Group Title: preparation and polymerization of certain diunsaturated phosphorus containing monomers
Title: The Preparation and polymerization of certain diunsaturated phosphorus containing monomers
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Title: The Preparation and polymerization of certain diunsaturated phosphorus containing monomers
Physical Description: vii, 66 l. : illus. ; 28 cm.
Language: English
Creator: Bond, William Cargill, 1938-
Publication Date: 1964
Copyright Date: 1964
 Subjects
Subject: Polymers and polymerization   ( lcsh )
Organophosphorus compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
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Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 63-65.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Bibliographic ID: UF00097921
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
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Resource Identifier: alephbibnum - 000433707
oclc - 11213568
notis - ACJ3381

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THE PREPARATION AND POLYMERIZATION

OF CERTAIN DIUNSATURATED PHOSPHORUS

CONTAINING MONOMERS










By
WILLIAM CARGILL BOND, JR.


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
April, 1964










DEDICATION



This dissertation is dedicated to my grandfather,

Mr. Morton M. Boyd.











ACKNOWLEDGMENTS


The author wishes to express his gratitude to

Dr. G. B. Butler for his counsel and encouragement in

the undertaking and completion of this work.

The author also wishes to express his appreciation

to his advisory committee and fellow graduate students

for their assistance, as well as understanding advice and

criticism.

Special thanks are due Mrs. Thyra Johnston for

typing this manuscript.

The financial support of the United States Air

Force and the National Science Foundation are gratefully

acknowledged.


iii











TABLE OF CONTENTS


DEDICATION . . . . . . .

ACEKNOWLEDGMENTS. . . . . . .

LIST OF TABLES . . . .

LIST OF FIGURES. . . . . . .

Chapter

I. INTRODUCTION . . . . .

Historical. . . . .

Development of the Problem.

Statement of the Problem. .

Discussion. . . . .

II. DISCUSSION OF RESULTS ..

Monomers. . . . . .

Polymers. . . . . .

Infrared Data . . . .

III. EXPERIMENTAL . . . . .


Source and Purification of M

Chemical Analyses . ..

Physical Measurements . .

Preparation of Intermediates

Preparation of Phosphines .

Preparation of Phosphonium S


. .

. .

. .

. .


Page

ii

iii

vi

vii


. . . 1

. . . 1

. . . 6

. . . . ?

. . . . 8

. . . . 18

. . . 18


. . . . 25

. . . . 33

. . . . 35

materials. . 35

. . . . 35

. . . . 36

. . . 36

. . . 40

alts. .... 47






Chapter Page

Polymerization of Phosphonium Salts. . 52

Preparation of Copolymers. . . . . 60

IV. SUMMARY ................... 62

BIBLIOGRAPHY. . . . . . . . . . 63

BIOGRAPHICAL SKETCH . . . . . . . . 66










LIST OF TABLES


Table Page

1. Physical Properties, Analytical Data, and
Yields of Intermediate Unsaturated
Phosphines . . . . . . . . 10

2. Physical Properties, Analytical Data, and
Yields of Unsaturated Phosphonium Salts. . 12

5. Physical Properties, Analytical Data, and
Yields of Phosphonium Polymers . . ... .52










LIST OF FIGURES


Figure Page

1. Intrinsic Viscosity Determination of
Phosphorus Containing Monomers . . ... 30


vii










CHAPTER I


INTRODUCTION


Historical


Walling (1) noted as early as 1945 that the gel-

point for some dienes should occur later than calculated

by Stockmayer's (2) equation, as the equation failed to

account for occasional cyclization. Later Butler and

Ingley (3) found that diallyl quaternary ammonium salts

showed no gel-point and were water soluble, while under

similar conditions, triallyl salts gave crosslinked polymers

and monoallyl salts did not polymerize. These results

seemed in direct contradiction to Staudinger's (4)

hypothesis that polymers of non-conjugated dienes would

yield only crosslinked polymers. Further study of the

poly-diallylammonium salts revealed little or no residual

unsaturation; thus, it seemed that complete polymerization

had taken place and yet the polymer had not crosslinked.

Butler and Angelo (5) proposed an alternating intra-

molecular-intermolecular chain process to explain how both

double bonds could be polymerized and yet a linear polymer

produced. According to their mechanism, one double bond






2

reacted with the initiator and the resulting radical, anion,

or cation in turn attacked intramolecularly the double bond

at the opposite end of the molecule. This produced a cyclic

secondary reactive site which attacked an adjacent monomer

molecule intermolecularly to give a polymer with saturated

cyclic recurring units separated by methylene groups. The

process, termed "Cyclopolymerization," can be illustrated

as follows:




P N B-CH B-CH-O
+ R" )


I II III




III H+ n


IV n+1



To prove the presence of the piperidinium ring,

Butler, Crawshaw, and Hiller (6) degraded poly-(diallyl-

ammonium bromide). The nitrogen was first benzoylated in

the presence of sodium hydroxide and then oxidized to open

the ring as shown:













2 IlHTTaOH "2
C6H COC1
0 5

IH OC65
n 6 5 n
V VI







VI + 4n04 ) C OOH

OC,H
o 5 n
VII




The structure of the product was proven by elemental

analysis, potentiometric titration, infrared spectra, and

upon heating it slightly above its melting point benzoic

acid was sublimed and the residual polymer was found to be

crosslinked and insoluble.

Since the cyclopolymerization mechanism was proposed

it has been extended to systems more numerous than can be

listed herein. However, a few of the more important should

be mentioned. marvel and Vest (7) polymerized a,a'-

dimethylene pimelate derivatives to essentially saturated

linear polymers. marvel and Stille (8) used a Ziegler type








initiator to polymerize 1,5-hexadiene and 1,6-heptadiene

which were the first hydrocarbon cyclic polymers prepared

by this mechanism. 1,6-Heptadiene showed no crosslinking

and was 90 per cent or more cyclic polymer. 1,5-Hexadiene,

as would be expected, gave more crosslinking and showed

less cyclization. Acrylic (9,10,11) and methacrylic (12)

anhydrides were polymerized to give molecular weights as

high as 95,000. Marvel and Gall (15) and Field (14) re-

ported the cyclopolymerization of 2,6-diphenyl-l,6-

heptadiene, which had a melting point of 300C. Not only

1,6- and 1,5-dienes have been cyclopolymerized, but Marvel

and Garrison (15) even obtained polymers from higher a-

diolefins giving rings with seven to twenty-one members.

All types of initiation have been used to produce

cyclic polymers; for example, acrylic anhydride (11), by

free radical initiation; diisocyanates (16,17) by anionic

initiation; diallylsilanes by (18) Ziegler initiation, and

2,6-diphenyl-l,6-heptadiene (14) by cationic initiation.

Besides the homopolymers referred to above, 1,4-

dienes have been shown to undergo cyclic copolymerization

to produce copolymers in which there are two moles of comer

to each mole of diene (19). The mechanism below has been

suggested for the reaction of divinyl ether with maleic

anhydride:







CH2==CH O- H Z* + ZCH2---CH -H2

VIII IX

HCO
CHCO Z- O--CH C
-2 CCH-CRI -2
I I
V0

x

/HCO IH-H

-4"
IH I
C pO


Alternate
repetition


XII


Monomer reactivity ratios (20,21) for certain of these co-
polymerizations have been calculated and are consistent
with the above mechanism.


I I
cVo








One of the most recent and more interesting phases

of cyclopolymerization is that in which doubly stranded or

ladder polymers are produced. Angelo (22) reported the

cyclopolymerization of poly-3,4-isoprene; Overberger (23),

the preparation of a ladder polymer of vinyl isocyanate by

either of the two mechanisms shown below.


0 0 0
II II II
--C-CH2 H_ Co60 N N N N

NCO
n

XIII XV

0 0 0 0 0
CH2==CH-N=C=0 | II It I

I NeCN_ ATBN
-550 8 ^

XIV XV
Soluble, 90% ladder polymer

The above polymers show a much higher thermal stability than

cyclic polymers connected by methylenes, and the latter tend

to be more stable than regular straight chain polymers.

Development of the Problem

Previously, several 1,6-diunsaturated phosphonium
bromides were prepared and polymerized by Skinner (24) to

give polymers containing repeating six-membered rings in








the backbone of the chain. These were either diallyl or

dimethallylphenylphosphonium bromides with the fourth sub-

stituent being either phenyl or alkyl.



H CH 2
R- --R

2 H2 BrR

C65NR'

6 5

)VI

R = H or CH ; R' = CH C2H5, C3H7, or C6,H


The polymers formed were soluble in ethanol and

dimethylformamide and their infrared spectra indicated

that they were free of unsaturation. Two of these were

converted to phosphine oxides and their infrared spectra

were found to be identical with phosphine oxide polymers

synthesized by another route (25).

Along with the six-membered rings it was decided to

determine if five-, unsymmetrical six-, seven-, and eight-

membered rings could be formed during polymerization. Thus,

the present project was initiated.


Statement of the Problem

The objectives of this investigation were as follows:









1. To synthesize a series of phosphonium salts which
could conceivably undergo cyclic polymerization to
give linear soluble polymers.

2. To determine the possibility of forming five-, six-,
seven-, and eight-membered rings from functional
groups other than diallyl or dimethallyl.

5. To isolate and study the properties of any soluble,
saturated polymer.

4. To show that cyclic copolymers of phosphines can be
formed and to study the copolymer obtained therefrom.


Discussion


The method of preparation of phosphonium halides

used in this research was that which had been previously

proven successful by Skinner (24), who prepared the diallyl-

and dimethallylphosphonium halides. The procedure des-

cribed by Jones and Davies (26) was followed in the

preparation of the phosphines. To these phosphines was

added an alkyl halide in dry ether, which usually resulted

in a good yield of the phosphonium salt.

Some of the phosphines prepared were diphenyl

substituted; thus, for example, diphenylchlorophosphine

was reacted with the appropriate Grignard reagent to yield

the unsaturated phosphine. The phosphine was then reacted

with an olefinic halide in ethyl ether to yield the di-

olefinic phosphonium salt. A generalized synthetic scheme

is shown below.









S5 65 R'X C65
C, CH CH R+

P--C1 + RI-gX ---- P--R P

CH CH C,HZ R'
o 5 o 5 o 5


XVII


XVIII


XIX


R = C-=CK- or CH=CHCH2CH-


X = Cl or Br


CH
1 3


R' = CH HC-, CH =-CH2, or CH2=CHCHCR

It was found in the literature that diphenylvinyl-

phosphine (27) had been previously synthesized but that

3-butenyldiphenylphosphine had not. The phosphonium

compounds prepared were all new compounds, none of which

were found in the literature. The monomers were used as

obtained from the last reaction in the scheme. Those

isolated were characterized by use of infrared spectra,

elemental analyses, and melting points. The values ob-

tained may be found in the experimental section, and in

Table 2.


The

work, were

refractive

analysis.

The values


phosphines, which were not isolated in previous

isolated and characterized by boiling point,

index, density, infrared spectra, and elemental

They were found to be pure and fairly stable.

obtained may be found in Table 1.













Lr( 0






H1 0


ON a\





C o
H 0

M3 M3
*s s
WW;
*T **


4 P
-d-


O0




s 0


m















rid-













0 4-
C
0)






















P-1
i-l )
tO p
,c29
(^ p


\D\D





CO 01
\Dn
*s *




COO
mO a\











Lr1
0'0'
a a





r4
o
0
















* C)
6 o
O C
CO *
O
H 0-


HH
H o
-drlrFp


H

p4
E-


H
a,
c


(1 H



C C







p-I (

a \
a\ CN


0 U












r I
LO











H
tu
e H



0 L-\


4 O





OF0
(e 0 p
O OMfy


Cc o(


CD a\





* *














C I
0 0






0 0

















O
0 *

















H0
H D
u u






























p..
4-1




















Hd






Od
0
= H h
rI C C

Fd (Ta 01



c
H H
0^0

ff^W



ff


CO
CM


p i
cu
H

















0I-


H
rJ-l


I 6

O 0





P-4 \ 0
p O







SI\ 11
r(u t U\ Lr\
(cO r-I






0 oH


I- rI-













00
** LC





rdo


V) 0 0

0 O



P4
flu l -

















0 o


1-1 0-% 01%



4 CO*
pi u p






















r








cO c




0 b CP4 '
HH H
~~ P C
*r4I ***























0


CO





0


H









P4



0
S






















-4














0
a
:








ca
B
p;


H H






co


.1-*


0
.a a"


to C o










.--t..
H CuH






p4



0
m \0 \0










Od -
iH





























i
*^t q,
*i c ^
PtU ^


m co
cu -











I'D'
.' .\


p4p
**. **.






COH
H H

0 0




0


0
I







p 4







o
In


CO
CO






c6c6












0
U CL1






**% **%

H


00
Sw












a'
m en

0







u





























H
r &


oJo
'D 0




*s *






0
0H 0















o
00
C u


om
0







0\
O 0




* 4





04
*H


-,- to






CO CO


00



pO

00i
CU
0

C4-4


p4
=I
S







a)


cO






UCO
k* *







u0










,l
\O\0

0














oS
0
c










p4



















4
Ld'
r^









I rO
rd




































m)
i-l


















































0
.Z
Pi4
O









.,,
p-'p








on4-


m




OJ r-I





6 H











Cr)
*" t *
-1 \


CO





CO 1-

co

CO 01


0101



H Hm












Cuj


r-I

0
0
Cu




















* 4












HO
P1-


0

1C


a~


0O

ir\ Ur1


P.r P4,

m *j
J .-r






CO Cu



0 0


t-
*














H
p;








*



rt
H


~IH
3


S.
s


0
\

OJ
Lrx


Cu













a,
24






r-I
rd
H


O



p4



Ck


O
rl1








A free radical initiator was used to start the
polymerization of the salts; tert-butylhydroperoxide in
water solution or a : '-azodi-iso-butyronitrile in dimethyl-
formamide was used respectively with the ammonium, and the
diallyl substituted phosphonium salts. However, neither
of these gave good results with the monomers prepared.
Benzoin and an ultraviolet light source gave more effective
initiation and a polymer which was easily recovered.
The mechanism for the polymerization of these
compounds would be expected to be similar to that proposed
by Butler and Angelo (5) in the polymerization of the
diallylammonium compounds. It can be represented, for
example, by the diphenyl substituted phosphonium compounds
in the following equations:


CH =C CH
(CH(c) (C ) + I. -..

CH +x-
(C6H5)2


R CH
I
I--H2-. CH

(cH2) (CH2)


(C6H5( +H












(cH2)
(C2 ) (C )



xxI
(mmH5 2










I I


+ -
(C6H52 n
R = H or CH XXIII
X = Br or CI
y or z = 0, 1, or 2


The study of the polymers produced consisted of an

elemental analysis, softening and melting range, infrared

spectra, and the intrinsic viscosity. The viscosities of

polyelectrolytes are difficult to determine due to ioni-

zation; however, usually this can be suppressed by using a

common ion. Even under these conditions, the viscosities

of the ionic polymers were ambiguous. To overcome this








difficulty, one of the phosphonium salts was converted to

the phosphine oxide which gave a more accurate viscosity

determination.

A number of 1,4-dienes have been cyclocopolymerized

with a variety of comers. For this reason, an attempt was

made to copolymerize divinylphenylphosphine with acrylo-

nitrile. According to the mechanism described earlier,

Butler (19) suggests that two moles of comer polymerize

with each mole of diene. This, however, was with maleic

anhydride which does not tend to homopolymerize. Using a

comer such as acrylonitrile, a mole percent greater than

two times the diene concentration is always obtained in

the polymer, due to the pronounced tendency of it to homo-

polymerize. The copolymer prepared had approximately three

times the mole percent of acrylonitrile and no residual

unsaturation. Thus, it is felt to be consistent with the

cyclocopolymerization mechanism but with a slightly greater

percent of acrylonitrile than predicted, due to its homo-

polymerization.

A sample of diallyldimethylphosphonium chloride was

prepared to determine if possibly in the aryl substituted

phosphonium compounds the phenyl groups were so large that

they restricted chain growth due to steric hindrance. The

method of synthesis of this monomer was entirely different

from that previously demonstrated. The procedure described








by Burg and Slota (28) was followed in which dimethylamino-

dichlorophosphine was reacted with a Grignard reagent,

producing the disubstituted dimethylaminophosphine. This

product was then reacted at a higher temperature and for

a longer period with another Grignard reagent which cleaved

the phosphorus-nitrogen bond and produced the trisubstituted

phosphine. This phosphine was then reacted with an alkyl

halide to yield the phosphonium salt desired. The total

synthesis is shown below.


CH3" 1
3(~


+ 2CH3MgBr --
1 hr.


CH3-NCH3
CH'C CH
3 3
XXv


+ CH2=CHCH2MgBr


XXVI + CHC -H-C1 -


330
Xay XVI 3
)3a1n:


C H2==CH-CH CH


C=CH- -C CH3

XXVII


XXV











CHAPTER II


DISCUSSION OF RESULTS


Monomers


In order to obtain the 3-butenyl substituted monomer

it was necessary to synthesize 4-bromo-l-butene. The

bromination of allylcarbinol was the only feasible route

found; however, the synthesis of this alcohol gave unde-

sirable by-products which at times constituted the entire

yield.

In the synthesis of allylcarbinol through the

reaction of vinylmagnesium halides with ethylene oxide,

it was observed that under certain conditions the pre-

dominant product was the halohydrin derived from ethylene

oxide rather than the expected alcohol. A further study

of this reaction indicated that a specific halogen ion

effect existed. Use of vinylmagnesium chloride leads to

better yields of allylcarbinol and to none or to minor

amounts of the ethylene chlorohydrin, while under the same

conditions, use of vinylmagnesium bromide leads to yields of

ethylene bromohydrin varying from 10 to 40 per cent, with a

corresponding reduction in the yields of allylcarbinol. In








both cases, the yields of allylcarbinol increased with

ethylene oxide/Grignard ratio, and with increasing

temperature of the reaction. The mechanism of this re-

action was not determined, as the results obtained were

not consistent. Two runs under apparently the same

conditions produced different yields of both halohydrin

and allylcarbinol.

The allylcarbinol obtained from the reaction could

be recovered in about 97 per cent purity, as analyzed by

vapor phase chromatography. It was converted to the

bromide by a modification of the reaction proposed by

Gaubert, Linstead, and Rydon (29). The bromide obtained

was also found to be about 97 per cent pure; thus, very

little had isomerized to crotyl bromide, as might be

expected. The 4-bromo-l-butene was then converted to the

Grignard reagent and reacted with the appropriate chloro-

phosphine to produce the 3-butenyl substituted phosphines.

Phosphines, as a group, are very reactive substances,

which is characteristic of all derivatives of trivalent

phosphorus. The lower aliphatic substituted derivatives

are, in fact, spontaneously combustible when exposed to

atmospheric oxygen. The tri-aryl phosphines are, on the

other hand, stable to air oxidation and can be stored for

long periods of time with no special precautions. The

mixed aryl-alkyl phosphines prepared lie between these two








extremes. Usually, the monophenyl substituted phosphines

were transferred and all open manipulations were carried

out in a nitrogen flushed dry box. The diphenyl substituted

derivatives were transferred under a flow of nitrogen and

did not oxidize appreciably. At elevated temperature both

types of phosphines oxidized readily. For this reason,

distillations were performed under nitrogen. Even small

amounts of oxygen present during distillation caused hazy,

impure distillates which were contaminated by the solid,

insoluble phosphine oxide.

After distillation, the aryl substituted phosphines

were usually reacted immediately with an alkyl halide dis-

solved in ether. In order to run refractive indices and

density measurements on the phosphines a small sample was

distilled and sealed under nitrogen. This fraction was

then placed in a nitrogen filled dry box where the refrac-

tive index was taken and a pychnometer, for density measure-

ments, could be filled without oxidation.

The aryl substituted phosphonium salts produced were

not extremely hygroscopic; however, presence of the smallest

amount of the very hygroscopic phosphine oxide impurity

caused deliquescence of the phosphonium salt. Therefore,

if a sample of phosphonium compound was contaminated to any

extent with the phosphine oxide it would form an oil and

could not be recrystallized, as the solubility of both the








salt and oxide were very similar. In the infrared region,

the phosphorus-oxygen bond in the phosphine oxide gave a
-l
broad, strong absorption at 1170 cm- and was found in a

number of the impure salts. Usually, when this peak was

present, it was also possible to see a strong absorption

at 3500 cm- due to water. When pure phosphonium salts

were produced, however, they showed neither absorption

and could be opened to the atmosphere and still remain

relatively free of water.

The dimethylphosphines prepared were extremely

sensitive to oxygen, and any exposure to the atmosphere

caused immediate oxidation of the product. The samples

were sealed in ampoules after distillation and neither the

refractive index nor density of the pure phosphine were

obtained. An infrared spectrum was run on allyldimethyl-

phosphine and it was found to contain a large amount of

oxide; however, the polymer of diallyldimethylphosphonium

chloride does not show the characteristic peak at 1170 cm-1

Thus, the phosphine must have oxidized during the spectral

analysis. The diallyldimethylphosphonium chloride produced

from the phosphine above was deliquescent and had to be

kept in a drying pistol over phosphoric anhydride. Even

with these precautions the elemental analysis was consistent

with the hypothesis that there was water in the sample and

the melting point, taken in a sealed tube, showed a wide









melting range and water condensed in the tube.

Discussion of the phosphines and phosphonium compounds

produced will be divided into three groups dependent upon

the number of phenyl substituents in the compound. Exami-

nation of the chemical structures, boiling points, and

reactivity of the phosphines suggests placing them in these

groups. Considering the diphenyl series first, allyl,

methallyl, and 3-butenyldiphenylphosphine were readily pro-

duced by the method described by Jones and Davies (26).

Their physical characteristics were as noted and their

stabilities were as described previously. The properties

of diphenylvinylphosphine were surprising because it was the

least stable of all the diphenyl substituted phosphines

prepared. One would expect the vinyl group to increase the

stability of the phosphine in a manner somewhat analogous

to an aryl substituent rather than to an alkyl substituent

since it has the possibility of stabilizing the pair of free

electrons on the phosphorus atom by forming a resonance

hybrid similar to that of a phenyl group (30). In fact,

both nuclear magnetic resonance and infrared spectra show

that there is some type of interaction between the pi cloud

of the double bond and the pair of electrons on the

phosphorus atom. A similar interaction, but to a much

greater extent, was found in the ultraviolet spectra of

vinyl substituted amines (31). The vinyl substituted








phosphines, unfortunately, did not show an absorption

maxima within the reliable range of the instrument when

their ultraviolet spectra were run. Thus, they could not

be studied by this means.

The phosphonium salts obtained from diphenylvinyl-

phosphine were very difficult to isolate in any degree of

purity. Allyl bromide, which alkenyl bromide reacts most

rapidly with the phosphines, formed the purest salt. As

the rate of reaction decreased, so did the purity of the

monomer obtained directly from the reaction mixture.

Methallyl chloride, which is quite slow in its reaction,

did not give any isolatable salt in numerous attempted

preparations.

The diaryl substituted phosphonium salts prepared

for polymerization were all synthesized starting with one

of the four diphenyl phosphines mentioned above. The

phosphonium compounds produced from diphenylvinylphosphine

have already been mentioned; those from the other phosphines

were easily prepared in good yields and high purity. The

alkyl chlorides were always much slower to react with the

phosphines than the bromides but often gave a better yield

of monomer.

In the second group, the monophenyl substituted

derivatives, divinyl-, diallyl- and di-5-butenylphenyl-

phosphines were prepared. They all showed similar









characteristics: they were more reactive toward oxygen and

all had lower boiling points than the corresponding diphenyl

substituted phosphines. Divinylphenylphosphine, similar to

the diphenylvinyl derivative, showed much less stability

and colored rapidly on standing, even under nitrogen. The

diallylphenyl-, and di-3-butenylphenylphosphines were

prepared for use in the preparation of boron-phosphorus

intermediates in other work (32), and also as alternate

synthetic intermediates in this work. Diallylphenylphos-

phine had been previously prepared by Jones and Davies (26)

but di-3-butenylphenyl was a new compound and its physical

characteristics were determined.

The last group of phosphines prepared were the

dimethyl substituted. It was decided that perhaps the

large phenyl groups were causing steric hindrance during

polymerization and by replacing these with methyl groups

higher molecular weight polymers with superior character-

istics might be obtained. The procedure described by Burg

and Slota (28) had not been applied to the synthesis of

unsaturated methyl phosphines. The method did yield a

satisfactory phosphine which was readily converted to the

phosphonium salt. The phosphine and the salt produced from

it are both new compounds; however, their physical

characteristics could not be measured due to their extreme

sensitivity to the atmosphere.








Polymers


Since the phosphonium compounds are ionic in

character, the use of anionic or cationic initiation is

precluded. It is also known that Ziegler-Natta catalysts

are poisoned by this type of system (33). Therefore, free

radical initiation was chosen for the polymerization of

the monomers. This method of initiation presents the

complication that hydrogens a to the double bonds are

easily extracted by free radicals causing degradative chain

transfer and essentially termination of the polymer chain.

The choice of which free radical initiator to use

was dependent on previous work. The first choice was ac '

azodi-iso-butyronitrile in dimethylformamide. This had

been found to give polymers by Skinner (24) in his work

with diallyl and dimethallyl substituted phosphonium

bromides. He found that polymers obtained using this type

of initiation were difficult to isolate and none had an

intrinsic viscosity ([E]) above 0.04. Tert-butyl hydro-

peroxide had been used effectively with the quaternary

ammonium salts but was found to give much poorer yields of

phosphonium polymer. In an attempt to produce higher

molecular weight polymers which would be easier to isolate,

benzoin and ultraviolet irradiation were used. This

catalyst was indeed found to give higher molecular weight








polymers, ([q] = 0.025 for five-membered rings to 0.08 for

six-membered rings) which were easily isolated from acetone

as white amorphous solids. The infrared spectra of some of

the polymers indicated that they contained up to 10 per cent

residual unsaturation. This was difficult to explain since

the polymers described by Skinner had been reported to be

saturated. The difference between the polymers presented

here and those produced in Skinner's work is the result of

the difference in initiator concentrations used. His

polymerizations were all run using 4 per cent initiator,

while the benzoin concentration was 0.1 per cent in the

polymerizations which left residual unsaturation. Polymers

produced using 1 per cent or more benzoin as initiator were

found to be essentially saturated as determined by absorption

in the infrared spectra at 935 cm-1. Therefore, the majority

of polymerizations in this work were carried out using an

initiator concentration of 2 per cent.

Solution polymerization was used throughout this

study. In the benzoin initiated polymerizations, almost

saturated aqueous solutions (50%, by weight) were used. No

bulk polymerizations were attempted, as the phosphonium

monomers were very high melting.

The polymers obtained from the phosphonium monomers

discussed earlier were soluble in ethanol and dimethyl-

formamide. Those produced with more than 1 per cent








initiator showed little or no absorption in the infrared

region corresponding to residual unsaturation. The

softening points of the polymers were much higher than the

melting points of the corresponding monomers; the results

of the analyses indicated that the polymers were isolated

with one molecule of water per phosphonium unit.

The properties of these aryl phosphonium polymers

were consistent with those predicted by the cyclic mechanism

proposed by Butler and Angelo (5), since they were

essentially saturated and soluble. Their tendency to form

monohydrates 'was! consistent with the observations made by

Skinner (24). The conversion of poly-(diallyldiphenyl-

phosphonium bromide) to poly-diallylphenylphosphine oxide)

was an additional proof of cyclization since the infrared

spectrum of the phosphine oxide obtained was identical with

the spectrum obtained by Berlin (25) who polymerized

diallylphenylphosphine oxide to yield a cyclic polymer.

All of the diolefinic monomers synthesized produced

polymers, except vinyl-3-butenyldiphenyl, and di-3-butenyl-

diphenylphosphonium bromides. It is quite surprising that

the former compound did not polymerize, if not by way of the

cyclic mechanism to produce the six-membered ring structure,

by way of the vinyl group. The fact that the latter com-

pound did not polymerize is not too surprising since cyclic

polymerization would require formation of an eight-membered








ring. Also, the 3-butenyl double bond is not very reactive

toward free radical initiators.

The specific viscosities of the polymers were calcu-

lated using this equation (54):


t t
rsp = t


where t is the flow time of the sample and t is the flow

time of the solvent. The intrinsic viscosity [q] was de-

termined by graphically plotting specific viscosity divided

by concentration versus concentration and extrapolating to

zero concentration. Intrinsic viscosity is defined by the

following expression:


Sc = 0o

The viscosity data for the poly-phosphonium salts

were typical of the data for polyelectrolytes in general.

It was reported (35) that the viscosity curves ('sp/C vs. C)

of polyelectrolytes were strongly concave upward, in con-

trast to the behavior of uncharged linear polymers. This

was believed to be due to the dissociation of the ionic

bond in the solution which lead to large repulsive forces

between the positively charged groups remaining on the

chain. These forces gave rise to greatly expanded configu-

rations and very large intrinsic viscosities. At high







concentrations, the molecules in the polyelectrolyte had not

been significantly ionized and tended to partially overlap;

thus, they were not appreciably expanded. As the solution

is diluted, the molecules no longer filled all the space

and some of the halide ions left the regions of the chains.

This caused a development of charge and extension of the

chains. The addition of a strong electrolyte suppressed

the loss of halide ion and the viscosity behavior became

more normal. However, the intrinsic viscosity is dependent

on the volume of the polymer in the solution and it was

found that added electrolyte compressed the hydrodynamic

unit corresponding to the polyelectrolyte. The compression

changed the shape of the polymer and caused a marked de-

crease in the viscosity of the solution. Thus, the term

intrinsic viscosity, for a polyelectrolyte can not be used

in the same sense as for an uncharged polymer since it is

dependent entirely on the concentration of added salt.

This type of behavior was exhibited by the poly-phosphonium

compounds and is illustrated in Figure 1. In line I the

poly-phosphonium bromide was dissolved in ethanol, and as

was expected, sp/c tended to increase with dilution.

Addition of a strong electrolyte, such as a potassium halide,

provided a common ion effect which repressed the ionization

of the polymer. At this time the viscosity behaved similar

to a linear uncharged polymer, as shown by line III. Line II











0.40 -


0


0.30--

nsp/c


0.20 -
IV



0.10 -





0 0.4 0.8 1.Z
g./deciliter

Plots of nsp/ against c for:
c
I Poly-(diallyldiphenylphosphonium bromide) in 95% ethanol.
II Poly-(diallyldiphenylphosphonium chloride in a 1.0 M 1:1
ethanol-water solution of potassium chloride.
III Poly-(diallyldiphenylphosphonium bromide) in 1:1 ethanol-
water 0.1 M in potassium bromide.
IV Poly-(diallylphenylphosphine oxide) in 95% ethanol.






Fig. 1.-Intrinsic Viscosity Determinations of Phosphorus
Containing Monomers








represents poly-diallyldiphenylphosphonium chloride rather

than the bromide; but demonstrates an intermediate change

between line I and III where insufficient common ion was

present to completely repress ionization. Line IV represents

the viscosity of the phosphine oxide, which was produced from

the same sample of diallyldiphenylphosphonium bromide used

for the determination of line III. The intrinsic viscosity

for the phosphine oxide polymer was probably the most

reliable, as it was not a polyelectrolyte and can not be

affected by ion concentrations.

The intrinsic viscosity measurements for the phos-

phonium compounds will be given in the experimental section

and in Table 5.

Copolymers of divinyl compounds have been known for

some time. Divinyl ether (56) and divinylaniline (20) were

both copolymerized to yield cyclic copolymers with a variety

of comers. Since divinylaniline is very similar to divinyl-

phenylphosphine it was felt that copolymers could be easily

obtained. However, previous experiments with divinylphenyl-

phosphine and maleic anhydride had been attempted and no

polymer was produced (37). The copolymerization with

acrylonitrile gave a brilliant red, brittle, solid which

contained approximately three moles of acrylonitrile for

each mole of divinylphenylphosphine. The percent of

acrylonitrile in the polymer increased as the concentration







\, cY 0 o 0 co t-
H---. H CN Cj ON\D 0 t-
C( J1 H O 0 01 H H 0
1OJ OJ C\J C'J H CJ J1 H
- *. - *, 0. 1

-ri m r l u


CO 1 H co co o oo oo o\ H
CC H H 01 LA (1 LO -4

*H



O i H **





0 0 0
N PC01 O C O CO

2O H 1 H-









SII II II *rII H c
*fr








,4
O 0 o 0 0 0 0 0 0 0

d GJ4 4-3 4- 0)
P-i EP cvj o- P4 0 0U 200




0n ) m m
0 I I II *
P H 0 0 P- O 0
gu t" o a c t co s co f u

14-

H

a 'd




*H
m o o
j 0 a C 0 0 A 0
S)P *m *H *H *H *H *H








S 0 0 0 0 0
-4 N








N (U O
H

,Co (U a H H H


,, O Hj >' i-i 'dp ( C I dl








of that comer increased in the initial charge. The co-

polymer produced was soluble in dimethylformamide and showed

no residual unsaturation. Thus, it had. apparently undergone

cyclocopolymerization. The excess acrylonitrile in the

polymer was most likely due to its strong-tendency to under-

go homopolymerization. The copolymer also exhibited a

broad absorption in its infrared spectrum at 1170 cm- which

corresponds with the phosphine oxide; thus, the phosphine

probably was oxidized during the work-up of the polymer.


Infrared Data


Using infrared techniques it was possible to deter-

mine the presence of phosphine oxide in the monomers, the

amount or absence of residual unsaturation in the polymers,

and also the purity of the phosphines. These determinations

were mentioned earlier and also the use of this technique

was discussed in great detail by Skinner (24). The

spectral data obtained for the vinyl substituted phosphines

weredifferent, in that, the non-conjugated carbon-carbon

stretching vibration at 1640 cm-1 present in all the other

phosphine spectra was absent in the vinylphosphines. This

was probably due to the conjugation of the double bond with

the pair of electrons on phosphorus. The nuclear magnetic

resonance of these compounds did, indeed, show that there

was conjugation of this type present. The CH and CH2 out of







-I
plane deformations at 990 and 910 cm- respectively, were

present in the spectra of all the compounds, thus, it was

felt that the vinyl substituted phosphines merely did not

show the expected peak at 1640 cm-1 due to its conjugation.

In allyldimethylphosphine, a medium band was found

at 1290 cm-1 which corresponded to an asymmetric CH3 de-

formation mode. This peak had shifted in the polymer to

1305 cm-1. This shift was expected, due to the change from

trivalent to pentavalent linkages in the phosphorus molecule.

This had been described by Bellamy (38). A strong band at

1630 cm-1 was found for the vinyl stretching vibration in

the dimethyl substituted phosphine. This peak disappeared

in the polymer; thus, it was felt that the polymer was

essentially saturated.










CHAPTER III


EXPERIMENTAL


Source and Purification of Materials


The diphenylchlorophosphine and dichlorophenyl-

phosphine were generously donated by Victor Chemical

Company. They were distilled under nitrogen before use.

From Peninsular ChemResearch Incorporated was

purchased ethylene oxide, phosphorus tribromide, vinyl-

magnesium chloride in tetrahydrofuran, and methylmagnesium

bromide in ethyl ether, all of which were used as received.

Also purchased from the same source were dimethylamino-

dichlorophosphine, tetrahydrofuran, and allylbromide which

were redistilled before use.


Chemical Analyses


The majority of the chemical analyses were determined

by Galbraith Laboratories of Knoxville, Tennessee. The

analyses of the phosphonium salts and polymers were

generally low in carbon; therefore, a method was devised by

the university analytical department which in many cases

gave superior results. Where these are reported, it will

be so noted.








Physical Measurements


All temperatures reported are uncorrected and

reported in degrees centigrade. Pressures are expressed

in millimeters of mercury, having been determined by means

of either a Zimmerli or McLeod gauge.

Infrared spectra were obtained with a Perkin-Elmer

Infracord Double-beam Infrared Recording Spectrophotometer,

while Ultraviolet spectra were run on a Bausch and Lomb

Spectronic 505 Recording Spectrophotometer.

Refractive indices were determined on a Bausch and

Lomb Abbe 34 Refractometer equipped with an anchromatic

compensating prism.

Nuclear magnetic resonance spectra were obtained on

a Varian U-4302 High Resolution Nuclear Magnetic Resonance

Spectrometer.

Melting point determinations were carried out in

open capillary tubes in a Thomas-Hoover Melting Point

Apparatus.

Intrinsic viscosities were calculated from efflux

times of solution through a Cannon-Ubbelohde Semi-Micro

Dilution Viscometer at 250 in a constant temperature bath.


Preparation of Intermediates


Allylmagnesium bromide.-This reagent was prepared

by the method of Grummitt, Budewitz, and Chudd (39), To







a five-liter, three-necked flask, equipped with a reflux

condenser, addition funnel and mechanical stirrer, was

added 85 g. (3.5 g.-atoms) of magnesium turnings and 1.75

liters of dry ethyl ether. The flask was flushed with dry

nitrogen. Two hundred and twelve grams (1.75 moles) of

allyl bromide was weighed out and a few milliliters added

to the flask, with stirring. When the ether began to

reflux, the mixture was cooled with an ice bath, and the

remainder of the allyl bromide, diluted with an equal

volume of ether, was added dropwise over a period of nine

hours. During this time the flask was cooled in the ice

bath. When the addition was complete, the mixture was

stirred for an additional hour and then two 1 ml. aliquots

were titrated. The solution was found to contain 1.65

equivalents of the allylmagnesium bromide; yield, 94 per

cent.

Nethallylmagnesium chloride.-Using the same method

(59) as was used for the preparation of allylmagnesium

bromide, 48 g. (2 g.-atoms) of magnesium turnings were

placed in a one-liter, three-necked flask fitted with a

stirrer, condenser, and constant pressure addition funnel.

The flask was flushed with dry nitrogen and a constant

flow was maintained during the reaction. Dry ethyl ether

(500 ml.) was added and the flask placed in an ice bath.








One ml. of ethyl bromide was added and the reaction mass

was stirred for ten minutes. Ninety-one grams (1 mole) of

methallyl chloride in an equal volume of ether was added,

with stirring, over a four-hour period. The smooth

suspension produced was too thick to analyze by titration.

Allylcarbinol.-This compound was prepared by a

modification of the procedure of Ramsden, Leebrick, et al.

(40). To 382 ml. (1 mole of 2.62 molar) of vinylmagnesium

chloride in tetrahydrofuran was slowly added 44 g. (1 mole)

of ethylene oxide dissolved in 100 ml. of tetrahydrofuran.

The temperature rose immediately and was maintained'at

55-600 during the addition, after which the reaction

mixture was refluxed for one hour. The tetrahydrofuran

was then removed at water aspirator pressure until a thick

paste formed which was poured into a solution of 100 g. of

ammonium chloride dissolved in 500 ml. of water. The

hydrolysis was quite exothermic. The layers failed to

separate until 100 ml. of 37 per cent hydrochloric acid

was added. The organic layer was removed and the water

layer extracted with two 150 ml. portions of ether. The

organic portions were combined, dried over anhydrous sodium

sulfate, and fractionated. The alcohol was removed by

distillation at 112-1150 through an 80 cm. Vigreux at

atmospheric pressure to yield 48.2 g. (67%) of allylcarbinol,
20 20
nD 1.4255, lit. (41), n2 1.4234, b.p. 112-1140.








4-Bromo-l-butene.-The method of Gaubert, Linstead,

and Rydon (29), was used in this synthesis. To a nitrogen

flushed one-liter, four-necked flask, in an ice bath,

equipped with a stirrer, condenser, thermometer, and con-

stant pressure addition funnel was added a solution of

145 g. (2 moles) of allylcarbinol and 60 g. of pyridine.

To the solution was slowly added 300 g. (1 mole) of

phosphorus tribromide. The addition required three hours,

while the temperature was kept below 150. The reaction

was refluxed one-half hour and distilled until thick white

fumes appeared. The distillate was washed with 1001ml.

of 10 per cent sodium hydroxide and then two 100 ml.

portions of water. The product was distilled through an

80 cm. Vigreux column to yield 185.6 g. (69%) of 4-bromo-
20
1-butene, b.p. 98-1000, nD 1.4628, lit. (42), b.p. 99,

nD 21.4625.

3-Butenylmagnesium bromide.-To a nitrogen flushed

two-liter, four-necked flask, in an ice bath, equipped as

in the previous experiment, containing 36.5 g. (1.5 g.-

atoms) of magnesium and enough dry ether to cover it was

added 1 ml. of 4-bromo-l-butene. The reaction was started

and 150 ml. of dry ether added. A solution of 135 g. (1

mole) of 4-bromo-l-butene in 250 ml. of dry ether was added

over a three-hour period keeping the temperature below 200.








After complete addition the reaction was stirred another

three hours. The solution was titrated and found to be 95

per cent 5-butenylmagnesium bromide.


Preparation of Phosphines


A general method, developed by Jones and Davies

(26), was used in all the aryl substituted phosphine

syntheses. The phosphine preparations were carried out in

a one-liter, four-necked flask, equipped with a stirrer,

thermometer, condenser, and constant pressure addition

funnel allowing nitrogen to flow slowly through the system

at all times. The temperature during the reaction of the

Grignard reagent with the phosphorus halide was maintained

at 10-150. The phosphines were always prepared, stored,

and reacted under an atmosphere of dry nitrogen. If any

reactions were carried out under conditions which varied

from the above description, these changes will be noted

in the specific experiment.

Diphenylvinylphosphine.-One mole of vinylmagnesium

chloride in tetrahydrofuran was cooled in an ice bath and

88 g. (0.4 mole) of diphenylchlorophosphine in 100 ml. of

dry ether was slowly added. After complete addition, the

mixture was refluxed for two hours then cooled to 100. A

solution of 100 g. of ammonium chloride in 500 ml. of water







was slowly added (very exothermic). To the emulsion formed

was added 300 ml. ethyl ether and the layers separated.

The aqueous layer was extracted with two 100 ml. portions

of ether, and the organic portions were combined and dried

over anhydrous sodium sulfate. The solvents were removed

and the residual oil distilled through an 80 cm. Vigreux

column at 0.25 mm., to yield 56.2 g. (67%) of diphenyl-

vinylphosphine, b.p. 1040, n19 1.6289, d0 1.054 g./cc.,

lit. (43), b.p. 105.5-104.8/0.24 mm., n27 1.6229.
lit.n 16229.

Allyldiphenylphosphine.-To 1 mole of allylmagnesidm

bromide in 250 ml. of dry ether, at ice temperature, was

added 88 g. (0.4 mole) of diphenylchlorophosphine over a

two hour period. The mixture was refluxed one-half hour

and again cooled in an ice bath. The reaction mass was

hydrolyzed using a solution of 100 g. of ammonium chloride

in 500 ml. of water. The organic layer was separated and

combined with two 100 ml. ether extractions of the water

layer. The combined ether solutions were then dried over

anhydrous magnesium sulfate. The liquid was decanted into

a distilling flask fitted with a nitrogen bubbler and a

vacuum-jacketed Vigreux column. The ethyl ether was

stripped off at reduced pressure and the product distilled

at 0.4 mm. to yield 60 g. (66%) of allyldiphenylphosphine,
21 20
b.p. 106-108, n21 1.6197, d0 1.033 g./cc., lit. (44),

b.p. 114/0.7 mm.









Diphenylmethallylphosphine.-To a solution of 1 mole

of freshly prepared methallylmagnesium chloride in ethyl

ether, at ice temperature, was added 88 g. (0.4 mole) of

diphenylchlorophosphine in 250 ml. of dry ether over a two-

hour period. The mixture was then refluxed for one-half

hour and again cooled in an ice bath. It was hydrolyzed

with a solution of 100 g. of ammonium chloride in 500 ml.

of water. The organic layer was removed and the aqueous

phase extracted with two 150 ml. portions of ethyl ether.

The ethereal extracts were combined with the organic

portion and this solution was dried over anhydrous sodium

sulfate. The ether was removed at atmospheric pressure

and the product distilled through an 80 cm. Vigreux column

at 0.25 mm. to yield 61 g. (63%) of diphenylmethallyl-

phosphine, b.p. 110-111, n20 1.6089, d0 1.051 g./cc; lit.

(24), b.p. 118-1200/0.45 mm.

Anal. Calcd. for C16H17P: C, 79.98; H, 7.13;

P, 12.89. Found: C, 79.78; H, 7.25; P, 12.81.

3-Butenyldiphenylphosphine.-To 0.7 mole of freshly

prepared 3-butenylmagnesium bromide in ethyl ether, at ice

temperature, was added 88 g. (0.4 mole) of diphenyl-

phosphinious chloride in 200 ml. of dry ether. The reaction

was very exothermic and the addition required four hours.

The solution was allowed to come to room temperature and







was stirred overnight under nitrogen. It was then

hydrolyzed with a solution of 100 g. of ammonium chloride

in 500 ml. water. The organic layer and three 100 ml.

extracts of the water layer were combined and dried over

anhydrous sodium sulfate. The ether was stripped off at

reduced pressure and the product fractionated through an

80 cm. Vigreux column. The yield of 3-butenyldiphenyl-

phosphine was 79.5 g. (85%), b.p. 115-1150/0.3 mm., nD

1.5991, d0 1.028 g./cc.
Anal. Calcd. for C16H17P: C, 79.98; H, 7.13;

P, 12.89. Found: C, 79.80; H, 7.02; P, 12.95.

Divinylphenylphosphine.-To a solution of 1 mole of

vinylmagnesium chloride (2.56 molar in tetrahydrofuran)

was added 45 g. (0.25 mole) of dichlorophenylphosphine in

50 ml. of dry benzene; the addition required six hours.

At the end of this time the solution was refluxed one hour

and then cooled to ice temperature. The reaction mass was

decomposed by adding a solution of 100 g. of ammonium

chloride in 500 ml. of water. An emulsion and a large

quantity of yellow solid were formed. The solid was

filtered off and washed with 150 ml. of ether. The layers

were separated, and the water layer extracted with two

150 ml. portions of ether; the combined organic portions

were dried over anhydrous magnesium sulfate. The solvents

were removed at water aspirator pressure and the residue

was distilled under vacuum. The product was a water white








liquid boiling at 520/0.8 mm., giving a yield of 19 g. (47%)
20
of divinylphenylphosphine, n20 1.5822; lit. (27), b.p.

54.5-550/1o5 mm., n2 1.5832.

Diallylphenylphosphine.-To 1.75 moles of freshly

prepared allylmagnesium bromide, at ice temperature, was

added 87 g. (0.486 mole) of dichlorophenylphosphine in

150 ml. of dry ether. The temperature was kept at 20-250.

The addition required two hours. The reaction was then

refluxed two hours, cooled in an ice bath, and hydrolyzed

with a solution of 100 g. of ammonium chloride in 500 ml.

of water. The layers were separated and the aqueous layer

extracted with two 200 mli portions of ether. The organic

portion and ether extracts were combined and dried over

anhydrous sodium sulfate. The ether was distilled and the

residue fractionated at 0.7 mm. through an 80 cm. Vigreux

column to yield 41.2 g. (44.6%) of diallylphenylphosphine,

bp. 790, n25 1.5676; lit. (45), b.p. 1180/7-8 mm.,
25
n5 1.5670.

Di-3-buteniylhenylphosphine.-To a solution of 0.38

mole of 3-butenylmagnesium bromide in ether, cooled in an

ice bath, was added 27 g. (0.15 mole) of dichlorophenyl-

phosphine. The temperature was held at 5-100 during

addition and then raised to reflux for two hours. At this

time, there was a large quantity of white pasty solid,








which had precipitated out of the solution. The reaction

was cooled to ice temperature and 250 ml. of 20 per cent

ammonium chloride solution was slowly added. The layers

separated and the water layer was extracted with two 100 ml.

portions of ether. The organic portion was combined with

the ether extracts and dried over anhydrous sodium sulfate.

The product was fractionated through an 80 cm. Vigreux

column at 0.3 mm. to yield 13 g. (535) of di-3-butenyl-
20 21
phenylphosphine, b.p. 85-88, nD2 1.5448, d 0.9467 g./cc.

Anal. Calcd. for C H- P: C, 77.00; H, 8.78;
-- 14 -9
P, 14.20. Found: C, 76.39; H, 9.34; P, 14.07.

Dimethylaminodimethylohosohine.o-This compound was

prepared by the method described by Burg and Slota (28).

To 97 g. (0.66 mole) of dichlorodimethylaminophosphine in

1 liter of dry ether at -500 was added 460 ml. (1.32 moles

of 2.87 molar) of methylmagnesium bromide in ethyl ether.

A white solid formed immedia-ely upon addition. After

about three-fourths of the Grignard solution had been added,

the stirrer was stopped by the solid material which formed.

When the addition was complete, the flask was allowed to

warm to room temperature and th. solid suspension could be

stirred. After stirring one day, the ether was removed by

use of a filter stick and the solid washed with three 250 ml.

portions of ether. The solutions were combined, dried, and









the ether removed by distillation. The product which was

distilled through a Vigreux column at 990 resulted in a

yield of 14 g. (18.5%) of dimethylaminodimethylphosphine.

Lit. (28), b.p. 99.40.. Densities and refractive indices

were not run for the non-aromatic phosphines, as they were

spontaneously ignited in air.

Allyldimethylphosphine.-Following the general method

described by Burg and Slota (28), 11.5 g. (0.10 mole) of

dimethylaminodimethylphosphine and 20 ml. of dry ether were

added to a nitrogen flushed flask and cooled to 100. To

this solution was added 60 ml. (0.102 mole) of allyl-

magnesium bromide. There was no exothermic reaction, so

the flask was allowed to warm to room temperature. After

about five hours, a dark colored oil had separated from

the solution and the ethereal layer was clear. After one

day of stirring, the oil had become solid and the ethereal

solution was removed by use of a filter stick which was

dipped into the solution. The ether was distilled and the

residual oil fractionated on a spinning band column. The

fraction boiling from 91-990 gave 3.6 g. (35.2%) of dimethyl-

allylphosphine. The infrared spectrum indicated that the

desired product was obtained; however, a strong band at

1170 cm-1 indicated that some oxidation to the oxide had

occurred.








Anal. Calcd. for C 5H P: C, 58.80; H, 10.86.

Found: C, 58.42; H, 11.58.


Preparation of Phosphonium Salts


The general method for preparation of phosphonium

compounds, as described by Skinner (24), was followed. A

solution of the appropriate alkyl halide was added to a

100 ml. three-necked flask containing the phosphine.

Following this, the flask was removed from the distillation

apparatus and stoppered under an atmosphere of nitrogen.

All analyses referenced with an (*) were determined by

C. D. Miller of the Analytical Division, Department of

Chemistry, University of Florida.

3-Butenyldiphenylvinylphosphonium bromide.-To 10 g.

(0.047 mole) of diphenylvinylphosphine in a nitrogen flushed

flask was added 20 ml. of dry reagent grade acetone and

21 g. (0.16 mole) 4-bromo-l-butene. The flask was stoppered

and allowed to stand at room temperature for three days, at

which time the solid which had been produced was filtered,

washed with acetone and collected. A yield of 10 g. (61%)

of 3-butenyldiphenylvinylphosphonium bromide, m.p. 163-170,

was obtained. The sample was slightly impure but further

attempts at purification were unsuccessful.

Anal. Calcd. for C18H20PBr: C, 62.26; H, 5.81;

P, 8.72. Found: C*, 61.07; H, 6.12; P, 8.85.








Allyldiphenylvinylphosphonium bromide.-To 24.6 g.

(0.11 mole) of diphenylvinylphosphine in a nitrogen

flushed, ice cooled, flask was added 15 g. (0.123 mole)

of allyl bromide in 40 ml. of dry ether. The reaction

was exothermic and even in an ice bath was very rapid.

Within two hours, the flask was filled with a white solid.

The solid was removed and washed in an Erlenmeyer flask

with a large excess of acetone. A yield of 12.5 g.

(32.3%) of allyldiphenylvinylphosphonium bromide, a white

powdery solid, m.p. 169-1710, was collected.

Anal. Calcd. for C17H18PBr: C, 61.28; H, 5.44;

P, 9.23. Found: C, 61.18; H, 5.87; P, 9.18.

Diphenylmethallylvinylphosphonium chloride.-To 10 g.

(0.047 mole) of diphenylvinylphosphine in 50 ml. of dry

ether was added 17 g. (0.16 mole) of methallyl chloride.

The flask was sealed and allowed to stand twenty days,

under nitrogen. At this time, a small amount of white

crystalline deposit had formed, was collected and washed

with dry ether. In this and three other attempts it was

not possible to isolate a pure sample of the phosphonium

compound desired.

Allyl-3-butenyldiphenylphosphonium bromide.-To 30 g.

(0.155 mole) of freshly distilled 3-butenyldiphenyl-

phosphine in 50 ml. of dry ether was added 48.5 g. (0.4 mole)








of allyl bromide. The flask was placed in a beaker of ice.

After the ice melted the reaction was allowed to come to

room temperature. It was left three days, filtered, washed

with ether and collected. The product was dried in a

vacuum desiccator and gave a yield of 37 g. (87.8%) of

allyl-3-butenyldiphenylphosphonium bromide, melting at

139-1420.

Anal. Calcd. for C19H22PBr: C, 63.17; H, 6.14;

P, 8.57. Found: C, 63.15; H, 6.24; P, 8.57.

3-ButenyldiDhenylmethallylphosphonium chloride.-To

24 g. (0.1 mole) of 3-butenyldiphenylphosphine was added

36.2 g. (0.4 mole) of methallyl chloride in 50 ml. of dry

ether. The flask was sealed under nitrogen and allowed to

stand twelve days, at which time long needle like crystals

were collected and washed with ether. The mother liquor

and washings were allowed to stand another twelve days and

more crystals were collected. The total yield was 32 g.

(97%) of 3-butenyldiphenylmethallylphosphonium chloride,
melting at 175-1770.

Anal. Calcd. for C20H24PCl: C, 72.60; H, 7.31;

P, 9.36. Found: C, 72.06; H, 7.07; P, 9.60.

Di-3-butenyldiphenylphosphonium bromide.-To a

nitrogen flushed flask containing 22.5 g. (0.093 mole) of

3-butenyldiphenylphosphine was added 13.5 g. (0.1 mole)









4-bromo-l-butene in 25 ml. dry ether. The flask was sealed

and allowed to stand at room temperature for fifteen days,

after which the crystalline solid was filtered, washed,

and dried. The product was 9.3 g. (35%) of di-3-butenyl-

diphenylphosphonium bromide, m.p. 115-117.

Anal. Calcd. for C20H24PBr: C, 63.85; H, 6.45;

P, 8.25. Found: C, 63.36; H, 6.74; P, 8.57.

Diallyldiphenylphosphonium bromide.-To 22.6 g.

(0.1 mole) of allyldiphenylphosphine in 100 ml. of dry

ether, at 0, was added 48 g. (0.4 mole) of allyl bromide.

The reaction was quite rapid and fairly exothermic. After

two hours, it was allowed to come to room temperature.

Three days later the precipitate which formed was filtered,

washed with ether, collected and dried in a vacuum desic-

cator. A yield of 30.5 g. (88%) of diallyldiphenyl-

phosphonium bromide, m.p. 173-1760; lit. (24), 155-1570,

was obtained.

Anal. Calcd. for C18H20PBr: C, 62.25; H, 5.80.

Found: C*, 62.29; H*, 5.78.

Diallyldiphenylphosphonium chloride.-To 22.6 g.

(0.1 mole) of freshly distilled allyldiphenylphosphine,

under nitrogen, was added 31 g. (0.4 mole) of allyl

chloride in 100 ml. of dry ether. The salt did not

crystallize at first; instead, a thick oil formed. After








a week, fine white crystals began to form and in approxi-

mately a month the white needle like crystals were

collected. These crystals, which smelled strongly of

phosphine, were shaken for three hours, with a large

excess of dry ether. They were recollected and dried,

yielding 12.5 g. (53%) of fine white crystals, m.p. 152-

1600. Attempted recrystallizations were unsuccessful.

Anal. Calcd. for C18H22PBr: C, 71.46; H, 6.64;

P, 10.25. Found: C*, 71.87; H', 6.96; P, 10.19.

Ally ldiphen.,ylropy7lphosphonium bromide.-To 22.6 g.

(0.1 mole) of freshly distilled allyldiphenylphosphine in

a nitrogen flushed flask was added 48.8 g. (0.4 mole) of

n-propyl bromide in 100 ml. of dry ether. The sealed flask

was allowed to stand for ten days. The white crystals

which had separated were collected, washed with 200 ml. of

dry ether, and dried in a vacuum desiccator at 600. A

yield of 10 g. (28%) of long white crystals, m.p. 134-1570

was obtained.

Anal. Calcd. for Co8H22PBr: C, 61.90; H, 6.51;

P, 8.88. Found: C, 61.67; H, 6.53; P, 9.01.

Diallyldimethylphosphonium chloride.-In a nitrogen

filled dry box 2.0 g. (0.019 mole) of allyldimethyl-

phosphine was added to 5.7 g. (0.075 mole) of allyl

chloride dissolved in 5 ml. of dry ether in a flask. The








flask was sealed and removed from the dry box. After four

days the white crystals which formed were removed by

filtration and washed with 25 ml. of dry ether. The salt

was very hygroscopic and was dried in a drying pistol over

phosphoric anhydride at 550. A yield of 2.9 g. (82%) of

a solid, melting at 76-820 in a sealed tube, was obtained.

It was found to be impossible to remove the last traces

of water from this compound under the conditions used.

Thus, the analysis indicates the molecule crystallized with

one mole of water of hydration.

Anal. Calcd. for C8H16PC1: C, 53.88; H, 9.03;

P, 17.34. Calcd. for C8H16PC1-H0: C, 48.85; H, 9.23;

P, 15.40. Found: C, 48.27; H, 9.42; P, 15.40.


Polymerization of Phosphonium Salts

All of the phosphonium compound polymerizations were

run in solution in 5 ml. sealed ampoules. The solution

in the ampoule was always frozen and thawed twice under a

flow of dry nitrogen to remove dissolved oxygen from the

reaction. The ampoule was then sealed and the polymeri-

zation completed. Three different free radical initiators,

designated A, B, and C in the discussion which follows,

were used in the case of certain of the monomers. The

analyses of all the polymers indicated that they retained

one mole of water per phosphonium unit. These results are

consistent with the work reported by Skinner (24).








Poly,-(3-butenyldiphenylvinylphosphonium bromide).-To

1 g. of 5-butenyldiphenylvinylphosphonium bromide dissolved

in 1 g. of water was added 2 per cent (0.02 g.) of benzoin,

and the solution was placed in front of an ultraviolet

light source, in a sealed ampoule, in an oven at 600 for

a period of six days. The ampoule was opened and the

contents poured into 200 ml. of stirred reagent grade

acetone. No polymer was produced. The polymerization was

repeated using ethanol as solvent, but again no polymer

was obtained.

Poly-(allyldiphenylvinylphosphonium bromide).-To a

solution of 1 g. of allyldiphenylvinylphosphonium bromide

dissolved in 1 g. of water, in an ampoule, was added 1.8

per cent (0.018 g.) of benzoin. The ampoule was sealed

and placed in front of an ultraviolet light source in an

oven at 600 for five days. The contents of the ampoule

were then poured into 200 ml. of stirred reagent grade

acetone and the solid which separated was recovered. The

product was dried in a vacuum desiccator at 600. After

drying, 0.42 g. (42%) of a white powder, softening at 2200

and melting at 5100, was obtained. The intrinsic viscosity

[n], run in 1.0 M potassium bromide in ethanol-water (1:1)

was 0.025.

Anal. Calcd. for (C17H18PBr-H20)n: P, 8.82; Br,

22.76. Found: P, 8.71; Br, 22.45.








Poly-(allyl-3-butenyldiphenylphosphonium bromide).-

A-.-To a solution of 1 g. of allyl-5-butenyldiphenyl-

phosphonium bromide in 1 g. of water, in an ampoule, was

added 2 per cent (0.02 g.) of benzoin. The ampoule was

then sealed and placed in an oven at 600, in front of an

ultraviolet light source, for a period of three days.

The solution produced was poured into 200 ml. of stirred

reagent grade acetone and the solid which separated was

recovered. The product was dried in a vacuum desiccator

and gave 0.58 g. (58%) of a solid which softened at 2000,

and melted at 2600. The intrinsic viscosity [t] run in

0.5 M potassium bromide in ethanol-water (3:1) was 0.046.

Anal. Calcd. for (C19H22PBr-H20)n- P, 8.18;

Br, 21.10. Found: P, 8.12; Br, 20.90.

-B.-To a solution of 1 g. of allyl-5-butenyldiphenyl-

phosphonium bromide in 1 g. of dimethylformamide, in an

ampoule, was added 2 per cent (0.02 g.) of a, c~-azodi-iso-

butyronitrile (AIBN). The ampoule was then placed in an

oven at 620 for seven days. During this time the solution

darkened considerably and did not gain noticeably in

viscosity. The solution was decanted into stirred ethyl

ether and a very small amount of tan solid was produced.

It was recovered, dried, and gave a yield of 0.02 g. (2%).









-C.-To a solution of 1 g. of allyl-3-butenyldiphenyl-

phosphonium bromide in 1 g. of water, in an ampoule, was

added 1 drop of 60 per cent tert-butylhydroperoxide. The

solution was allowed to stand at 620 for seven days. The

slightly orange solution produced was decanted into 200 ml.

of stirred acetone. The flocculent precipitate was re-

covered and dried in a vacuum desiccator. While drying,

the product became very brittle. It gave a yield of 0.1 g.

(10%;) of polymer, softening at 1800 and melting at 2200.

Poly-(3-butenyldiphenylmethallylphosphonium chloride.-

A-. A solution of 1 g. of 5-butenyldiphenylmethallyl-

phosphonium chloride was treated as in part A above. After

seven days the sample was poured into 200 ml. of stirred

acetone. The product was a voluminous white solid which,

upon recovery, turned to an oil. The oil was redissolved

in ethanol and reprecipitated twice from acetone. A yield

of 0.60 g. (60S) of brittle white solid, softening at 2100

and melting at 3000 was recovered after drying in a vacuum

desiccator. The intrinsic viscosity [I], run in 1.0 H

potassium chloride in ethanol-water (1:1) was 0.058.

-B.-A solution of 1 g. of 5-butenyldiphenylmethallyl-

phosphonium chloride was treated as in part B above. After

seven days in the oven at 620 the temperature was raised

to 800 for two additional days. The dark orange solution









produced was then poured into 250 ml. of dry ether and the

precipitate recovered. During its drying in a vacuum

desiccator, however, it became very brittle. A yield of

0.15 g. (15%) of polymer, softening at 2600 and melting

at 3000, was obtained.

-C.-A solution of 1 g. of 3-butenyldiphenylmethallyl-

phosphonium chloride was treated as in part C above. After

seven days in the oven at 620 the temperature was raised

to 800 for two additional days. The light orange solution

produced was then poured into 200 ml. of dry acetone. The

white amorphous solid produced was collected and on drying

acted in the same manner as those described above. A

yield of 0.08 g. (8%) of polymer, softening at 2750 and

melting at 3030, was obtained.

Poly-(di-3-butenyldiphenylphosphonium bromide)-A.-A

solution of di-3-butenyldiphenylphosphonium bromide in 1 g.

of water was treated as in A above. After seven days in

front of an ultraviolet light source at 620, the solution

was poured into 200 ml. of acetone; but, no precipitate

formed. Impure monomer, melting at 97-1040, was recovered

by evaporation of the solvent and decanting the oil formed

into ether.

-B.-A solution of 1.2 g. of di-3-butenyldiphenyl-

phosphonium bromide was treated as in B above. The sample,







after nine days, seven at 60 and two at 800, was decanted

into dry ether and no precipitate formed. The solvent was

evaporated, the residue dissolved in ethanol, and then

dropped slowly into stirred ether. The oil formed was

stirred until an impure dark solid formed, melting at 88-

950. This dark solid was probably impure monomer.

-C.-A solution of 1 g. of di-3-butenyldiphenylphos-

phonium bromide was treated as in C above. Again, no

polymer was recovered; however, the impure monomer could be

reisolated.

Poly-(diallyldiphenylphosphonium bromide)-A.-A solu-

tion of 1 g. of diallyldiphenylphosphonium bromide was

treated as in A above, except that only 0.1 per cent of

benzoin initiator was used. After seven days in front of an

ultraviolet light source, at 600, the water and oil had

separated into two layers. The water layer was decanted and

the oil dissolved in ethanol. The solution was then dropped

slowly into dry ether. A viscous sticky oil was formed,

which upon continued stirring became a white flaky solid.

The product was washed with 100 ml. of dry ether and dried

giving 0.80 g. (80%) of white solid, softening at 190-2000

and melting at 3050. The intrinsic viscosity [q], run in

0.1 M potassium bromide in ethanol-water (1:1) was 0.052.

-B.-A solution of 1.44 g. of diallyldiphenylphos-

phonium bromide was dissolved in three times its weight of







dimethylformamide. It was placed in an ampoule, charged

with 1 per cent (0.0144 g.) AIBN, and heated in an oven at

700 for four days. The solution was then poured into 200 ml.

of dry acetone and a white flocculent precipitate was ob-

tained. The solid was dried and a yield of 0.28 g. (19%) of

polymer, softening at 2500 and melting at 3200, was obtained.

-C.-A solution of 2.35 g. of diallyldiphenyl-

phosphonium bromide was dissolved in a similar amount of

water. The solution was treated as in C above, using 2 per

cent initiator. The sample was left at room temperature

for one day and then at 700 for three days. After this time

it was poured into 200 ml. of acetone and no precipitate was

recovered. Monomer was recovered by the previously described

method, m.p. 170-178.

Poly-(diallyldiphenylphosphonium chloride).-To a

solution of 1 g. of diallyldiphenylphosphonium chloride,

dissolved in 1 g. of water, in an ampoule, was added 1 per

cent (0.01 g.) of benzoin. The ampoule was sealed and ir-

radiated at 600 by an ultraviolet light source for seven

days. The solution produced was poured into 200 ml. of dry

acetone and the solid precipitate collected. A yield of

0.74 g. (74%) of polymer, softening at 2700 and melting at

3000 was obtained. The intrinsic viscosity [is], run in 1 M

potassium chloride in ethanol-water (1:1) was 0.079.

Anal. Calcd. for (C18H20PC1*H20)n: P, 9.67; Cl,

11.08. Found: P, 9.41; Cl, 10.77.








Polyr-(diall7ldimethylohorphonium chloride) .-To a

solution of 1 g. of diallyldimethylphosphonium chloride,

dissolved in 1 g. of water, in an ampoule was added 1 per

cent (0.01 g.) of benzoin. The ampoule was sealed and

irradiated at 500 by an ultraviolet light source. After

two hours the solution was still very fluid. One day

later, the sample was a transparent gel. The gel was

insoluble in ethanol. It was ground and extracted with

ethanol in a soxhlet extractor. The solid was then removed

and dried. Eighty per cent (0.80 g.) of crosslinked polymer

was obtained. The extraction solvent was evaporated and 5

per cent (0.05 g.) of soluble polymer was obtained. The

soluble portion softened at 1500 and melted at 270.

Poly-(diallylphenylphosphine oxide).-To 7.35 g. of

poly-(diallyldiphenylphosphonium bromide) dissolved in

25 ml. of methanol was added a solution of 4 g. of potassium

hydroxide in 25 ml. of water. The colorless solution

immediately changed to yellow and, on heating, to orange,

then red, and after three days at reflux a gummy brown

solid separated out of the clear solution. The solution

was decanted and the solid extracted in a soxhlet extractor

with ethanol. The solution was evaporated until approxi-

mately 10 ml. was left. This solution was then dropped

slowly into stirred ether and a fine precipitate was col-

lected. An infrared spectrum showed strong absorption at








1170 cm-1, thus, indicating that poly-(diallylphenyl-

phosphine oxide) was the product. A yield of 4.2 g. (96%)

of a light tan solid, softening at 2600 and melting at

3200 was collected. The intrinsic viscosity [rk], determined

in ethanol, was 0.109.

Anal. Calcd. for: (C12H17PO-H20): C, 64.39; H,

7.64; P, 13.80. Found: C, 64.89; H, 7.39; P, 12.67.

This analysis was run by Schwarzkopf Microanalytical

Laboratory.

Preparation of Copolymers


Divinylphenylphosphine and acrylonitrile-A.-To a

solution of 1.34 g. (0.0083 mole) of divinylphenylphosphine

and 0.456 g. (0.0087 mole) of acrylonitrile dissolved in

5 g. of dimethylformamide, in an ampoule, was added 1 per

cent (0.0183 g.) of AIBN. The ampoule was sealed and

allowed to stand in an oven at 600 for four days. The

very fluid red solution was poured into 250 ml. of dry

ether. An orange solid precipitated, was filtered, and

dried in a vacuum desiccator. A yield of 0.6 g. (34%) of

a brittle red solid softening at 1100 and melting at 2000

was obtained. The infrared spectrum indicated that the

phosphine had been largely converted to the phosphine oxide.

The intrinsic viscosity [k], determined in dimethylformamide,

was 0.144.








Anal. P, 9.535 = 0.265 mole fraction of divinyl-

phenylphosphine oxide; i, 11.89S = 0.732 mole fraction of

acrylonitrile.

-B.-To a solution of 1 g. (0.00625 mole) of divinyl-

phenylphosphine and 0.67 g. (0.0128 mole) of acrylonitrile

dissolved in 5 g. of dimethylformamide, in an ampoule, was

added 1 per cent (0.0161 g.) of AIBI. The ampoule was

sealed and allowed to stand in an oven at 600 for three

days. The brilliant red solution which formed was then

poured into 200 ml. of stirred ether and the precipitate

collected and dried in a vacuum desiccator. A yield of

1.10 g. (65?') of an orange solid, which softened at 1200

and melted at 1950 was recovered. The infrared spectrum

showed that the phosphine had been converted to the

phosphine oxide during the work-up. The intrinsic

viscosity, determined in dimethylformamide, was 0.108.

Anal. P, 8.54% = 0.215 mole fraction divinylphenyl-

phosphine oxide; IT, 14.40% = 0.785 mole fraction of

acrylonitrile.










CHAPTER IV


SUMMARY


Monomers functionally capable of forming five-, six-,

seven-, and eight-membered rings, when polymerized by the

cyclic mechanism, were synthesized. A free radical

solution polymerization of the monomers gave polymers which

were soluble, and essentially saturated in all cases except

for the case of an eight-membered ring. This, as might

have been expected, did not form a polymer. The solubility,

saturation and resemblance to the polyammonium compounds

seemed to indicate that these polymers contained cyclics

which were produced during polymerization by the intra-

molecular-intermolecular mechanism. The copolymer of

acrylonitrile with divinylphenylphosphine showed that the

phosphines, like the related ethers and amines could be

used in cyclocopolymerization. Conversion of the poly-

phosphonium compound to the phosphine oxide showed that

the term "intrinsic viscosity" of the salt is an ambiguous

statement and actually has little correlation with the term

used for non-electrolyte polymers.









BIBLIOGRAPHY


1. C. Walling, J. Am. Chem. Soc., 67, 441(1945).
2. H. Stockmayer, J. Chem. Phys., 12, 125(1944).

>. G Butler and F. L. Ingley, J. Am. Chem. Soc., 73,
894(1951).
4. H. Staudinger and W. Heuer, Ber., 67, 1159(1934).

5. G. B. Butler and R. J. Angelo, J. Am. Chem. Soc., 79,
5128(1957).

6. G. B. Butler, A. Crawshaw, and W. L. Miller, ibid., 80,
3615(1958).

7. C. S. Marvel and R. D. Vest, ibid., 79, 5771(1957).

8. C. S. Marvel and J. K. Stille, ibid., 80, 1740(1958).

9. J. F. Jones, Italian Pat., 563,941, June 7, 1957, to
B. F. Goodrich Company.

10. J. F. Jones, J. Polymer Sci., 33, 15(1958).

11. A. Crawshaw and G. B. Butler, J. Am. Chem. Soc., 80,
5464(1958).
12. G. B. Butler and M. D. Barnett, U. S. Dept. Com., Office
Tech. Serv., P. B. Report, 145, 435(1959).

13. C. S. Marvel and E. J. Gall, J. Org. Chem., 25,
1784(1960).
14. N. D. Field, ibid., 25, 1006(1960).

15. C. S. Marvel and W. E. Garrison, J. Am. Chem. Soc., 81,
4737(1959).
16. W. L. Miller and W. B. Black, Division of Polymer
Chemistry Preprints, 142nd National Meeting of the
American Chemical Society, Atlantic City, N. J.,
September, 1962, p. 345.








17. C. King, J. Am. Chem. Soc., 86, 437(1964).
18. G. B. Butler and R. W. Stackman, J. Org. Chem., 25,
1643(1960).

19. G. B. Butler, J. Polymer Sci., 48, 279(1960).

20. E. Y. Chang and C. C. Price, J. Am. Chem. Soc., 83,
4650(1961).

21. J. M. Barton, G. B. Butler, and E. C. Chapin, Division
of Polymer Chemistry Preprints, American Chemical
Society, Philadelphia, Pa., April, 1964, p. 216.

22. Chemical and Engineering News, Dec. 16, 1963, p. 42.

23. Ibid., Dec. 30, 1963, p. 33.

24. D. L. Skinner, Ph.D. Dissertation, University of
Florida, January, 1961.

25. K. D. Berlin and G. B. Butler, J. Am. Chem. Soc., 82,
2712(1960).

26. W. J. Jones, W. C. Davies, et al., J. Chem. Soc., 1947,
1446.

27. M. I. Kabacknek, Chung-Yu Chang, and E. N. Tsvetkov,
Proceedings of the Academy of Sciences USSR. (English
Translation), 135, 1309(1960).

28. A. B. Burg and P. J. Slota, J. Am. Chem. Soc., 80,
1107(1958).

29. P. G. Gaubert, R. P. Linstead, and H. N. Rydon,
J. Chem. Soc., 1937, 1921.

30. J. R. Van Wazer, Phosphorus and its Compounds, Inter-
science Publishers, Inc., New York, 1958, Vol. I, p. 43.

31. N. J. Leonard and D. M. Locke, J. Am. Chem. Soc., 77,
437(1955).

32. G. B. Butler, G. L. Statton, and W. C. Bond, unpublished
work.


33. J. K. Stille, Chem. Revs., 58, 541(1958).








34. F. \W. Eillmeyer, Tex:tbook of Pol:ymer Chemistry, Inter-
science Publishers, Inc., iew York, i;7, p. 128.

35. R. I. Fuoss and U. P. Strauss, J. Polv-er Sci., 3,
602(1948).

36. G. E. Butler, Abstract of Paper, 153rd alstional
meeting c the Armeric.an Cnemical Society, San
Francisco, California, April, 1958, p. 6R.

37. G. E. Butler, C. F. Hauser, et al., Technical Report
io. ASD-TR-61-237, part I, September, 1961.

38. L. J. Bellamy, The Infra-red Spectra of Complex
Molecules, John Wiley and Sons, Inc., ilew Yor:, 1950,
p. 521.

39. 0. Grummitt, E. P. Budewitz, and C. C. Chudd, Org. Syn.,
36, 61(1956).

40. H. E. Ramsden, J. R. Leebrick, et al., J. Ore. Chem.,
22, 1602(1957).

41. D. J. Foster and E. Tobler, ibid., 27, 834(1962).

42. N. S. Johary and L. N. Owens, J. Chem. Soc., 1955,
1292.

43. D. N. Paisley and C. S. Marvel, J. Polymer Sci., 56,
533(1962).
44. M. C. Browning, J. R. Mellor, et al., J. Chem. Soc.,
1962, 693.

45. H. H. Sisler, H. S. Ahuja, and N. L. Smith, J. Org.
Chem., 26, 1819(1961).










BIOGRAPHICAL SKETCH


William C. Bond, Jr. was born on August 4, 1938,

at Bethesda, Maryland. He attended elementary school at

Bethesda, Maryland and Evanston, Illinois. He received

his high school education while in attendance at Admiral

Farragut Academy at St. Petersburg, Florida. The author

registered in Wheaton College, Wheaton, Illinois, in

September, 1956, and was graduated in 1960 with a Bachelor

of Science degree in Chemistry. He entered the graduate

school at the University of Florida in September, 1960.

The author is a member of Gamma Sigma Epsilon and

the American Chemical Society.

Donna Allen Bond is the wife of the author and they

have two sons, William C. Bond, III, and Harold Bruce Bond.









This dissertation was prepared under the direction
of the chairman of the candidate's supervisory committee
and has been approved by all members of that committee.
It was submitted to the Dean of the College of Arts and
Sciences and to the Graduate Council, and was approved as
partial fulfillment of the requirements for the degree of
Doctor of Philosophy.

April 18, 1964



Dean, College of Arts;a~d Sciences



Dean, Graduate School

Supervisory Committee:


Chairman



S/
'I _

g




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