Preparation of stereospecific polymers through a cyclic polymerization mechanism.

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Title:
Preparation of stereospecific polymers through a cyclic polymerization mechanism.
Uncontrolled:
Stereospecific polymers, Preparation of
Physical Description:
vii, 56, 1 l. : ill. ; 28 cm.
Language:
English
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Miller, W. Lamar, 1935-
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s.n.
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Gainesville
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Polymers   ( lcsh )
Polymerization   ( lcsh )
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bibliography   ( marcgt )
theses   ( marcgt )
non-fiction   ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida.
Bibliography:
Bibliography: l. 53-54.
Statement of Responsibility:
By Lamar W. Miller.
General Note:
Manuscript copy.
General Note:
Vita.

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University of Florida
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Full Text
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

Approved:


II



Izxandutria2. 'ng.




[t-r ,.,l oh .- i i / ,
t


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

POLYMERIZATION MECHANISM










By
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
January, 1961









ACKNOWLMEDOMNTS


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 . . .

CHAPTER

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 *


* .

* U

* *

* .

* U

* 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 .* *


Page

ii

vi

vii



1

2

3

3

3

5

5

5

6

6

7

8

8

14

15

15

16

19


iii








TABLE OF CONTENTS (continued)


Page

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)

Page

G. Interpretation of Results .- 45

VI. SIMMARY ................ ... ... 51

BIBLIOGRAPHY........ .*.... 53

BIOGRAPHICAL NOTES *. ..... ..... 56









LIST OF TABLES


Table Page

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


Figure Page

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









CHAPTER I


INTRODUCTION




1.09 8-18
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.









CWATER II


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.









A. Nomenclature



All nomenclature in this work will follow that used by

Chemical Abstracts.





B. Materials



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

brick).

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,

Knoxville, Tennessee.









D. Preparation


0

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.

0
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.
0

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.
0
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.
0
II
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.









0

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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CHAPTER III


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
27,28
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

nitrogen atom.

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

this section.









A. Materials



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

Company.





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

to occur.

A description of the reactions and the results obtained from

this study follow.

1. Addition of Ethyl Bromoacetate to Diallylacetamide and Diallyl-

propionamide

a. Diallylacetamide

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.

b. Dially1propionamide

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

Diallylpropionamide

a. Diallylacetamide

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.

b. Diallylpropionamide

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

diallylpropionamide.

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

were unsuccessful.

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
-1
group in the 700-800 cm. region was present. However the absorption
-l
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.








CHAPTER IV


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 H2
R 1t. i


I I

CH CH
2 /A2


I 11



_CH2 -CH
2 1/
x
a










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









TABLE IV

ABSORPTION FREQUENCY OF IN-PLANE-DEFORMATION VIBRATION

OF TERMINAL 1ETHTLENE GROUP


Sample
Sample Absorption Frequency Thickness
SL[cBm."1] [Fan*

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








0 0
1+ I+
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:
8+
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




28




electron withdrawing power of the groups substituted on the central

nitrogen atom.









CHAPTER V


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
16
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

diffraction studies.










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

subsequent esterification.




A. Materials



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









TABLE V

RESULTS OF METHACRILIC ANHYDRIDE POLYMERIZATIONS


Sample
Number Temperature Initiator Time Conversion
[c,] [(wt. %J] [hr.)

33-D 1 1.0 19 78

33-Ca 20 1.0 14.5 96
a
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


lamp.
29% solution of
prepared by









TABIa VI

HTROLYSIS OF POLY-(METHACRILIC ANHDRIDE) TO POLY-(METHACRYLIC ACID)



Sample
Number Weight Volume Yield Recovery
[g. polymer] [al. vater] Lg. oly-(aoid)]


31-A

31-BC

31-c

31-D


31-F

33-A

33-B

33-C

33-D

3,-Aa

34-B

34-Ca


0.30
0.25

0,20

0.30

0.25

0.25

0.40

0,50

0.25

0.50

1.00b

1.000

1.00d


100

25

100

100

25

25

100

100

25

100

50

50

50


0.23
0.20

0.17

0.31

0.22

0.19

0.34

0.37

0.20

0.39


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

hours.

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









TABLE VII

CONVERSION OF POLY-(IETHACRYLIC ACID) TO

POLY-(METHL IETHACRYLATE) BY REACTION WITH DIAZOMETHANE


Sample
Number Volume Yield Conversion
[mole diazomethane/ [ml. bnenene] [g. poly-(ester)]
mole poly-(acid)]


31-A

31-B

31-C

31-D

31-E

31-F

33-A

33-B

33-C

33-D

34-A

31-B
34-C


19

23

37
23
21

23
12.5

12

16

11

6.5

5

7.5


0.17

0.10

0.05

0.15

0.11

0.14

0.33
0.34

0.09

0.36
0.54

0.44

0.45









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

and Evanse.

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
412
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

sequences.
















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

position 5.

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.


0.80





0.60


0.40





0.20


Figure 1.









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

MR results.

2. Measurements

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.









TABLE VIII

FRACTIONS OF POLY-(METHYL METHACRLATE) IN

THE THREE STEREO CONFIGURATIONS AS DETERMINED BY NMR


Sample Polymerisation
Number Temperature Concentration i h a a
oc,)] [g./ml.] l[] i%) [% [based on
i peak]


33-D

33-C

33-Ba

31-Da

33-A

31-A

31-B

31-E

31-F

34-A

34-B
21

9-1

40

41 d


a.
b.
G.
d.
b,c,d.


1

20

30

30
40

50
60

70
80

65

65

15
- 80b

100

-70


0.20

0.10

0.15

0.10

0.14

0.20

0.20

0.10

0.10

0.20

0.2Q

0.22

0.26

0.15

0.15


17.9

31.3

24.2

39.0
34.0

35.8
42.4

49.3

66.7

18.9

20.8

7

78

3.2

0


43.5

38*5
40.7

31.5
35.7

36.3
32.2

29.2

20.3

48.3

47.8

44

11

14.5

5.0


38.6

30.2

33.9
29.2

30.2

28.0

25.5
21.5

13.0

32.8

31.3
48

11

82.3

95.0


0.420

0.557

o.56oa
o0560a

0.583

0.597
0.655

0.705

0.815

0.435

0.455

0.265

0.882

0.090

0.02


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.


Figure 2.









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.






















40-

Log '0i
30-


0 0


Polymerization Temperature *C.


Figure 3.


Plot of log of the percentage of isotactic
fraction in the poly-(nethyl methacrylate)
samples versus the temperature of polymerization.


60-

50-


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.









CH&PT=R V1


SUMMARY




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
polymerization system.

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

51









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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BIOGRAPHICAL NOTES


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

period.

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

SUPERVISORY COMMITTEE



Chairman








Cl .\ 0#
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UNIVERSITY OF FLORIDA
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