal. aole1 dog. retention time,
8.45 minutes at 200, helium flow rate, 70 ml./min.; 9.06 minutes at
2270, helium flow rate, 20 ml./min.
Anal. Calod. for C13H23 NO %C, 74.59; %N, 11.08; %N, 6.69.
Found: %C, 74.66; sH, 11.11; N, 6.72.
6. N,N-Diallylnonanamide, (CH2 CIH2)2NCC) gB7
Nonanoyl chloride (40 g., 0.28 mole), prepared by the same
method as heptanoyl chloride above, was added dropwise with stirring
to a benzene solution (100 ml.) of diallylamine (63 g., 0.65 mole) over
a one hour period. After addition was completed, the reaction mixture
was heated to reflux and stirred for an additional four hour period.
The solid diallylamine hydrochloride was filtered off, washed with
30 Al. of benzene and discarded. The two benzene portions were combined,
and the benzene was removed under reduced pressure. The remaining
crude material was fractionally distilled to yield a clear, water-white
liquid (37 g., 55.4%), diallylnonanamide, b.p. 101-102 at 0.5 mm.
Refractionation gave b.p. 137 at 7.8 mm., 144 at 10.0 am., 151*.5
at 15.1 mm., 159.5 at 20.4 m.; ni 1.4664; d2 0.8860; MR 74.274,
calod. 74.357; AH 13,700 1,700 cal. mole- deg.-l; retention time,
10.30 minutes at 2000, helium flow rate, 20 ml./min.
Anal. Calad. for C15H27NO: C, 75.89;s %, 11.47; fN, 5.90.
Found: %c, 75.89; %H, 11.33; N, 5.96.
7. N, -Diallyl-N-tricyanovinylamine
The general procedure used was as outlined by McKusick, et al.23
for preparation of N,l-dialkyl-N-tricyanovinylamines. Diallylamine
(7.6 g., 0.0785 mole) was added dropwise with stirring to tetracyano-
ethylene (10 g., 0.0780 mole) dissolved in tetrahydrofuran (200 al.).
The addition rate was adjusted so that the temperature of the reaction
mixture did not rise above 350. After addition was completed, the
mixture was heated to reflux for a three hour period. The solvent was
removed under reduced pressure to yield a black, viscous oil, soluble
in acetone and ethanol, slightly soluble in benzene and insoluble in
water and pentane. All attempts to crystallize this material were
unsuccessful. The crude reaction mixture was degassed at less than
0.1 mm. for twenty-four hours. An attempt to sublime the product out
of the crude mixture at 0.05 mm, and 900 was unsuccessful. A five gram
sample was deposited from a warm, saturated, benzene solution onto a
chromatographic column prepared from benzene and activated alumina.
Elution with 200 ml. of benzene gave a clear, yellow solution. Attempts
to precipitate a solid from the benzene solution by addition of
non-solvents or by cooling were unsuccessful. Evaporation of the benzene
under reduced pressure yielded a yellow-red oil. The product was
identified as diallyltricyanovinylamine by infrared, ultraviolet and
elemental analyses. An ethanol solution was used to determine the
ultraviolet absorption spectrum: A max. 3340 A; C 14,300.
Anal. Called. ClR0114: %, 66.65; %H, 5.09; %N, 28.27.
Found: %C, 66.90; Ai, 5.38(; *, 27.94.
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POLYMERIZATION STUDIES ON DIALLYLAM4IDES
It was expected that the amides described above would undergo
homopolymerization via the cyclic polymerization mechanism with varying
degrees of success. This was expected because of the observations,
pointed out earlier, that the diallyl quaternary ammonium halides did
undergo cyclic polymerization while diallylamine did not. Also, other
compounds such as the diallylphosphorus compounds, mentioned earlier,
and diallylphthalate8v2-26 have been polymerised to soluble polymers
by free radical initiators.
Several other workers have described soluble copolymers from
diallyl systems, such as diallyl alkylamine oxides and acrylonitrile,27
and a variety of other copolymer systems.228
The results obtained from attempts to polymerize the amides
under a variety of conditions are given in this section. The monomers
all contain the diallylamine unit with various substituents on the
Friedlander29 has described the preparation of substituted
tetrahydropyrans and tetrahydrothiopyrans via a cyclic reaction of
allyl ether and allyl sulfide with chain transfer reagents, such as
bromotrichloromethane, under free radical conditions. This line of
approach was tried with the diallylamides in an attempt to prepare
cyclic telomers. The results of these studies are also included in
The preparations of the amides and tricyanovinylamine used in
this study were described in a previous section of this work. Heptane,
methanol, and xylene were from stock; benzene was stock, reagent grade,
and was dried over sodium ribbon before use. The other chemicals were
purchased: benzoyl peroxide and tert-butyl hydroperoxide from the
Lucidol Division, Wallace and Tiernan, Incorporated; a,~-diazoisobutyro-
nitrile from Eastman Organic Chemicals; bromotrichloromethane from the
Dow Chemical Company; and ethyl bromoacetate from the Fisher Scientific
B. Polymerization Procedure
Weighed quantities of the reactants, and solvent if used, in
20 ml. ampoules were flushed with dry nitrogen gas, and the ampoules
wer cooled in a Dry-Ice-acetone mixture before sealing off by use of
an oxygen-methane torch. Polymerizations were carried out in an oven
at the temperature and for the period of time indicated in Table III.
This procedure was followed in all of the polymerisation attempts
except those in which the initiator was tert-butylhydroperoxide. In
these experiments the samples were contained in a 100 ml. tube fitted
with a reflux condenser and with a standard taper ground glass joint
suitable for fitting into a refluxing xylene bath. In this way a constant
temperature of 140 was maintained during these runs.
The polymers were isolated by addition of the reaction mixture
to a large excess of methanol. The methanol mixtures were then filtered
through a medium porosity sintered glass filter. The filters were
dried in vacuo for twenty-four hours and the increase in weight taken
as the yield of polymer in each case.
C. Homopolymerization Attempts
The conversions for the diallylamides, along with the conditions
employed for each polymerization attempt are shown in Table III. The
conversions are approximate values only but may be taken as indicative
of the polymerizability of the monomers in a homopolymerization system.
A blank in the table indicates less than 0.2% conversion and "trace"
indicates conversions of 0.2-0.5%. The only samples which resulted
in appreciable conversions were the tricyanovinyl and trifluoroacetyl
derivatives. These two groups are also the two most electron
withdrawing groups in the series. Since trace quantities of polymer
were obtained from the formyl derivative, the next most powerful
electron withdrawing substituent, there seems to be a definite
correlation between the electron withdrawing power of the substituent
on the nitrogen atom of diallylamine and the polymerizability of the
monomer. Thus, it is observed that the stronger the electron withdrawing
power of a substituent the more readily the monomer undergoes
homopolymerization in a free radical system.
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D. Telomerization Reactions
The workers who have reported addition of polyhalogenated
compounds to olefins under free radical conditions would be too
numerous to list in this work. However, Kharasch30 should be mentioned
for both his large volume of work as well as his original contribution
in this field. An attempt was made in this work to carry out cyclic
telomerization reactions on two of the diallylamides by reaction under
free radical conditions with chain transfer reagents such as bromotri-
chloromethane and ethyl bromoacetate. Friedlander9 has observed in
cyclization reactions of this type that the activity of the chain
transfer reagent is important in determining the degree to which
addition is accompanied by cyclization. Thus, he points out that if
an active reagent such as bromotrichloromethane is used, the
concentration of the transfer agent must be low to allow cyclization
A description of the reactions and the results obtained from
this study follow.
1. Addition of Ethyl Bromoacetate to Diallylacetamide and Diallyl-
Ethyl bromoacetate (0.42 g., 0.00252 mole), diallyl-
acetamide (1.42 g., 0.0102 mole), and bensoyl peroxide (0.14 g.) were
dissolved in heptane (14.42 g.) and sealed in a 20 ml. vial. The reaction
mixture was heated in an oven at 700 for a period of twenty-four hours.
A dark, oily layer separated out of the reaction mixture which presumably
was a mixture of the various adducts possible in the reaction.
Ethyl bromoacetate (21 g., 0.125 mole) and diallyl-
propionamide (20 g., 0.13 mole) were added dropwise to benzoyl peroxide
(1 g.) dissolved in heptane (100 ml.) and contained in a 300 ml., three-
necked flask fitted with a stirrer and a reflux condenser. The reaction
mixture was heated to reflux with stirring for a twelve hour period.
Upon cooling the reaction mixture to room temperature, a dark, viscous
oil separated out as a bottom layer.
2. Addition of Bromotrichloromethane to Diallylacetamide and
Following the same procedure as in the addition of
ethyl bromoacetate the following materials and quantities were used:
diallylacetamide (1.42 g., 0.0102 mole), bromotriohloromethane (0.5 g.,
0.00268 mole), benzoyl peroxide (0.014 g.), and heptane (14.42 g.).
As before, the sealed tube containing the reaction mixture was maintained
at 700 for a period of twenty-four hours. A dark, viscous oil resulted.
Diallylpropionamide (200 g., 1.30 mole), bromotrichloro-
methane (242 g., 1.22 mole), benzoyl peroxide (10 g.), and heptane
(1300 al.) were combined in a 3 liter, three-necked flask fitted with
a reflux condenser and a stirrer. The reaction mixture was heated to
reflux with stirring for fifteen hours. The reaction mixture was cooled
to room temperature and the solvent and unreacted bromotrichloromethane
were removed under reduced pressure. The remaining crude reaction
product amounted to 324 g. of a viscous, dark oil.
3. Attempted Separation of Adducts
The addition of bromotrichloromethane, or other chain transfer
reagents, to the diallylamides can yield any or all of the three possible
adducts which contain only one monomer unit. The reaction can yield
two one'-to-one adducts, one via the cyclic mechanism and one in which
only one of the allyl double bonds has undergone reaction. A two-to-one
adduct is also possible if both of the allyl double bonds undergo an
addition of the chain transfer reagent.
Several attempts were made to separate a cyclic product from
the viscous oil obtained by reaction of bromotrichloromethane to
An attempt to separate the mixture by passage through a two
inch centrifugal type, molecular still failed to yield definable
products. Repeated passage of the reaction product from a typical
run through the still gave the following fractions 1) recovered
monomer (393), 2) viscous, yellow oil (30%), distilled over at less
than 200 and 100 microns pressure, and 3) black tar (37%), non-
volatile at 2000 and 100 microns pressure. Further efforts to obtain
good fractions from fraction 2) by successive passage through the still
An attempt was also made to separate the reaction mixture by
elution chromatography through a column of activated alumina prepared
with hexane. A portion of the reaction mixture was dissolved in acetone,
filtered to remove any insoluble material, and the acetone evaporated.
Ten grams of material so treated was dissolved in 10 ml. of acetone
and deposited on the column. The column was elated in order with the
following solvents: hexane, benzene, heptane, butanol, iso-propanol,
and acetone. The solvents were gradually changed from one to another.
Thus, elution began with hexane, followed with a 254 benzene-75% hexane
mixture, etc. The material which was not eluted by hexane, benzene,
or heptane but which was eluted by a 15% butanol-85% heptane mixture
was collected and amounted to 2.06 g. or 21% of the total. This sample
was dissolved in 3 ml. of acetone and deposited on a freshly prepared
hexane-alumina column. The column was eluted with heptane, followed
with acetone. The acetone-eluted material was separated; and the solvent
was evaporated to yield 1.5 g. of a light yellow, viscous oil. The
molecular weight of this sample was determined, by measuring the molar
depression of the freezing point of benzene, to be 346. The calculated
value for a one-to-one adduct is 351.5. An examination of the infrared
spectrum of this sample failed to confirm the presence of only the
eyclized product. The spectrum differed significantly from the spectrum
of the monomer in that the expected absorption for the trichloromethyl
group in the 700-800 cm. region was present. However the absorption
corresponding to the terminal methylene group at 920 cm. in the
nonomer had been split into two separate peaks at 890 and 920 cm.-1,
and greatly diminished in intensity. Thus, it can only be concluded
that the attempt to isolate a pure cyclic adduct was unsuccessful.
INFRARED INVESTIGATIONS OF THE DIALLYLAIDES AND RELATED COMPOUNDS
One of the stated objectives of this work is to gather evidence
to explain the strong tendency of 1,6-heptadienes to undergo polymeri-
zation via the cyclic polymerization mechanism. Workers in this
laboratory have proposed a structure for the various monomers which
involves intramolecular electronic interaction of some sort. This
interaction can be represented by the following structure:
SCH .- CH
CH -c3H NCH- CH -CH CH
2 2 i I
CH CH2 CH2 /C
R 1t. i
The proposed intramolecular interaction is supported by the
work of Mikulasova and Hvirik2 in which they determined that the total
activation energy for radical polymerization of diallyldimethylsilane
is about 9 kilocalories per mole double bond less than that for
allyltrimethylsilane. Additional support for this interaction has
been offered by Marvel and Stille.I These workers have studied the
polymerization of non-conjugated dine systems such as 2,5-dimethyl-
l,5-hexadiene by metal alkyl coordination catalysts. This study also
included the mono-olefin, 2-methyl-l-pentene, which did not yield high
molecular weight materials. The investigators considered both of these
systems as 1,1-disubstituted ethylenes and suggested that the driving
force afforded by the formation of the cyclic structure was responsible
for the success in polymerization of the diene and the lack of success
in the case of the mono-olefin.
In the course of this investigation, an examination of the
infrared spectra of the several monomers prepared in this study was
made. The results of this examination seem to offer additional support
for the proposed interaction between the two allyl groups in the monomers.
The infrared spectra were run en; a Perkin-Elmer modell 21 double
beam spectrometer containing a high dispersion calcium fluoride prism.
The spectra were used as confirming evidence for the identification
of the diallylamides prepared in the study and contain the absorption
frequencies which one would normally expect from this type of compound.
The information used as evidence for the proposed interaction was not
the appearance or disappearance of any of the expected peaks but rather
the pattern exhibited by the observed shifts in frequency of absorption
by the amides and related compounds.
The absorption frequencies for the in-plane-deformation
vibration of the terminal methylene group in the diallylamide series
and related compounds are shown in Table IV.
Bellamy in his comprehensive text on infrared spectra assigns
this group to the 1420-1410 cm.-1 region and further reports
"...... the band near 1415 cm.1 is usually strong in the infrared and
is very stable in position, so that it serves as a useful guide in
analysis. The substitution of -CH2OR and -CH2OCOR groups has little
or no effect upon this frequency, but in case of acrylates and
methacrylates it shows a slight fall to 1405 cm. -."
It will be observed from the values in Table IT that there is
a definite shift in the frequency of absorption in the series of diallyl
compounds listed. This shift may be correlated well with the results
from polymerization studies. It is seen that the shift to a higher
absorption frequency for the group under consideration parallels the
polymerizability of the monomer. Thus, the more readily the monomers
undergo polymerisation the higher the absorption frequency for the
in-plane-deformation vibration of the terminal methylene group.
The shifts are not large in absolute magnitude, but the trend
which is exhibited seems to be significant. This shift in frequency
can probably best be explained by a combination of two electrical
effects present in the molecules. These two effects are the inductive
effects exerted through the chain, and the mesomeric effect exhibited
by the amide group in the sharing of the lone-pair electrons of the
nitrogen with the carbonyl carbon atom. Thus, canonical forms such as
ABSORPTION FREQUENCY OF IN-PLANE-DEFORMATION VIBRATION
OF TERMINAL 1ETHTLENE GROUP
Sample Absorption Frequency Thickness
Diallylformanide 7.062 1416 0.015
Diallylacetamide 7.078 1413 0.015
Diallyl-trifluoroacetamide 7.038 1421 0.015
Diallylpropionamide 7.078 1413 0.015
Diallylheptanamide 7.078 1413 0.015
Diallylnonanamide 7.078 1413 0.015
Diallyl-tricyanovinylamine 7.052 1418 0.015
Diallylcyanamide 7.037 1421 0.015
Diallylammonium bromide 6.917a 1437 KBr disc
Diallylmethylphosphine oxide 7.040b 1420 0.015
Diallylphenylphosphine oxide 7.057b 1417 0.015
Diallylmethylphenylphosphonium bromide 7.045c 1419 melt
Dimethyl-4-pentene amine 7.080 1411e plates
a. Value from R. Silas, h.D. dissertation,
University of Florida, June, 1954
b. Sample furnished by Dr. K. D. Berlin
o. Sample furnished by Mr. D. L. Skinner
d. LiF prism
e. t!aCl prism
R-C04R and I-COR will contribute to the structure of the amides.
Bellamy' points out that this contribution is most marked with the
amide type of compounds. The combination of these two effects, the
mesomeric effect to give a positive charge or at least a partial charge
on the nitrogen atom and the inductive effect to distort the electron
cloud normally distributed between the terminal carbons, can be offered
as plausible support for structures of possible forms supporting the
proposed interaction between the two allyl groups.
Thus, the combination of the two electrical effects may be
illustrated as follows:
S CH 8+ a-. ."
S0 ..+ .. -- 6 2\
CH CH C -- CH-CH ***CH ---* CH -CH .
CH C C2 CH2 C
2IA /CH 2 2 \+
R R R
The definite trend in the amide series, that of increasing
polymerizability with decreasing basicity of the nitrogen atom, is
further born out by inclusion of the quaternary aamonium salt which is
the least basic of the series, and the most polymerizable. Absorption
occurs at the highest frequency in this compound.
Several other compounds are included in the table on which
polymerization reactions have not been run but which seem to fit in
well with the trend of absorption frequency and the usually accepted
electron withdrawing power of the groups substituted on the central
STUDIES ON POLY-(METHACRYLIC ANHEDRIDE)
Workers in both these and other laboratories independently
demonstrated that acrylic anhydride could be polymerized via the cyclic
polymerization mechanism to yield linear, soluble polymers. This was
the first evidence that monomers, usually considered as highly reactive
monomers, could be polymerized in such a manner. Jones6 has also
described poly-(diacrylylmethane) resulting from an attempted Claisen
condensation of methyl vinyl ketone with ethyl acrylate in an attempt
to prepare the monomer diacrylylmethane. He attributed the result to
an anionic polymerization of the monomerio compound as it was formed.
Stereoregular polymers have been prepared under a variety of
conditions to yield polymers of vastly different properties than so
called "atactie" or random polymers. An excellent review of this
field is available in the text by Gaylord and Mark, Linear and Stereo-
regular Addition Polymers.35 Until recently the bulk of the stereo-
regular polymers prepared had resulted from anionic, cationic or
Ziegler-type coordination catalysts. The work by Crawshaw" demonstrated
that there may be some stereoregulating influence in the cyclic
polymerization mechanism. He obtained poly-(acrylic acid) by hydrolysis
of poly-(aerylie anhydride) which was substantially more crystalline
than conventional poly-(acrylic acid) as demonstrated by x-ray
In this work, methaerylic anhydride was polymerised via the
cyclic polymerization mechanism to poly-(methacrylie anhydride) under
a variety of conditions. This was undertaken in an effort to determine
whether any stereo-control is exerted via this mechanism and if so to
what extent this stereo-control will manifest itself in the configuration
of the polymers so prepared.
Some time after this work was undertaken, Bovey and Tiers3
observed that the nuclear magnetic resonance (NMR) spectra of
poly-(methyl methacrylate) in chloroform solution at 900 showed three
a-methyl proton peaks. They determined that these three peaks correspond
to those a-methyl groups in isotaetic, heterotactic and syndiotactic
placements. The terms above, denoting the stereo configuration of
the polymer segments, have been redefined by Bovey in his paper.
Thus, he terms an isotactic configuration as one which the a-methyl
group is flanked on both sides by units of the same configuration.
This gives rise to the peak at lowest field strength. A heterotactic
configuration is designated as one in which the central a-methyl group
is flanked on one side by a similar configuration and on the other by
a dissimilar configuration, and results in the middle peak observed.
The syndiotactic configuration is defined as one in which the central
a-methyl group is flanked on each side by monomer units of the opposite
configurations, and is observed as the peak at highest field strength.
Thus, in this system isotactic configurations are described as 111 or
ddd units, heterotactic configurations as Idd, dll, ddl, or lid units
and syndiotactic configurations as idl or did units. The area described
by each peak will be proportional to the number of isotactic, heterotactic
and sydiotactic units.
This method of analysis lends itself well to this problem since
Fox and his co-workers have prepared samples of isotactio and
syndiotactie poly-(methyl methacrylate) of nearly pure stereoregular
configurations. These workers also determined the identity of each
type by independent x-ray analysis. This work made it possible for
Bovey to assign the various peaks observed in the NM spectra to the
a-methyl protons in the three types of configurations.
In this section a description is given of the polymerization
of methaorylic anhydride under various conditions and the results
obtained from NMR investigation of poly-(methyl methacrylate) derived
from the poly-(anhydride) by hydrolysis to the poly-(acid) and
The solvents used in this study were all dried prior to use.
Benzene (reagent grade), ethyl ether and hexane were from stock and
were dried over sodium ribbon. Methanol was also from stock and was
distilled from sodium metal before use. Dimethylformamide, purchased
from Matheson, Coleman and Bell, was distilled and stored over Drierite.
Methacrylio anhydride, purchased from The Borden Company, was distilled
before use; and gas chromatographic and infrared analysis indicated
that its composition of a single component was in excess of 97%- The
remaining materials were also purchased: bensoyl peroxide from the
Lucidol Division, Wallace and Tiernan, Inoororrated; a,a'-diasoiso-
butyronitrile from Eastman Organic Chemicals; N-methyl-nitrosourea
from K and K Laboratories; and chloroform, spectroanalysed grade,
from Fisher Scientific Company.
B. Polymerization Procedure
Measured volumes of the monomer and solvent along with weighed
quantities of initiator, a,a'-diasoisobutyronitrile, were sealed in
20 ml. ampoules after cooling in a Dry-Iee-acetone mixture and flushing
with dry nitrogen gas. Polymerizations were carried out in a water
bath maintained at a temperature constant within 0.10 for the period
of time indicated. In those runs in which the samples were irradiated
with ultraviolet light the source was a Blak-RBy Model x-4 lamp placed
approximately 8 cm. away from the sample vial. This procedure was
followed in all of the polymerizations except those in which the solvent
was dimethylformamide. In these experiments the samples were contained
in a 25 ml. tube fitted with a gas inlet tube arranged to bubble
nitrogen gas through the solution during the course of the reaction.
The samples were irradiated and maintained at the indicated temperatures
in the same manner as previously described. The polymers were freed
from monomer and solvent by trituration with methanol. The polymers
were then filtered and dried in vacuo. A number of the polymers were
dissolved in dimethylfonrmaide and precipitated by addition to ethyl
ether or methanol in order to demonstrate that the poly-(methaerylic
anhydride) so prepared was a soluble polymer. The polymers dissolved
very slowly in dimethylformamide with solution usually requiring from
forty-eight to seventy-two hours in a closed system.
The results of the polymerizations are summarized in Table V.
C. Idrolysis to Pol-(Methacryli Acid)
The samples prepared above were hydrolysed to yield poly-
(methacrylic acid). The general procedure used in the hydrolysis
reaction is outlined below. There is also included in this section
a description of the conditions used in comparative hydrolysis studies
which were undertaken in an effort to demonstrate that the conditions
employed during hydrolysis did not affect the configuration of the
pseudo-asymmetrio carbon atoms in the final product, poly-(methyl
methacrylate). This would be true if no racemization occurs during
the course of the hydrolysis reaction. The NMR measurements which
are given in a later section demonstrated that this was indeed the
case and similar poly-(anhydride) samples gave NMR measurements very
nearly the same in each ease regardless of the method of hydrolysis
employed. The results of the hydrolysis of poly-(methaerylic anhydride)
to yield poly-(nethaorylic acid) are summarized in Table VI.
1. General Procedure
Poly-(methacrylic anhydride) was added to distilled water in a
flask fitted with a reflux condenser. The water to polymer ratio
(volume/weight) was approximately 100 ml./1 g. in each ease. The
mixtures were allowed to stand at room temperature overnight and then
RESULTS OF METHACRILIC ANHYDRIDE POLYMERIZATIONS
Number Temperature Initiator Time Conversion
[c,] [(wt. %J] [hr.)
33-D 1 1.0 19 78
33-Ca 20 1.0 14.5 96
33-B 30 1,0 7.3 68
31-D 30 1.0 22 33
33-A 40 1.0 3 45
31-A 50 1.0 2 37
31-B 60 1.0 1.5 70
31-E 70 1.0 0.5 75
31-F 80 1.0 0.22 88
6 65 1.0 -
21 15 0.?50 2 46
a. Irradiated with ultraviolet
b. Bensoyl peroxide initiator,
monomer in benzene. Sample
M. D. Barnett.
e. Benzoin as photoinitiator
29% solution of
HTROLYSIS OF POLY-(METHACRILIC ANHDRIDE) TO POLY-(METHACRYLIC ACID)
Number Weight Volume Yield Recovery
[g. polymer] [al. vater] Lg. oly-(aoid)]
Identical samples hydrolysed under different conditions.
Mild hydrolysis, see text.
tydrolyzed by General fydrolysis Procedure, see text.
Basic hydrolysis, see text.
-- I -- ~~-~-~~-~- --~-
refluzed for approximately twenty-four hours. After refluxing, the
solutions were allowed to stand for an additional twenty-four hours.
The solutions were then filtered through a medium-porosity, sintered
glass filter and the water evaporated under heat of an infrared lamp
and reduced pressure employing a Lab-Drier. The resulting clear films
of poly-(methaorylic acid) were removed from the flasks, ground to a
fine powder, and dried in vacuo for a period of at least twenty-four
2. Basic Ifdrolysis
Poly-(methacrylic anhydride) (1 g.) was added to 50 ml. of
distilled water and the mixture made strongly basic by addition of
(solid) sodium hydroxide pellets. The mixture was stirred for a few
minutes until solution was complete. The solution was filtered and
the clear filtrate heated almost to boiling. To the hot solution,
concentrated hydrochloric acid was added dropwise until the solution
became strongly acid. The coagulated solid portion was stirred and
removed from the acidic solution. The solid mixture of poly-(methacrylio
acid) and sodium chloride was dried in vacuo overnight, ground to a
fine powder and then redried in vacuo for twenty-four hours.
3. Mild Hydrolysis
Poly-(methaorylio anhydride) (1 g.) was added to 50 al. of
distilled water and stirred at room temperature until solution was
completed. The solution was filtered and the water removed in vacuo.
The resulting poly-(methacrylio acid) was ground to a fine powder and
dried in vacuo for a period of twenty-four hours.
D. Esterification of Poly-(Methaorylic Aoid)
The poly-(methaerylio acid) samples were converted to poly-
(methyl methaorylate) following the method of Katchalsky. 3 The
diasomethane was prepared in a benzene solution by basic decomposition
of metbylnitrosourea according to the method given in Organio Syntheses.
An outline of the general method used is given below and the results
of the various preparations are summarized in Table VII.
A sample of poly-(methaorylic acid) (0.205 g., 0.0012 mole)
contained in a 50 ml. test tube was covered with a benzene solution
of diasomethane (20 ml., 5.6 g./300 ml.). The tube was stoppered with
a loose fitting cork and allowed to stand overnight at room temperature.
At the end of a fifteen hour period the solution was essentially
colorless but some gelatinous material, presumably unreacted poly-
(methaarylie acid), was evident in the bottom of the benzene solution.
A second addition of diasomethane solution (20 ml., 5.6 g./200 ml.)
was made after the initial fifteen hour reaction period. After the
second addition of diasomethane solution, the reaction mixtures were
stirred at thirty minute intervals for three hours and then allowed
to stand overnight at room temperature. The reaction mixtures wer
filtered through a high speed filter paper on a Buchner funnel. The
unreacted material was washed on the filter with 50 ml. of benzene
and the washings combined with the original filtrate.
The poly-(methyl methacrylate) was isolated by dropwise
addition of the benzene solution (ca. 80 ml.) to four times its volume
of rapidly stirred hexane. The hexane-polymer mixtures were centrifuged
CONVERSION OF POLY-(IETHACRYLIC ACID) TO
POLY-(METHL IETHACRYLATE) BY REACTION WITH DIAZOMETHANE
Number Volume Yield Conversion
[mole diazomethane/ [ml. bnenene] [g. poly-(ester)]
and the hexane decanted. The poly-(methyl methacrylate) was dried
in vaauo for at least twenty-four hours.
E. X-Ray Diffraction Studies
Sufficient poly-(methyl methacrylate), prepared as described
in the previous sections, was dissolved in bensene to prepare a solution
of approximately 2% concentration. This solution was allowed to
evaporate slowly at room temperature from a shallow cup formed from
aluminum foil to yield a slightly opaque film. The poly-(methyl
methacrylate) had been prepared at 650 with benzoyl peroxide as the
initiator. This sample had a molecular weight of 124,000 as determined
by viscosity measurements, using the relationship of Baxendale, Bywater
The film was dried in vaeuo at room temperature for several
days and then at higher temperatures, up to 900, for several hours at
approximately thirty degree intervals. This film was submitted to
Dr. W. F. Loranger at the General Electric X-Rta Laboratories for
x-ray diffraction measurements. A Laue diffraction pattern showed
four distinct diffraction lines. A diffractometer trace showed broad,
diffuse peaks at 14 to 16 and 28 to 300 and aso sharp peaks at
21.50 and 24.1. The patterns, as interpreted by Dr. Loranger, indicate
that the sample was approximately 50% crystalline.
F. Nuclear Magnetic Resonance Studies
Included in this section are the general methods of sample
preparation, measurements and a discussion of the results as well as
a discussion of the relationships between the various stereo
configurations possible in the polymers.
An examination of molecular models of the poly-(methacrylic
anhydride) polymers prepared from the LaPine-type models shows that
all three of the possible types of configurations can be constructed.
Of the models of the three configurations, isotactic, syndiotactic and
heterotactio, that of the isotactic polymer was the easiest to construct
and seemed to be the least sterically hindered. In all of the models
there seemed to be considerable steric hinderance between a-methyl
groups on adjacent anbydride rings. The models also indicated that
in the isotactic polymer the carbonyl oxygen atoms are quite close
while the preferred arrangement in the syndiotactic and heterotactic
polymers was one in which the carbonyl oxygen toms on adjacent rings
are farther apart from one another. This would place the anhydride
portion of one ring in the same relative position as the cyclic
methylene group in the next ring.
An examination of models of the various polymer segments
with respect to the methylene group connecting adjacent cyclic
anhydride units indicated that it was possible for the methylene groups
to assume all of the several possible conformational arrangements.
Thus, the methylene group could be in an axial-axial, equatorial-
equatorial, axial-equatorial or equatorial-axial information with
respect to the two rings which it joined together. This relationship
is an extension of the above discussion inasmuch as the fixing of the
conformation of the methylene group between two rings fixes the
configuration of the pseudo-asymmetric carbon atoms. An examination
of the above would show that an axial-axial or equatorial-equatorial
conformation would lead to an isotactic configuration for the polymer.
An axial-equatorial conformation would lead to alternation of
configuration and gives rise to heterotactic or syndiotactic polymer
segments. A third placement is necessary in each case to define an
isotactic, syndiotactic or heterotactic unit.
Thus, a polymer which is predominantly isotactic will be biased
toward successive placements or conformations being the same as the
preceding one. A conformation in which the methylene group is axial
to one ring and equatorial to the other or a conformation in which
one methylene group attached to a ring is axial and the other methylene
group attached to the same ring is equatorial would lead to alternation
of configuration of the pseudo-asymmetric carbon atom. If these
sequences are favored over those which are opposite to them then the
probability of a syndiotactie placement will exceed the probability
of a heterotactic placement. The probability of a heterotactic placement
would be the larger if a syndioduotactic structure as proposed itg Hwa
predominated. In this eas there would be a bias toward an axial-axial-
equatorial-equatorial sequence. This sequence can arise from either
of two types of conformations as in the ease of the syndiotactic
The methylene group connecting rings I and II would be equatorial at
positions 2 and 3 while the methylene group connecting rings II and III
would be axial at positions 4 and 5. The other sequence would be one
in which the methylene group connecting rings I and II is axial at
position 2 and equatorial at position 3 while the methylene group
connecting rings II and III is equatorial at position 4 and axial at
Coleman and Bovey6 have derived the relationships of the
various probabilities in random chain growth. They designate by a the
probability that a growing chain will add a monomer unit to give the
same configuration as that of the unit at the growing end. The
assumptions are made that a is controlled by only the configuration
of the end unit and not by the preceding one and that the propagation
is adequately described by a single value of a. The probabilities
(P) are: Pi = a2 p2 = (1- )2 and Ph = 2(a 2). The subscripts
i, s and h refer to isotactic, syndiotactic and heterotactic placements,
respectively. Figure 1 is a plot of these relationships. Bovey6 has
compared the results of free radical polymerizations of methyl methacrylate
to anionic polymerizations of methyl methacrylate as described by Fox.37
He determined that "atactic" poly-(methyl methacrylate) or material
polymerised by free radical initiators is predominantly syndiotactio
(77-87%) in character. These polymers fit the probability curves well
The probabilities of occurrence of isotactic,
Pi, heterotactic, Ph, and syndiotactic, Ps,
sequences of monomer units as a function of a,
the probability of isotactic placement of
monomer units during propagation.
and thus the assumptions seem to be valid in this case. However, the
poly-(methyl methacrylate) samples prepared using anionic initiators
did not fit the probability curves and these were termed "non-sigma"
systems or systems not described by a single probability value. He
attributed the failure to the tendency of the metal ion to complex with
both the solvent system and the growing chain.
Workers in this field have also observed that solvents and
temperature both affect the stereo-control in polymerization systems
in type and degree. It has been shown in all previous work that a
decrease in temperature is accompanied by an increase in stereoregularity
in the products in both anionic3 and free radical polymerizations. 36',95
It has also been observed, in both anionic7 and free radical
polymerizations that the solvent determines to a large extent which
form of polymer results. In the polymerization of methyl methacrylate
with toluene as the solvent anionic initiators yield isotactic
products; with polar solvents such as dimethoxethane the syndiotactic
products are formed; while in systems of mixed solvents such as toluene-
dimethoxyethane a large proportion of all three configurations results.
As a result of the above observations the main portion of this
work constitutes a study of the effect of temperature of polymerization
on the stereoregularity of the products obtained.
1. Preparation of IRlR Samples
The poly(methyl methacrylate) described in the previous sections,
along with several samples for comparative purposes, were used in this
work. Weighed quantities of the polymers were placed in 5 u. (O.D.)
Pyrex glass tubes approximately 9 in. long and sealed at one end.
Sufficient spectroanalysed chloroform was added to give a 20% (w/v)
mixture. The tubes were sealed and the mixture heated in a water bath
at 1000 to facilitate solution of the polymers. A few of the samples
failed to give a homogeneous solution and were subsequently diluted by
addition of solvent in order to get useful results from the NMR
measurements. The concentrations are listed in Table VIII with the
The NMR spectra were run on a Varian V-4302 high resolution
spectrometer, operating at 56.4 megacycles. The temperature of the
samples was maintained at 90-98D during the measurements.
The relative peak areas were determined by visual division of
the overlap area and measuring the designated areas with a planimeter.
The results obtained in this manner suggested that the area described
by each peak was proportional to the three-halves power of the peak
heights. Since the second method was deemed the most reproducible as
well as the most rapid, it was used in all of the measurements recorded.
Several traces of the a-methyl proton peaks were obtained in each case
and the average values of the peaks are recorded. The results of the
measurements are shown in Table VIII.
G. Interpretation of Results
Figure 2 is a plot of the percentage of isotactic units in the
poly-(methyl methaerylate) samples versus the polymerisation temperature.
FRACTIONS OF POLY-(METHYL METHACRLATE) IN
THE THREE STEREO CONFIGURATIONS AS DETERMINED BY NMR
Number Temperature Concentration i h a a
oc,)] [g./ml.] l i%) [% [based on
Average of the two 300 samples plotted.
Sample prepared by Dr. H. G. Clark, n-butyl lithium in toluene.
Value from F. A. Bovey, benzoyl peroxide initiator in toluene.
Value from F. A. Bovey, sodium naphthalene in glyme solution.
This refers to polymerization of methyl methacrylate.
0.20 0.40 0.60 0.80
The probabilities of occurrence of isotactic,
heterotactic and syndiotactic sequences of
monomer units as a function of a, the
probability of isotactic placement of monomer
units during propagation. The fraction of
isotactic is placed on the isotactic line to
determine the value of a.
This group of samples is listed in Table VIII. All of these samples
were prepared under identical conditions except for the temperature
of polymerization and the fact that some of the samples prepared at
low temperatures were irradiated with ultraviolet light. The trend
is unmistakable. There is a definite increase in the percentage of
isotactic character with an increase in temperature.
In Figure 3, a plot of the probability values, the results of
the same series of polymerizations are plotted on the curves. The
observed value for the isotactic point is placed on the isotactic
plot and the values for per cent syndiotactic and heterotactic
placements are allowed to fall where they may. It is quite obvious
that the syndiotactic and heterotaotic points do not fall within
acceptable limits of their predicted values. From this it can only
be concluded that this system is a "non-sigma" system as described by
Bovey. However, the cause for the failure in this case must be
ascribed to the failure of the assumption that the placement is
unaffected by the penultimate unit. It can be concluded from this
that the cyclic mechanism does indeed affect the steric path in
polymerization reactions and it may even do so in a different manner
that is observed in conventional mechanisms.
It has previously been pointed out, in a prediction by Huggins4
in 1944, that a preponderance of segments of chains of either isotactic
or syndiotactic configuration may arise in homogeneous free radical
polymerizations if the free energy of activation for an isotactic
placement is different from that for a syndiotactic placement.
Polymerization Temperature *C.
Plot of log of the percentage of isotactic
fraction in the poly-(nethyl methacrylate)
samples versus the temperature of polymerization.
I 1 __
This has been developed to some extent by Fox and eo-workers in their
work on free radical polymerization of methyl methacrylate.
In the analysis by Fox the suggestion was made that an
isotactic placement, in the polymerization of methyl methaerylate,
may be more favored with relation to energy while the syndiotactic
placements are more favored with relation to entropy. If the reactions
are kinetically controlled the parallel reasoning may be applied in
this work. However, since the opposite results are observed in the
polymerization of methacrylia anhydride via the cyelic mechanism,
the isotactic placement would be less favored with respect to energy
and more favored with respect to entropy. The numerical interrelation
of these two factors, which are influenced by the steric considerations
mentioned earlier, determines the free energy of activation for the
polymerization process and thus the temperature dependency of the
stereoconfiguration of the polymeric products.
An alternative explanation, if the reactions are controlled
by both kinetic and equilibrium considerations, may also be offered.
If a combination of these two factors do control the polymerization,
then an examination of the results would lead to the following
conclusion. In view of the fact that the isotactic structure
predominates at the higher temperatures while the more random results
are observed at lower temperatures, the syndiotactic structure seems
to be the more readily formed, in a kinetic sense, while the isotactic
structure is the thermodynamically more stable configuration.
Three areas of interest concerning the polymerization of diene
monomers via a cyclic polymerization mechanism were investigated.
These considerations are t 1) the relation of the structure of the
monomer to the polymerizability of the monomer, 2) the determination
of the existence of stereo regulation via this mechanism and,
3) the investigation of the extent of this stereo regulation in a
A series of diallylamides, some of which had not been previously
reported, were prepared and the physical constants of these compounds
are listed. A structurally related compound, N,N-diallyl-N-trieyano-
vinylamine was also prepared. Included in this study was an investi-
gation of the infrared spectra and the polymerizability of the diallyl
substituted compounds. A correlation of the results of the polymeri-
zation study and infrared investigation is offered. This correlation
is presented as substantiating evidence for an intramolecular interaction
in the monomeric compounds which is believed to offer a partial
explanation for the success of the accepted intranolecular-intermoleoular
cyclic polymerization mechanism.
Nethacrylic anhydride was polymerized, in high yields, at
temperatures ranging from 10 to 800, in bensene solution, to linear,
soluble polymers. The poly-(methacrylli anbydride) so prepared was
hydrolyzed to the corresponding poly-(methacrylic acid) and this
poly-(acid) esterified by reaction with diasomethane to yield
poly-(methyl methacrylate). The result of an x-ray diffraction
study of an unstretched film of poly-(methyl methacrylate) prepared
in a similar manner is given. The determination of the fraction of
the polymer present in each of the three possible stereo configurations,
isotactic, syndiotactic and heterotactic, was made from a nuclear
magnetic resonance investigation of the derived pol-(methyl
methacrylate). The results indicate that the stereo configuration is
influenced by the cyclic polymerization mechanism. The results also
indicate that there is a bias toward increasing isotactio character
in the polymers with an increase in polymerization temperature.
Two possible explanations are offered. One in terms of a kinetic
control of the steric placements and the other in terms of a balance
between equilibrium and kinetic considerations.
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W. Lamar Miller was born January 20, 1935, in Aokerman,
Mississippi. He received all of his early training in the public
schools of that state. He graduated from Clinton High School,
Clinton, Mississippi, in June, 1953.
In June, 1952, he entered Mississippi College, from which he
received the Bachelor of Science degree in June, 1955.
He entered the Graduate School of the University of Florida
in September, 1955, where he was employed as a research assistant for
some time. He received the degree Master of Science in Chemistry
in February, 1958.
He held the Chemstrand Fellowship for Research in High Polymers
during the academic year 1959-1960 and prior to that had been appointed
a teaching assistant in the Department of Chemistry for the same
He is a member of the American Chemical Society and Alpha
Chi Sigma, the Chemical Professional Fraternity*
This dissertation was prepared under the direction of the
chairman of the candidate's supervisory committee and has been
approved by all members of the committee. It was submitted to the
Dean of the College of Arts and Sciences and to the Graduate Council
and was approved as partial fulfilment of the requirements for the
degree of Doctor of Philosophy.
January 28, 1961
Dean, College of Arts f Sciences
Dean, Graduate School
Cl .\ 0#
UNIVERSITY OF FLORIDA
S 1262 III08553 7974III
3 1262 08553 7974