• TABLE OF CONTENTS
HIDE
 Title Page
 Acknowledgement
 Table of Contents
 Historical
 Statement
 Introduction
 Materials, chemical analyses and...
 Experimental
 Dicussion of results
 Summary
 Bibliography
 Biographical sketch
 Copyright














Title: preparation and polymerization of some diallyl- and dimethallylphosphonium bromides.
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Title: preparation and polymerization of some diallyl- and dimethallylphosphonium bromides.
Series Title: preparation and polymerization of some diallyl- and dimethallylphosphonium bromides.
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Creator: Skinner, David Lloyd,
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Table of Contents
    Title Page
        Page i
    Acknowledgement
        Page ii
    Table of Contents
        Page iii
        Page iv
        Page v
        Page vi
    Historical
        Page 1
        Page 2
    Statement
        Page 3
    Introduction
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
    Materials, chemical analyses and physical measurements
        Page 9
        Page 10
    Experimental
        Page 11
        Page 12
        Page 13
        Page 14
        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
        Page 23
        Page 24
        Page 25
        Page 26
        Page 27
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
    Dicussion of results
        Page 34
        Page 35
        Page 36
        Page 37
        Page 38
        Page 39
        Page 40
        Page 41
        Page 42
        Page 43
        Page 44
        Page 45
        Page 46
        Page 47
        Page 48
        Page 49
        Page 50
        Page 51
        Page 52
        Page 53
        Page 54
    Summary
        Page 55
    Bibliography
        Page 56
        Page 57
    Biographical sketch
        Page 58
        Page 59
    Copyright
        Copyright
Full Text










THE PREPARATION AND

POLYMERIZATION OF SOME DIALLYL- AND

DIMETHALLYLPHOSPHONIUM BROMIDES










By
DAVID LLOYD SKINNER


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















ACKNOWLEDGMENTS


The author wishes to express his deep appreciation to

Dr. George B. Butler for his encouragement and direction

which greatly contributed to the completion of this work.

An expression of gratitude is due the author's supervisory

committee for valuable criticisms and suggestions. The

author is indebted to his fellow graduate students for their

advice and assistance.

A special expression of thanks goes to Mrs. B. S.

Endsley and Mrs. W. H. Cribbs for typing the manuscript.

The author is indebted to the United States Air Force

for its financial support of this project.
















TABLE OF CONTENTS


ACKNOWLEDGMENTS .

LIST OF TABLES .

CHAPTER


I

J


. . 0 0 v 4


4 0 0 4 *


v a 0 0 v 0 0 0 #


I. HISTORICAL * . . .

EI. STATEMENT . . ...

II. INTRODUCTION . . . .

IV. MATERIALS, CHEMICAL ANALYSES
AND PHYSICAL MEASUREMENTS .

A. Materials . . .

B. Chemical Analyses . .

C. Physical Measurements o 9 .

D. Quantities and Yields . o

V. EXPERIMENTAL *. E . . .

A. Diallylphosphonium Bromides

1. Allylmagnesium bromide .

2. Diallylphenylphosphine .


* 4 0 4 0 0 9







. . U U . .



. . . 0

* a o o o .

. 0 0 0 0 9 0 .
OOr













S 0 o0 .




S 0 9 .
.rrro*ro

o

ro r o

roroo

roeeoo


3. Diallylphenylmethylphosphonium
bromide. . . . . . .* # ,

4. Diallylphenylethylphosphonium
bromide. * * * a . .

5 Diallylphenylpropylphosphonium
bromide. *. . . . . . .* *

B. Triallylphenylphosphonium Bromide,. .. ,


iii


Page

ii

vi



I
1

3




9

9

9

9

10

11

11

11

12






13


13

14










Page

C. Dimethallylphosphonium Bromides 1. . 15

1. Methallylmagnesium chloride . . . 15

2, Dimethallylphenylphosphine . . . 15

3 Dimethallylphenylmethylphosphonium
bromide * * . . . . . 16

4* Dimethallylphenylethylphosphonium
bromide . . . . . . 16

5* Dimethallylphenylpropylphosphonium
bromide *. . *. .# . . 17

D. Diphenylphosphonium Bromides . . . 17

1. Allyldiphenylphosphine . . . 17

2. Diallyldiphenylphosphonium bromide. . 18

3. Methallyldiphenylphosphine . . 18

4. Allylmethallyldiphenylphosphonium
bromide .* . * * * . 19

5. Dimethallyldipnyphenylphosphonium
bromide . . . .. *. * 20

E. Comparison of Initiators. . . * . 20

F. Poly-(Phosphonium Bromides) . . . 21

1i Poly-(Diallylphenylmethylphosphonium
bromide). . . . . . . o 21

2. Poly- (Diallylphenylethylphosphonium
bromide). . . . . 22

3. Poly-(Diallylphenylpropylphosphonium
bromide). * . * * * 22

4. Poly-(Triallylphenylphosphonium
bromide). . o o * 2 23

5* Poly-(Dimethallylphenylmethylphos-
phonium bromide).e . . . 23









Page


6. Poly-(Dimethallylphenylethyl-
phosphonium bromide). . . . . 24

7. Poly- (Dimethallylphenylpropyl-
phosphonium bromide). . .. . . 25

8, Poly-(Diallyldiphenylphosphonium
bromide). . o . . 25

9. Poly-(Allylmethallyldiphenyl-
phosphonium bromide). . . . 26

10. Poly-(Dimethallyldiphenylphos-
phonium bromide). . . . . . 26

G. Poly-(Phosphine Oxides) . . . 26

1. Poly-(Diallylphenylphosphine
oxide) . . . *. . . 26

2. Poly-(Diallylmethylphosphine
oxide). . . . . . 27

HU Hydrogenation . . . . .. . 28

I. Triphenylmethylphosphonium Bromide* . 29

J. Viscosity Measurements . . . . 29

VI. DISCUSSION OF RESULTS. . . . .. 34

A. Monomers . . . . . . 34

B. Polymerizations . . . . *. 39

C. Polymers .. . . * * . . . 41

D. Infrared Data. . . . 50

E. Poly-(Phosphine Oxides). . . . 52

VII, SUMMARY . . o . . . .0 * 55

BIBLIOGRAPHY .. . . . .* 56

BIOGRAPHICAL SKETCH. . . . . . 58















LIST OF TABLES

Page

TABLE

1. .MONOMERS * * *, 0 . 31

2. POLYMERIZATION CONDITIONS & & . < 32

3. POLYMERS . . . **, 33
















CHAPTER I

HISTORICAL


Previous work in this laboratory has shown that free

radical initiated polymerization of allyl substituted

quaternary ammonium compounds in which three or four allyl

groups were present gave infusible, water-insoluble poly-

mers.112 Non-cross linked, water soluble polymers were

obtained from monomers containing two allyl groups. Until

this observation was made, it was believed that diene

systems in which the double bonds were not conjugated gave

cross linked polymers.3 Study of the soluble polymers

obtained revealed that little or no unsaturation was

present in these polymers. To explain this unusual
4
property of diallylammonium compounds, Butler and Angelo

proposed a mechanism by which both double bonds would be

used and a linear polymer would be produced. An alter-

nating intramolecular-intermolecular chain propagation was

proposed. This mechanism involved an attack of a free

radical on the terminal position of one of the allyl groups,

generating a secondary free radical. The secondary radical

then attacked the other allyl group in the terminal position

in an intramolecular propagation step to form a piperidinium

ring. The intermolecular propagation step followed with an










attack on another monomer molecule. Termination can take

place in one of several of the usual free radical termi-

nation reactions

Linear polymers from non-conjugated diene monomers

have since been reported in several other systems. Cyclic

polymerization has been observed with o<,c>1'-dimethylene

pimelate5 It has also been found that 1,5-hexadiene and

1l6-heptadiene form linear polymers with Ziegler catalysts*

Acrylic anhydride has been polymerized under a variety of

conditions to yield cyclic polymers*7'8 Among the many

materials found to undergo this unique reaction may be found

compounds as diverse as diallylsilanes9 and diallylamidesi10

Both anionic and cationic initiators have been found to
11,12
produce cyclic polymers.

In addition to 15-and lj6-dienes, other diene mole

cules with a greater separation of the double bonds have

been polymerized to give rings of seven to fifteen members.

In order to prove that cyclic structures had been

obtained from ammonium diene monomersI Butler$ Crawshaw and

Miller4 undertook a series of reactions to identify the

cyclic component in the polymers. Poly-(diallylamine

hydrobromide) was benzoylated in the presence of sodium

hydroxide* The reaction product was oxidized in order to

open the ring Analytical data and potentiometric titra-

tions supported the presence of the predicted product .The

infrared spectrum also contained absorptions which corre-

lated with the structure expected.
















CHAPTER II

STATL'ICErT OF THE PROILr'.;


The objectives of this investigation were as follows:

1. To synthesize a series of diallylphosphonium com-

pounds and a series of dimethallylphosphonium compounds

which conceivably might undergo polymerization by a

cyclic mechanism to yield linear polymers.

2. To attempt the polymerization of the phosphonium

monomers obtained by means of free radical initiation,

and further, to study the effect of the groups, other

than the unsaturated radicals, attached to the phos-

phorus atom to determine the steric consequences on

the cyclic mechanism, if any.

3. To isolate any soluble polymer formed which is

relatively free of unsaturation and study its proper-

ties.

4. To show the cyclic nature of some of these polymers.















CHAPTER III

INTRODUCTION


It was decided to prepare the monomers by the well-

known reaction of alkyl halides with phosphines to yield

phosphonium halides. After considering the several methods

available for preparing phosphinest the method of Jones and

Davies,15 with minor modifications, was selected, The

method involved the reaction of allyl or methallyl Grignard

reagents with phenyldichlorophosphine or diphenylchloro-

phosphine. The allyl- and methallylmagnesium halides used

were obtained by means of the reaction outlined by Grummitt,

Budewitz and Chudd.16

These unsaturated phosphines were then reacted with an

alkyl bromide to produce the desired monomer. The literature

revealed that many phosphonium halides had been prepared in

the past. A few diallyl- and dimethallylphosphonium halides

had been prepared. The phosphonium halides were usually

prepared in order to obtain sharp melting derivatives of

phosphines. All of the compounds reported are new compounds.

A few, however, are different from phosphonium halides

previously reported only in that they contain bromide ion

rather than chloride or iodide*










The general scheme of reaction by which the monomers

were obtained is illustrated by the followingS


Cl

C611.5-p/\C


c65


R R-C C-R

+ CH2 ; C-CH2MgBr -i H2C \ 2


P



+
12

.R

3- d Br


R = H or CH3


R' = CH3, C2H5or C3H7


It was decided to initiate the polymerization of the

monomers obtained with free radicals from tert-butyl

hydroperoxide in water solution. The polymerization system

chosen, at least as a starting point, was that used for the

quaternary ammonium investigation and seemed a logical

choice It was found that cdcod' -azodii-so-butyronitile in










dimethylformamido solution was a more effective initiator

system for several of the monomers which were polymerizod.

The mechanism proposed by Butler and AngeloL for the

polymerization of 1i6-diene systems held for these com-

pounds? The mode of reaction may be represented by the

following equations


11 C CIH
211 11 2






C i RI2
c6 5


+ z --4


R CH
1/2
- Z-CII -C ,C-R




C IC
65


R CHI

Z-CII2-C C-R
IV I



C IIC \
6 5


+




Br


monomer
- 3-


- n











R = H or C113


= C3 C211 5, C311 or C6H5


The study of the polymers produced consisted of the

usual elemental analysis and infrared absorption spectra.

Since some work had been reported on intrinsic viscosity

measurements made on polyelectrolyteos819 it was de-

cided to investigate the behavior of poly-(phosphonium

bromides) by using a similar method. The values obtained

are listed in Table 3.

In order to show the cyclic nature of the polymers

obtained it was desirable to convert one of them to a

cyclic compound which had been synthesized by another

route or to open the ring by well-known reactions to give

easily identifiable functional groups. Reactions of phos-

phonium compounds with sodium hydroxide have boon shown to

give phosphine oxides*21'22e23 Berlin synthesized some

poly-(diallylphosphine oxides)20 at about the same time

this work was undertaken* One of the poly-(phospIiine

oxides) prepared by Berlin was prepared from the poly-

(phosphonium bromide) by the following reaction















+ I0--4


n


R R

-CII2-C C-
I I
1120 CIH
/ 2


0 R


R = II

R' = C6115



The conversion of the phosphonium polymer to a phos-

phine oxide polymer constituted an alternate synthesis of

the cyclic compound.















CHAPTER IV

MATERIALS, CHEMICAL ANALYSES AND PHYSICAL MEASUREMENTS


A. Materials

The diphenylchlorophosphine and phenyldichlorophos-

phine used were obtained from the Victor Chemical Works*

Alkyl bromides used were obtained from Columbia Organic

Chemicals Company, Incorporated with the exception of

methyl bromide, which was purchased from Dow Chemical

Company.

Solid materials, intermediates and products were dried

as noted in Chapter V. A vacuum desiccator which contained

Drierite was used under continuous aspiration to dry these

materials.


B, Chemical Analyses

All chemical analyses reported were determined by

Galbraith Laboratories of Knoxville, Tennessee.


C, Physical Measurements

All temperatures reported are uncorrected. Melting

points were found by using a heated block. Infrared spectra

were obtained by using a Perkin-Elmer model 21 spectropho-

tometer or a Perkin-Elmer Infracord spectrophotometer.

Viscosities of polyelectrolyte polymers were measured by











usinC a Ubbelohde Number 1-A137 viscometer, and viscosities

of the poly-(phosphine oxides) were measured by using a

Cannon-Ubbelohde Semi-Micro Dilution viscometer.


D. Quantities and Yields

Due to the difficulties encountered in isolating both

Grignard reagents and organophosphino compounds, no yields

are listed for them in the experimental section. The

quantities of these materials used are not given. The

intermediates obtained as outlined in the experimental

section were used with no attempt to measure the quantities

of them. The yields of phosphonium bromides obtained are

based on the phonyldichlorophosphine or diphenylchlorophos-

phine used to synthesize the phosphine intermediates.
















CHAPTER V

EXPERIMENTAL


A. Diallylphosphonium Bromides (Properties in Table 1)


1. Allylmagnesium bromide

Allylmagnesium bromide was prepared by the method of

Grummitt, Budewitz and Chudd.16 Forty-eight grams (two

moles) of magnesium turnings was placed in a flask fitted

with a stirror, condenser and a constant pressure addition

funnel. Two hundred ml. of dry ethyl ether was added and

the flask placed in an ice bath. The flask was flushed

with dry nitrogen which had been bubbled through concen-

trated sulfuric acid. Approximately one ml. of ethyl

bromide was added and the mixture stirred for several

minutes. One hundred and one grams of allyl bromide (one

mole) was added as a solution in 50 ml. of dry ether over

a period of three hours. A slow nitrogen flow was main-

tained throughout the reaction. The ether solution was

decanted from the excess magnesium turnings into a flask

previously flushed with dry nitrogen. A small portion of

the material was titrated and found to be 3.7 L (92.5 per

cent yield).










2. Diallylphenylphosphineo.

Freshly prepared allylmagnesium bromide was decanted

into a flask which had been flushed with dry nitrogen. The

flask was fitted with a stirrer, condenser and a constant

pressure addition funnel. A continuous flow of dry nitrogen

was maintained during the reaction* The flask was placed

in an ice bath. Thirty-six grams (0.2 mole) of phenyldi-

chlorophosphine was added to the reaction mass with stirring

over a two hctir period. The mixture was then refluxed for

005 hour and again cooled in an ice bath. The solution was

hydrolyzed by adding 100 grams of ammonium chloride in one

liter of water over a two hour period in an ice bath. Two

layers were formed which were separated by using a nitrogen

flushed separatory funnel. The organic layer was retained

and dried under nitrogen using anhydrous magnesium sulfate.

The dry ether layer was decanted into a distillation flask

equipped with a nitrogen bubbler and a vacuum-jacketed

Vigreux distillation column, The ether was removed under

reduced pressure and the product distilled. Over several

runs the boiling point was found to correspond with the

data given by Jones and Daviesl15 i.e., 1270 at 14 mm. of

mercury.


3. Diallylphenylmethylphosphonium bromide

Nineteen grams (0.2 mole) of methyl bromide was

bubbled into a solution of diallylphenylphosphine in dry










ethyl ether at 0-5 C. The solution was allowed to stand

five days at room temperature. A white solid material was

formed. The solid was isolated and recrystallized from

acotone-other solution. The recrystallized product was

dried in a vacuum desiccator. Thirty crams (53 per cent

yield based on PhPCl2) of a white solid melting at 98-99

was obtained.

Analysis. Calculated for C13II18PBrt P, 10.86;

Br, 28.03. Found: P, 10.86; Br, 28.22.


4. Diallylphonylethylphosphonium bromide

Twenty-two grams (0.2 mole) of ethyl bromide, as a

solution in 20 ml, dry ethyl ether, was added to freshly

distilled diallylphonylphosphine (D.P. 81-82o at 1.1-1.4

mm.). The pressure was increased to atmospheric pressure

with dry nitrogen. The solution was allowed to stand ton

days at room temperature. A white solid product was

isolated and washed twice with dry ethyl ether. The

material was dried overnight in a vacuum desiccator at

600. Fourteen Grams (23.2 per cent yield) of a white

solid material melting at 123-127 was obtained.

Analysis. Calculated for CII!20PBr: P, 10.37; Br,

26.76. Found: P, 10,31; Br, 25.87.


5. Diallylphenylpropylphosphonium bromide

Fifteen ml. of dry ethyl other was added under vacuum

to freshly distilled diallylphenylphosphine (B.P. 910 at 1.7 mm.).










Twenty-five grams (0.2 mole) of n-propyl bromide was also

added under vacuum. The pressure was returned to atmos-

pheric pressure with dry nitrogen. The solution was allowed

to stand for 14 days at room temperature, A white solid was

obtained which was washed with dry ethyl ether and dried in

a vacuum desiccator. Nineteen grams (30 per cent yield) of

a white solid melting at 850 was obtained.

Analysis. Calculated for C15H22PBrt Ps 9.901

Brp 25.5. Found P, 9.84; Br, 25.20.


B. Triallylphenylphosphonium Bromide

(Properties in Table 1)


Twenty-four grams (0.2 mole) of allyl bromide was added

to a solution of diallylphenylphosphine in ethyl ether. The

solution had been dried over magnesium sulfate and decanted

into a flask which had been flushed with dry nitrogen. The

flask was stoppered and allowed to stand five days at room

temperature. A white solid material was formed which was

isolated and recrystallized from acetone-ether solution.

Twenty-nine grams (47 per cent yield) of a material melting

at 109-1100 was obtained.

Analysis. Calculated for C15H20PBrt Pp 9.971

Br, 25.63. Found P, 10.12; Br, 25.37.










C. Dimethallylphosphonium Bromides

(Proporties in Table 1)


1. 'Methallylmagnesium chloridel6

Forty-eight grams (two moles) of magnesium turnings

was placed in a flask fitted with a stirrer, condenser and

constant pressure addition funnel. The flask was flushed

with dry nitrogen. A constant flow of dry nitrogen 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

ten minutes. Ninety-one grams (one mole) of methallyl

chloride was added with stirring over a four hour period.


2. Dimethallylphonylphosphine

To a freshly prepared slurry of methallylmagnosium

chloride was added 36 grams (0.2 mole) of phonyldichloro-

phosphine. The reaction was carried out in an ice bath,

under dry nitrogen. The addition required three hours.

The mixture was refluxed 0.5 hour and again cooled in an

ice bath. The mixture was then hydrolyzed by the dropwise

addition of 100 grams of ammonium chloride in one liter of

water. The two layers produced were separated and the

organic layer dried over anhydrous magnesium sulfate. The

dried solution was decanted into a distilling flask under

nitrogen. The ethyl ether was removed under reduced

pressure. The dimethallylphonylphosphine was distilled.










Boiling point data corresponded with that given by Jones

and Davies,15 i.e., 1480 at 14 mm. of mercury.


3. Dimethallylphonylmothylphosphonium bromide

A freshly prepared solution of dimethallylphonylphos-

phine in dry ethyl other was placed in a flask previously

flushed with dry nitrogen. Thirty-eight crams (0.4 mole)

of methyl bromide was bubbled into the solution below the

surface* The flask was stoppered and allowed to stand 40

hours. A white crystalline product was obtained which was

washed with dry ether and dried in a vacuum desiccator.

Thirty-two grams (51 per cent yield) of a white solid

which melted at 175-178o was obtained.

Analysis. Calculated for C H22PBr: P, 9#91;

Br, 25.32. Found: P, 9.63; Br, 24.81.


4. Diilethallylphenylethylphhsphonium bromide

To freshly distilled dimethallylphenylphosphine

(b.p. 980, at 1.5 mm.) was added 25 ml. of dry ethyl

ether and 40 grams (0.4 mole) of ethyl bromide under

vacuum. The pressure was raised to atmospheric pressure

using dry nitrolfcn. The materials were allowed to stand

14 days at room temperature. A white, waxy solid was the

product. The product was washed with dry ether and vacuum

dried at 400 in a vacuum desiccator. Seven grams (11 per

cent yield) of a white solid melting at 770 was obtained.









Analysis. Calculated for C16H24PBrI P, 9.48;

Br, 24.47. Found: Pt 9.40; Br, 24.63.


5. Dimethallylphenylpropylphohsponium bromide

Twenty ml. of dry ethyl ether and 25 grams of n-propyl

bromide was added under vacuum to freshly distilled dimeth-

allylphenylphosphine (b.p. 890 at 0.7 mm,) and the pressure

raised to atmospheric pressure using dry nitrogen. After

14 days at room temperature a waxy, white solid was precip-

itated, The liquid layer was decanted and the solid was

dried in a vacuum desiccator at 500, Four grams (7 per

cent yield) of a white, waxy material was isolated which

melted at 107-1100.

Analysis. Calculated for C17H26PBr: P, 9.09;

Br* 23.40. Found P, 9.18; Br, 23.07.


D. Diphenylphosphonium Bromides

(Properties in Table 1)

1. Allyldiphenylphosphine

One mole of allylmagnesium bromide in 250 ml. of dry

ethyl ether was prepared by the method of Grummitt, Budewitz

and Chudd.6 The allylmagnesium bromide was placed in a

nitrogen flushed flask fitted with a stirrer, condenser and

constant pressure addition funnel. The flask was placed in

an ice bath. The flask was flushed with dry nitrogen

throughout the reaction. Forty-four grams (0.2 mole) of










diphonylchlorophosphine was added over a two hour period.

The mixture was refluxed 0.5 hour and again cooled in an

ice bath. The reaction mass was hydrolyzed using 50 grams

of ammonium chloride in 250 ml. of water. The other layer

was separated and 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 removed under reduced pressure. The

allyldiphenylphosphine was distilled at ll4-16 at 0.5 mm.


2. Diallyldiphenylphosphonium bromide

An equal volume of dry ethyl other was added under

vacuum to freshly distilled allyldiphonylphosphine.

Twenty-four grams (0.2 mole) of allyl bromide was added

under vacuum and atmospheric pressure restored using dry

nitrogen. The reaction was allowed to stand overnight.

A white precipitate was obtained which was washed with dry

ethyl ether and dried in a vacuum desiccator at 800

Thirty-nine grams (57 per cent yield) of a white solid

melting at 155-1570 was obtained.

Analysis. Calculated for C18H20PBr: P, 8.94;

Br, 23.01. Found: P, 8.75; Br, 23.14.


3. Mothallyldiphonylphosphine

Forty-four grams (0.2 mole) of diphcnylchlorophos-

phine was added to one mole of freshly prepared mothallyl-

magnesium chloride in 250 ml. of dry other under dry











nitrogen over a one hour period in an ice bath. The

mixture was refluxed for 0.5 hour and again cooled in an

ice bath. The mixture was hydrolyzed with a solution of

50 crals of ammonium chloride in 250 ml. of water. The

organic layer was separated and dried over anhydrous

magnesium sulfate under dry nitrogen, The dried solution

was decanted into a distillation apparatus and the ether

removed under reduced pressure. Methallyldiphenylphos-

phine was distilled using a nitrogen bubbler. The product

boiled at 118-121 at 0.45 mm.


4. Allylrmethallyldiphonylphosphonium bromide

One hundred ml. of dry ethyl ether was added to freshly

distilled methallyldiphenylphosphine under reduced pressure.

Twenty-four grams (0.2 mole) of allyl bromide was also

added and the pressure restored to atmospheric pressure

with dry nitrogen. A white precipitate was formed after

allowing the reaction to stand three days at room temper-

ature. The solid was isolated, washed with dry ethyl

ether and dried at 600 in a vacuum desiccator. Twenty-

nine grams (42 per cent yield) of a white solid melting

at 162-1640 was obtained.

Analysis. Calculated for C 19122 Pr P, 8.59;

Br, 22.18. Found: P, 8.61; Br, 22.19.










5. Dimothallyldiphenylphosphonium bromide

Twenty-seven grams (0.2 mole) of mothallyl bromide,

obtained using the method of Taraole, Ott, Marble and
24
Hearne, was added along with 100 ml. of dry ethyl ether

to freshly distilled methallyldiphenylphosphine under

reduced pressure. Atmospheric pressure was restored with

dry nitrogen. The reaction mixture was allowed to stand

two days at room temperature. A white solid was formed.

The solid was isolated and recrystallized from dimethyl-

formamide and ethyl ether solution. The solid was washed

with dry ether and dried at 600 in a vacuum desiccator.

Fourteen grams (19 per cent yield) of a white solid melting

at 179-180o was obtained.

Analysis. Calculated for C20H24PBr: P, 8.27;

Br, 21.33. Found: P, 8.39; Br, 21.39.


E. Comparison of Initiators


Three samples of diallylphenylethylphosphonium bromide

(one :rar. each) were placed in separate tubes. Two grarms

of dimethylformamide was added to each tube to dissolve the

salt. Different initiatorswere added to each solution.

Five per cent by weight of t-butyl hydroperoxido, benzoyl

peroxide and o, o(-azodi-iso-butyronitrile were added. The

tubes were flushed with dry nitrogen and loosely stoppered.

The tubes were placed in an oven under nitrogen at 68 for

14 days. The solutions were poured into separate flasks










containing 20 ml. each of dry ethyl ether. The t-butyl

hydroperoxide initiated reaction product was a yellow

semi-solid. A white solid was obtained after three

reprecipitations from ethanol-ether. The solid was dried

overnight in a vacuum desiccator at 600. One-half gram

(50 per cent yield) of a white solid polymer was obtained.

The product of the benzoyl peroxide initiated reaction was

an amber oil after several precipitations from ethanol-

ether. The reaction initiated by c(oC'-azodi-iso-buty-

ronitrile yielded a white solid on its initial precipi-

tation. The solid was isolated and dried overnight in a

vacuum desiccator at 600, One gram (100 per cent yield)

of a white solid polymer which softened at 2900 was

obtained.


F. Poly-(Phosphonium bromides)

(Polymerization Conditions Table 2)

(Properties in Table 3)


1. Poly-(Diallylphenylmethylphosphonium bromide)

Six grams of diallylphenylmethylphosphonium bromide

was dissolved in three grams of water in a tube under dry

nitrogen. Tertiary butyl hydroperoxide (1.68 per cent by

weight of monomer) was added and the tube loosely stoppered.

The tube was placed in an oven at 680 for three days under

nitrogen. The product was dissolved in approximately ten

ml. of absolute ethyl alcohol. The alcohol solution was










poured into 100 ml. of dry acetone. A white precipitate

was formed which was washed three times with dry ether and

dried in a vacuum desiccator at 600. Three and six-tenths

grams (60 per cent yield) of a white solid which softened

at 2300 and formed a clear melt at 2850 was obtained.

Analysis indicated that a mono-hydrate was obtained.

Analysis. Calculated for C13188P3r.oI2 n: P, 10.22;

Br, 26.40. Found: P, 10.34; Br, 26.77.


2. Poly-(Diallylphenylethylphosphonium bromide)

One gram of diallylphonylethylphosphonium bromide was

dissolved in two grams of dimethylformamide in a tube.

Five per cent (0.05 Gram) of o.,o'-azodi-iso-butyronitile

(AI1; ) was added and the tube flushed with dry nitrogen.

The tube was loosely stoppered and placed in a nitrogen

flushed oven at 68 for 14 days. The resulting thick

solution was poured into dry ethyl ether giving a white

precipitate which was washed three times with dry ether

and dried in a vacuum desiccator at 600. One gram (100

per cent yield) of a white powder which softened at 2900

and formed a clear molt at 3400 was obtained.

Analysis. Calculated for Lc4lI20PBr*HeI2n P, 9.78;

Br, 25.20. Found P, 9.30; Br, 24.05.


3. Poly-(Diallylphenylpropylphosphonium bromide)

Two grams of diallylphonylpropylphosphonium bromide

was dissolved in four grams of dimethylforamide along with










0.2 gram (10 per cent) of ABN in a nitrogen flushed tube.

The tube was loosely stoppered and placed in a nitrogen

flushed oven at 680 for 13 days. The resulting solution

was poured into 100 ml. of dry ethyl other. The ambor oil

which separated was dissolved in ten ml. of absolute

ethanol and reprecipitated five times from dry ether. The

solid product was isolated and dried in a vacuum desiccator

at 600, One and two-tenths grams (60 per cent yield) of

a white solid which softened at 2000 and formed a clear

molt at 2550 was obtained.

Analysis. Calculated for p1C5122 PBr*o2Qn: P, 9.36;

Br, 24.10. Found: P, 8.80; Br, 23.34.


4. Poly- (Triallylphenylphosphonium bromide)

One :rar of triallylphenylphosphonium bromide was

dissolved in 0.5 gram of water alone with five drops of

t-butyl hydroperoxide (4.2 per cent). The solution was

placed in an oven at 680 for four days under nitrogen.

One gram (100 per cent yield) of an amber glass-like

material which decomposed with heating and was insoluble

in ethyl alcohol was isolated.

Analysis. Calculated for E15 20PPBr*H 2O nW P, 9.43;

Br, 24.30. Found: Pp 9.10; Br, 23.34.


5. Poly- (Dimethallylphenylmothylphosphonium bromide)

Two grams of dimethallylphenylmethylphosphonium bromide

was dissolved in one gram of water along with 0.1 cram (5 per










cent) t-butyl hydroporoxide. The solution was placed in

an oven under nitrogen at 1100 for a period of six days.

The product was dissolved in five ml. of absolute ethanol

and reprecipitated twice from dry ether. The product was

then dried in a vacuum desiccator at 80. One and nine-

tenths grams (95 per cent yield) of a white solid which

softened at 2200 and gave a clear melt at 3440 was

isolated.

Analysis. Calculated for C151ip22PBr.-HII2j P, 9.36;

Br, 24.18. Found: P, 9.41; Br, 24.08.


6. Poly,-(Dimethallylphonylethylphosphonium bromide)

Two grams of dimethallylphenylethylphosphonr.um bromide

was dissolved in two grams of dinmethylformamide along with

0.08 gram (4 per cent) of AnT:. The tube was placed in a

bath at 1100. The tube was allowed to remain in the bath

for six days during which a slow flow of dry nitrogen was

maintained. The resulting solution was poured into dry

ethyl ether. The light tan solid which formed was dis-

solved in ten ml. of absolute ethanol and reprecipitated

from dry ether four times. The white solid product was

washed with dry other and dried at 800 in a vacuum desic-

cator. Four-tenths of a gram (20 per cent yield) of a

white solid which softened at 1850 and gave a clear melt

at 2910 was obtained.










Analysis. Calculated for rC16IT29iPPBr.*H2n t P 8.98;

Br, 23.18. Found P, 8.46; Br, 23.40.


7. Poly- (Dimethallylphenylpropylphosphonium bromide)

Two grams of dimethallylphenylpropylphosphonium bromide

was dissolved in five grams of dimethylformamide along with

0.08 gram (4 per cent) of ABN in a nitrogen flushed tube.

The tube was loosely stoppered and placed in an oven under

nitrogen at 68 for 34 days. The resulting solution was

poured into 150 ml. of dry ethyl ether. The white pre-

cipitate was dissolved in ten ml. of absolute ethanol and

reprecipitated from dry ether. The product was dried in

a vacuum desiccator at 60. One and two-tenths crams (60

per cent yield) of a white powder which softened at 1700

and formed a clear molt at 2200 was obtained.

Analysis. Calculated for C17HI26PBr.H2in: P, 8.60;

Br, 22.18. Found: P, 8.46; Br, 21.6.


8. Poly-(Diallyldiphonylphosphonium bromide)

Two grams of diallyldiphenylphosphonium bromide was

dissolved in five grams of dimethylformamide along with

0.08 gram (4 per cent) of ABD in a nitrogen flushed tube.

The tube was loosely stoppered and stored 34 days in an

oven under nitrogen at 68. The resulting solution was

poured into 100 ml. of dry ethyl ether. The white solid

product was dissolved in 15 ml. of absolute ethanol and










reprocipitated twice from dry ether. The white solid was

dried in a vacuum desiccator at 80. Nine-tenths of a gram

(45 per cent yield) of a white solid product which softened

at 2500 and formed a clear melt at 295-315o was obtained.

Analysis. Calculated for Ic18on20PBr*1H2n: P, 8.50;

Br, 21.90. Found: P, 8.49; Br, 21.80.


9. Poly-(Allylmothallyldiphenylphosphonium bromide)

Two grams of allylmethallyldiphenylphosphonium bromide

was treated as above. One and ninety-three hundreths grams

(96 per cent yield) of a white solid which softened at 2400

and formed a clear melt at 2700 was obtained.

Analysis. Calculated for Cl9JH22PDBr-H2n: P, 8.19;

Br, 21.10. Found: P, 7.90; Br, 20.68.


10. Poly-(Dimethallyldiphenylphosphonium bromide)

Two crams of dimethallyldiphenylphosphonium bromide

was treated as above. Seven-tenths of a gram (35 per cent

yield) of a light tan solid which softened at 2560 and

formed a clear melt at 3260 was obtained.

Analysis. Calculated for E20H24PBr.IH2 n: P, 7.90;

Br, 20.35. Found: P, 8.05; Br, 20.48.


G, Poly-(Phosphine oxides)

(Properties in Table 3)

1. Poly-(Diallylphenylphosphino oxide)

Poly-(diallyldiphonylphosphonium bromide) (7*4 grams)









was dissolved in 50 ml. of methanol and placed in a flask

equipped with a reflux condenser. To this solution was

added four grams of sodium hydroxide dissolved in 50 ml.

of water. The solution obtained was refluxed for 17

hours.22 The reaction mass was extracted with benzene

in a liquid-liquid extraction apparatus over a 16 hour

period. The benzene solution was evaporated under reduced

pressure. Twenty ml. of absolute ethanol was used to

dissolve the residue and it was precipitated three times

from dry ethyl ether. The residue previously extracted

with benzene was neutralized using hydrochloric acid.

Amyl alcohol was used to extract the liquid layer. The

solution was evaporated under reduced pressure. Twenty

ml. of absolute ethanol was added. After filtering, the

ethanol solution was poured into dry ethyl ether. The

product was redissolved and reprecipitated three times.

The benzene extraction yielded 0.4 gram and the amyl

alcohol extraction yielded 0.9 gram of compounds with

nearly identical infrared absorption spectra.

Analysis. Calculated for [C12H15P n, C, 70.0;

H, 7.29; P, 15.03. Calculated for c12HlPOH.B2on:

C, 64.3; H, 7.59; P, 13.82. Found: C, 62.0; H, 7.20;

P, 12.35.

2. Poly- (Diallylmethylphosphine oxide)

Poly-(diallylphenylmethylphosphonium bromide) (7.5 grams)










was dissolved in 50 ml. of methanol and placed in a flask

equipped with a reflux condenser. A solution of four grams

of sodium hydroxide in 50 ml. of water was added. The

resulting solution was refluxed for 22 hours. The solution

was then extracted with 150 ml. of benzene in a liquid-

liquid extraction apparatus over 24 hours. The solution

was neutralized and extracted using 50 ml. of amyl alcohol.

Upon evaporation of the benzene extract, a trace of solid

was obtained. The amyl alcohol layer was evaporated and

yielded an oil which was reprecipitated five times from

ethanol-ether. The solid was dried in a vacuum desiccator

at 800 One and eight-tenths grams (45 per cent yield)

of a compound which softened at 193 and formed a clear

melt at 292-3100 was obtained. The infrared spectrum

contained absorptions which corresponded with other poly-

phosphine oxides and expected functional groups. The

compound is extremely hydroscopic and dependable analytical

data could not be obtained.


II. Hydrocenation

1. Poly-(Dimoithallylphenylmrethylospphonium bromide)

An attempt was made to hydro;enate poly-(dimethallyl-

phenylmethylphosphonium bromide) to remove unsaturation

believed to be present. One gram of polymer was dissolved

in 40 ml. of absolute ethanol and placed in a pressure

hydrogenation npparntus along with 0.1 gram of platinum










dioxide. The sample was shaken at room temperature under

25 p.s.i* of hydrogen for 64 hours. The polymer was iso-

lated by precipitation from dry ethyl ether* Infrared

analysis indicated that the material was unchanged by the

above treatment.


I. Triphenylmethylphosphonium bromide

1. Triphenylmethylphosphonium bromide

One hundred grams (0.38 mole) of triphenylphosphine

was dissolved in one liter of dry benzene in a flask fitted

with a stirrerg condenser and a gas inlet tube, Forty-

seven grams (0.5 mole) of methyl bromide was bubbled into

the solution with stirring over a 0.5 hour period at room

temperature. Stirring was continued for one hour. The

flask was allowed to stand two days at room temperature.

A solid product was obtained which was filtered and washed

with 500 ml. of dry benzene. The solid was dried 48 hours

in a vacuum desiccator at 800, Ninety-seven grams (71 per

cent yield) of a white solid melting at 228-2300 was

obtained. This compound has previously been reported to

have a melting point of 233.5-2340.12


J, Viscosity Measurements

Flow times at several polymer concentrations were

obtained for each polymer. The viscosities were run at

250 using an Ubbelohde viscometer for all polyelectrolytes.










The solvent chosen for poly-diallyl- and poly-(dimethallyl-

alkylarylphosphonium bromides) was 0.1 I KBr in methanol-

water (t11).

For poly-dially-, poly-allylmethally-, and poly-

(dimethallyldiarylphosphonium bromides), 0.1 N KBr in

methanol-water (2;1) was used.

The viscosity measurements of the poly-(phosphine oxides)

were taken at 250 using a Cannon Ubbelohde Semi-Micro

Dilution Viscometer. Absolute ethanol was the solvent in

this case.

Specific viscosity was calculated in each case using

the equationl18'19


t-t
n s
sp ---


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

time of flow of the solvent. Intrinsic viscosity was

determined graphically from a plot of specific viscosity

divided by concentration versus concentration. The intrin-

sic viscosities determined by this method appear in Table 3.








TA.0CLC 1

::o0o:0ns


Compound Yield Melting point Analytical

P "or
%OC. _ _..... _"

Cale. Found Cale. Found


(cI12=cICn,2) 2 (c615) (CB3) PBr

(112=CC0110112)(06"115) (C2115)PBr

(c20=cn01101) 2 (c6n5) (C3n7)PBr

(CI12=CHC112) 3 (C6H15) PDr

(C=cci3cn32) 2 g(C6115) (CIn3 )PoBr

(CI2=CC130GI2) 2 (C6115) (C2115) PBr

(112=CC0113 0112 ( C6115) (C317 ) PBr

(CH2=CHCH12) 2 (06115) 2PBr

(CI12=CItCII3) (Cg12=CC113CIIg) (06{f5)2PBr

(cI12=cc1n3CII) 2 (c615) 2P r r


98-99

123-130

85

109-111

175-173

77-79

107-110

155-157

162-164

179-180


10.86

10.37

9.90

10.12

9.31

9.483

9.09

8.94

8.59

9.27


10.86

10.31

9.84

9.97

9.68

9.40

9.18

8.75

8.61

8.39


28.03

26.76

25.20

25.63

25.32

24.47

23.40

23.01

22.18

21.33


23.22

25.87

25.50

25.37

24.81

24.63

23-07

23.14

22.19

21.39


- I ---------- -1------ --- -----------






TABLE
POLYMERIZATION


2
CONDITIONS


Monomer Solvent Initiator Time Temperature
days 0C.

(CH2=HCH2)2 (C6H5) (CH3)PBr 33% H20 1,68% BHP 3 68
(CH2=CHCH2) 2 (C065) (C2H5) PBr 67- DMF 5% ABN 14 68
(CH2=CHCH2)2(CgH5)(C3H7)PBr 67% DMF 10% ABN 13 68
(CH=CC13CHH2)Z (C6H5) (CH3)PBr 33% H20 5% ABN 6 110
(CH2=CCH3CH2)a (6H5) (C2H5)PBr 50% DMF 4 ABN 6 110
(CHa=CCH3CH2)2(C6H5) (C3H?)PBr 60o DMF 4% ABN 34 68
(CH2=CHCH2)2(C6H5)2PBr 60% DMF 4 ABN 34 68
(cH2=CHC2) (CH2=CC3CH12) (C6H5)2PBr 60% DMF 6% ABN 34 68
(CH2=CH3CHC2)2(C6H5)2PBr 60% DMF 4% ABN 34 68
(CH2=CHCH2)3(CgH5)PBr 33% H20 4.2% ABN 4 68


DMF = Dimethylformamide
BHP = t-Butyl hydroperoxide
ABN = -aEodi-iso-butyronitrile










POLY"."'.3

Intrinsic Analytical
olymer Yiold *oftoning Viscosity -- P --
Point oC. n -- -
Cale. Found Cale. Found


( "::8CI f2 .(C61.5. (f"3") "r' i2- n

-- nr: ) (c U5 )(cn3)Pr*;2 n
|(ci =cr3c:) f(cG6;) ({*u5) .rr n ;

C!:=3CI C2), (C615) (C311) P r.L2o n

c=ci-:3:2 ()3(CC6l5) 1* 3

c:i,-- 3 = -i:3cn )"2'(c6i"5) {cn3:-;r.n20] n

17c-:2C1 3C2) 2(0615) 1 2I5 Pt 15 20

'i2= 3"' ) 2 (C2)2 5 (Ci5) (C3H7)P nr*i20n







L 1:1;,) (c1)1'12 (n
IJ.*. ^-: 71:i ::)2 ICg1<;)2'i*





* Calculated: C 64.3; TI, 7.59. 7Foun;: C,
*~lo rollablo analysis could b- obtained.


6o

100

60



95

20

6o

45

96

35

60

45


230

;:go

200



::-

135

170





250

262

1,3


0.035

0.034

0.020



0.018

0.025

0.032

0.031



0.013

0.109

0.103


10.22

9.78

9.36

9.43

9.36

S.928

8.60

3.50
0.19

7.90

13. 2

*A


10.3-

9.30


-~,i
9.10

9.41

8*63



3.59

7.90

3.05

12.35


26. 0

25.20

24.10

24.30

24.13

23.13

22.18

21.90

21.10

20.35

b


26.77

24.05

23.34

23.34

24.03

21.50



21.630
21.S0

20.63

20. 4


...0; C, .
















CHAPTER VI

DISCUSSION : OF RESULTS


A. Monomers


It has been known for some time that tri-aryl phosphines

are stable to oxidation by air.25 These compounds may in

fact be stored for long periods of time with no special pre-

cautions. On the other hand, tri-alkyl phosphines have a

groat affinity for atmospheric oxygen. The mixed aryl-alkyl

phosphines prepared as intermediates in this study have

affinities for oxygen which lie between these extremes. Both

diallyl- and dimethallylphenyl phosphineo which wore prepared,

oxidize rapidly in the presence of traces of air. Exposure

to air of the ether solutions of either of these compounds

produced hazy solutions almost immediately due to the for-

mation of the corresponding phosphine oxides. "hen the

compounds were freed from solvent by distillation, the

oxidation took place even more readily. This property of

dialkylaryl phosphines made it necessary to handle them in

a dry nitrogen atmosphere. Distillation was performed under

nitrogen. Even a small leak in the vacuum train produced

hazy distillates. The phosphine oxides are only slightly

soluble in the phosphines, as they are in ether, and thus










oxidation can usually be detected.

The allyl- and methallyldiphenyl phosphines were found

to be loss susceptible to oxidation than their mono-phonyl

counter-parts. In other solution it was possible to trans-

fer these compounds without noticeable oxidation. However

removing the solvent increased their reactivity toward atmos-

pheric oxygen and distillation was accomplished under dry

nitrogen.

Upon obtaining any of the substituted phosphinos men-

tioned* the materials were immediately dissolved in dry

ether and an alkyl bromide added. This was accomplished

without admitting air. The phosphonium compounds produced

appeared to be very sensitive to traces of phosphine oxide

impurities. Although phosphonium halides are hygroscopic,

the phosphine oxides appeared to be even more hygroscopic.

Infrared examination of each product was used to detect the

phosphino oxide impurity. The phosphorus-oxygon bond in
-1 26
this case gave a broad, strong absorption at 1150 cm. .

Compounds containing phosphino oxide impurities were found

to form oils. The hylroscopic nature of the impurity appeared

to be a contributing factor in this behavior. Solid products

could be obtained only when the impurity was in trace amounts

or was removed by repeated reprecipitations from alcohol-

ether. Large amounts of the impurity could not be removed

by this technique. Infrared spectra revealed that the solid











materials obtained by reprecipitations did not contain

phosphorus-oxygen bonds, Upon removal of the phosphine

oxide impurity, it was possible to obtain materials which

were also free of water as shown by the absence of an in-

frared absorption at 3500 cm.-1 corresponding to the -OH

group.

The monomers prepared during this work fall into three

series, The first consists of three diallyphonylalkylphos-

phoniun bromides. The second is a series of three dimethallyl-

phonylalkylphosphonium bromides. In both of those the alkyl

groups are methyl, ethyl and propyl. The last series con-

sists of three diphenyldialkylphosphonium bromides. The

alkyl groups involved are diallyl in one case, dimethallyl

in another and, finally, allylmothallyl.

Examination of the chemical formulas of these compounds

leads to the grouping of them into these series. It was

found that they exhibit properties consistent with this

arrangement. In each group the phosphonium bromides obtain-

ed became more waxy in appearance as the molecular weight

increased. The melting points observed, however, do not

indicate a constant change as a function of molecular weight

alone.

The phosphonium bromides were prepared by the reaction

of a phosphine with an alkyl bromide. The reaction may be

considered to be the displacement of a bromide ion of the

alkyl bromide by the pair of electrons of the phosphorus











atom which are not involved in bonding. The two new species

are a bromide ion and a phosphonium ion. These two then

combine to give a compound of the correct stoichiomotry.

Regardless of the exact mechanism of this reaction, it is

necessary for the phosphorus, with its pair of electrons,

to approach the carbon to which the bromine atom is bonded.

A reaction of this type has steric requirements involving

both species. The steric hindrance about both the electron

pair of phosphorus and the carbon to which the new bond is

formed dictates the extent of the reaction. This factor is

found to play a role in each series synthesized. As the

size of the alkyl bromide is increased, the phosphine makes

fewer collisions at the reaction site. An inspection of

reaction times and yields obtained in a series seems to be

consistent with this reasoning. In the case of the diallyl-

phenylalkylphosphonium bromide series it appears that the

increase in steric requirements is of little consequence

for the reactions involving ethyl bromide and propyl bromide.

The yields from these reactions are of about the same magni-

tude as can be seen in Table 1. The yields obtained in the

dimethallylalkylarylphosphonium bromide series and the

dialkyldiarylphosphonium bromide series show a pronounced

steric effect as the alkyl bromide increases in size.

An attempt was made to extend the diallylphonylalkyl-

phosphonium bromide series. Reactions wore carried out to

obtain diallylphenylhydroeonphosphonium bromide by reacting










diallylphenylphosphine with hydrogen bromide. The product

of the reaction was a solid, the infrared spectrum of which

contained absorptions characteristic of the expected product.

Elemental analysis for the product could not be obtained

which agreed with the theoretical values. After several

attempts to purify the product, the results were still

inconclusive. The product obtained may either contain an

impurity which has a similar infrared spectrum or may be

too unstable to undergo the reactions required for analysis.

Since a sample with acceptable elemental analysis could not

be obtained, further work on this monomer was abandoned.

Another compound which belongs to the diallylphenyl-

alkylphosphonium series is diallylphenyl-tert-butylphos-

phonium bromide. Several attempts to prepare this compound

led to solids which contained large amounts of diallyl-

phenylphosphine oxide. The phosphorus-oxygen absorption at

1150 cm.-l in the infrared spectrum was very large and broad

for all of these products. The steric requirements for the

reaction which produces phosphonium compounds can not be met

in this case, due to the bulk of the tert-butyl group. Even

after long reaction time in concentrated solution a large

amount of unreacted phosphine was evidently present in the

equilibrium mixture. Exposure to air then converted the

phosphine to the phosphine oxide. All attempts to separate

these materials failed.

One other monomer was prepared* Triallylphenylphosphonium










bromide was obtained by reactions similar to those used to

prepare other monomers. Although this compound is not a

member of any of the series prepared, the polymerization

product of this material should be cross-linked and add

support to the theory of cyclization for the diunsaturated

phosphonium compounds.


B. Polymerizations


Free radical initiation was chosen as the method for

polymerizing the monomers prepared. Since the phosphonium

compounds are somewhat ionic in characters the use of anionic

or cationic initiation is precluded* Compounds of this type

are also known to poison the Ziegler catalyst system 27

Free radical initiation then becomes the only remaining

choice. This is unfortunate because of difficulties which

have been observed28 in attempting the polyiwerization of

allylic materials by means of free radicals. The phenomenon

known as degradative chain transfer arises due to the labile

hydrogen atoms attached to the carbon alpha to the double

bond. Abstraction of one of these hydrogens by a free

radical leads to a new radical which is stabilized by free

radical resonance. Due to this stability, the new radical

is not active enough to act as a chain carrier. Although

degradative chain transfer leads to a new radical, it in

effect is a chain termination step.

The radicals first used to polymerize the monomers









prepared were obtained by the thermal decomposition of tert-

butyl hydroperoxide, This material is water soluble and was

convenient because of the solubility of the monomers in polar

solvents such as water and alcohols. Tertiary butyl hydro-

peroxide was successfully used in polymerizing some of the

monomers as shown in Tables 2 and 3. This material, however,

gave polymerization products in some cases which were low

melting and contained considerable unsaturation as shown in

the infrared. In order to obtain saturated polymers, an

experiment was undertaken using diallylphenylethylphosphonium

bromide with three different initiators* Three polymeri-

zations were run under identical conditions with t-butyl

hydroperoxide, benzoyl peroxide and of, c'-azodi-iso-buty-

ronitrile (ABN) in dimethylformamide solutions. It became

obvious upon isolation of the products from these reactions

that the initiators had produced polymers which varied con-

siderably* The product from t-butyl hydroperoxide was a

semi-solid which yielded a white solid only after several

precipitations. Benzoyl peroxide initiation yielded a

highly unsaturated oil which did not produce a solid after

several reprecipitations. The polymer obtained from ABN

initiation was a white solid when precipitated and gave an

infrared spectrum which contained no absorptions correspond-

ing to terminal unsaturation. From this data it seemed that

radicals produced by the thermal decomposition of ABN were

more selective than the radicals produced from the other










initiators. Due to this selectivity, fewer allylic hydro-

gens were abstracted and, therefore, fewer chains were

terminated by degradative chain transfer. In cases where

t-butyl hydroperoxide initiation had failed or had given

only oils as products, ABN was used. This initiator gave

cleaner reactions and through its use, polymers containing

very little unsaturation were produced from all monomers

used in this work.

Solution polymerization was used throughout this study.

It is not known definitely if other free radical initiated

systems will produce linear polymers from these compounds.

Bulk polymerization has been found to yield linear polymers

from 1,6-diunsaturated phosphine oxides.20 No bulk poly-

merizations were attempted using phosphonium type monomers

due to the high melting points of these compounds, The

concentrations used for the solution polymerizations were

near saturation* The solvent acted only to bring the monomer

and initiator into a single phase.


C. Polymers


The polymers prepared from the monomers discussed

earlier have several things in common. All of them are

soluble in ethanol and dimethylformamide. All had infrared

spectra which contain very little or no absorption corres-

ponding to unsaturation. The softening points of the polymers










are higher than the melting points of the monomers. The

analyses of the polymers were, in every case, consistent

with the analyses calculated for the monohydrates,

The increased softening points indicate an increase in

molecular weight. The analyses corresponding to hydrated

products are also indicative that larger molecules were

formed by the polymerization reaction. Phosphonium com-

pounds are known to form hydrates and water of hydration

would be more difficult to remove from high molecular weight

compounds. The fact that the materials formed are soluble

indicates that they are linear. The cyclic mechanism pro-

posed by Butler and Angelo4 accounts for the reaction of

two double bonds per repeating unit in the polymer chain.

The infrared data and solubility of these materials is then

consistent with the formation of cyclic units, separated by

methylene groups# for these materials.

It had been thought that sterio factors contributed to

the ease of formation of cyclic units from 1,6-diene systems.

One of the objectives of this study was to test this hypo-

thesis. By varying the groups attached to phosphorus, other

than the allyl functions, it is possible to make the molecule

more crowded. That is, an increase in the bulk of these

groups would allow the allyl groups less volume through which

to rotate and force them into a position more favorable for

intra -molecular reaction. The phenyl group was chosen as one

group in all cases and methyl, ethyl and propyl groups









introduced as the fourth group for both the diallyl- and

dimethallylphosphonium bromide series. It was found that

some steric forces are involved as it was not possible to

place both phenyl and tert-butyl groups on the same phos-

phorus atom. The product formed did not possess sufficient

stability to be isolated by the methods employed. The

volume available about the phosphorus in these substituted

phosphines could not accommodate the bulk of the tert-butyl

group. Another group of substituted phosphonium salts was,

however, prepared which contained two phenyl groups. In

the polymerization of the monomers there was no direct

steric effect upon oyclization. In no case was more than

a trace of insoluble presumably cross-linked materials

isolated. Intrinsic viscosity measurements, shown in Table

3i made on the polyelectrolyte polymers from diallylphenyl-

alkylphosphonium bromides show a decrease in chain length

as the alkyl group increases in size. The amount of residual

unsaturation was negligible for all the polymers. The primary

steric effect of aiding cyclization is then non-existent for

this series. A secondary steric effect can be seen through

the intrinsic viscosity data. Although cyclization is not

aided by an increase in size of the alkyl group, the chain

length appears to be shortened, It appears that in some way

the larger alkyl group partially prohibits the initial free

radical attack and thus lowers the efficiency of the polymeri-

zation*









No steric effect is noted, which aids cyclization in

the series of polymers obtained from dimethallylphenylalkyl-

phosphonium bromide monomers. Only negligible unsaturation

is shown in the infrared for these polymers, and no insoluble

materials were formed. A steric factor affecting chain

length, however, is operating, as shown by intrinsic viscos-

ity data. One mechanism by which polymer chains may terminate

is by means of degradative chain transfer. This method of

termination becomes very important in the case of dimethallyl-

phenylalkylphosphonium bromide monomers. Each monomer mole-

cule contains ten aliylic hydrogens. The intrinsic viscosity

values (Table 3) for these polymers increase as the size of

the alkyl group increases. The added size of these groups

offered steric protection against the abstraction of these

allylic hydrogens and thus reduced the amount of termination

due to degradative chain transfer.

In the series of diphenyl monomers, the nature of the

olefinic groups attached to phosphorus was varied while the

non-olefin groups remained constant. As found for the

previous series, the infrared spectra of these polymers

contained negligible absorption due to olefinic unsaturation

and no cross-linked materials were formed. Since the non-

olefinic groups remained unchanged, any change in intrinsic

viscosity among the members of this series is a result of

the nature of the olefinic groups. The diallyldiphenylphos-

phonium bromide monomer yielded a polymer with an intrinsic









value similar to that found for the first two members of the

diallylphenylalkylphosphonium series. Poly-(allylmethallyl-

diphenylphosphonium bromide) also had an intrinsic viscosity

of similar magnitude, It might be expected that this polymer

would have an intrinsic viscosity considerably lower due to

the increase in the number of allylic hydrogens, Earlier

mention was made of polymerizations initiated with

o<0oc'-aeodi-iso-butyronitrile as opposed to other radical

initiators. It appeared from this experiment that this

initiator yielded radicals which were more specific. Polymers

obtained using this initiator showed degradative chain trans-

fer to be less important as a termination mechanism. The

mixed monomer, allylmethallyldiphenylphosphonium bromide,

offers the attacking radical a choice of position for its

attack. From the data obtained, it appears that the radical

prefers the allyl terminal carbon to the methallyl terminal

carbon or the larger number of hydrogens in the allyl position*

The allylmethallyl monomer yields a polymer very similar in

chain length to diallyl polymers. The additional number of

allylic hydrogens evidently does not influence the chain

length in this case. In other cases# when the radical is

forced to attack a methallyl group some degradative chain

transfer is noted* The radical attack in this case then

most probably takes place at the allyl group.

In the case of dimethallyldiphenylphosphonium bromide,

no choice of attack exists. The intrinsic viscosity is









considerably less due to the large number of allylic hydro-

gens available for abstraction.

This and other work10 have indicated that steric factors

play either a very small part or no part at all in the for-

mation of cyclic units by this mechanism* In an effort to

explain the cyclization of 1,6-diene systems, a structure

has been proposed which involves some sort of intramolecular

electronic interaction between the olefinic linkages*29

This interaction would require partial bonding between the

olefin functions of the monomer. This bonding provides for

a proximity of these double bonds, thus the steric effect

due to bulky substituents in other parts of the molecule

does not modify the cyclization step in the reaction.

The partial bonding due to the interaction of the ole-

finic linkages appears to be very important in the polymeri-

zation of these 1,6-diene systems. Olefinic linkages which

contain different substituents generally also have different

reactivities. One might expect the mixed allylmethallyldi-

phenylphosphonium bromide monomer to give polymers in which

the more reactive double bond would homo-polymerize to the

exclusion of the less reactive one, This would produce a

linear material capable of cross-linking which does not

necessarily contain cyclic units. The electronic inter-

action between these non-equivalent double bonds, however,

appeared to remain the governing factor as with equivalent

double bonds, and a linear cyclic polymer was obtained in

high yield.









Poly-(triallylphenylphosphonium bromide) was also pre-

pared as part of this study. In the light of information

gained from the polymerization of triallylammonium bromides,

triallylphenylphosphonium bromide was expected to form a

cross-linked material. Poly-(triallylphenylphosphonium

bromide) was indeed cross-linked. The material is an amber,

glass-like, insoluble solid. The similarity between the

ammonium and phosphonium type polymers is strengthened by

the production of this cross-linked material.

Two of the polymers prepared appeared to be highly

unsaturated upon first examination. Both poly-(diallyl-

phenylmethylhospsphonium bromide) and poly-(dimethallphnylpnyl

methylphosphonium bromide) gave infrared spectra which

showed strong absorption in the 930 cm.-1 region. This is

the region where absorption due to terminal unsaturation was

expected. All of the monomers prepared absorbed in this

area, The polymers produced, however, did not absorb in

this area with these two exceptions. Poly-(dimethallyl-

phenylmethylphosphonium bromide) was catalytically hydro-

genated at 25 p.s,i. in order to eliminate the infrared

absorption at 930 cm."l. The product of the hydrogenation

gave a spectrum which was identical with the spectrum of

the material before hydrogenation. The failure to produce

a change in the infrared spectrum leads to the conclusion

that the absorption was due to some anomaly of these methyl

substituted compounds rather than to unsaturation in the










polymers. Infrared spectra of triphenylmethylpposphonium

bromide and triphenylallylphosphonium bromide were compared

with the spectra from the monomer and the polymer of di-

methallylphenylmethylphosphonium bromide and diallylphenyl-

methylphosphonium bromide. These spectra show a strong

absorption at 916 cm.," which may be assigned to phosphorus-

methyl bonds, Double bond absorptions for these compounds

are found at 1017 and 872 cm."1. These two absorption,

which appear in the spectra of the methyl-substituted mono-

mers, do not appear in the spectra of the polymers. It has

been concluded from this evidence that what had appeared to

be unsaturation in poly-diallyl- and poly-(dimethallylphenyl-

methylphosphonium bromide) is due rather to phosphorus-methyl

bonds. These polymers are now thought to be saturated

materials.

It has been established that amines act as inhibitors

for free radical reactions.30 It was assumed that phos-

phines would act in a similar fashion. If this were true

it would not be possible to polymerize diallylphenylphos-

phine by a free radical reaction. An attempt was made to

polymerize diallylphenylphosphine using a free radical

initiator in order to test this assumption. The monomer

was placed in a benzene solution along with five per cent

ABN and refluxed 11 days. The product, which was isolated,

possessed physical properties and an infrared spectrum










nearly identical with diallylepenylphosphine oxide.20

Since no polymeric material was isolated it was concluded

that the phosphine had acted as an inhibitor*

Reference was made earlier to intrinsic viscosity

values obtained for the polyelectrolyte polymers obtained.

Polyelectrolyte materials behave differently in solution

than non-electrolyte materials, In solutions the poly-

electrolytes obtained are free to ionize. The bromide

ions formed by ionization are free to move about in solu-

tion. The positive phosphonium ions formed are not free

to move about as they are bound together by the polymer

chain. These positive ions repel each other and force the

polymer chain to uncoil, The greater the extent of ioni-

zation, the more the polymer chain is extended. Dilution

of a sample of polymer causes greater ionization. Intrinsic

viscosity can not be measured under these conditions due to

the change in interaction between molecules in the system.

Ionization of these polyelectrolytes was held constant

enough for viscosity measurements to be made through the

use of added electrolyte. Intrinsic viscosity values were

obtained by the usual method. These values are small when

compared to values obtained for other polymer systems. The

magnitude of these values may have several meanings. First

the polymers may be of a low degree of polymerization. Or*

the degree of polymerization is large but the added electrolyte










has supressed the ionization to a point where the polymer

molecules remain tightly coiled and do not act as long chains.

Two polyelectrolyte polymers were degraded to give non-electro-

lyte polymers. This reaction and the polymers obtained by

this method will be discussed later. The intrinsic viscosities

obtained for non-electrolyte polymers obtained by degradation

are shown in Table 3. These values are considerably larger

than values obtained from the polyelectrolytes from which

thoy were obtained. Due to the change in intrinsic viscosity

between the compounds it was thought that both types of

polymers have longer chains than was indicated by the

intrinsic viscosities of the electrolyte materials, It

then seems that the added electrolyte is suppressing ioni-

zation and that the coiled molecules give very little indi-

cation as to their degree of polymerization in this system.


D. Infrared Data


Three methods were used to establish the identity of

the compounds synthesized. These were elemental analysis,

alternate synthesis and infrared absorption spectra. Infra-

red data has been mentioned throughout the discussion. A

more comprehensive account of the information gained by use

of infrared absorption spectra seems appropriate at this

point.


Absorptions corresponding to methylene groups were









found at 2900 cm."1 for all compounds. Several absorptions

appeared which may be assigned to the phenyl group* They

were found at 1600, 1580, 1480, 1115 and 750 cm."1 These

absorptions were found for all compounds synthesized which

contain phenyl groups. They varied only slightly from com-

pound to compound in intensity and position. Two peaks

were found which appear to be due to a phosphorus to phenyl

bond. They appeared at 1435 and 1215 cm.'. These absorp-

tions were not found in compounds in which the phenyl was

not directly bonded to phosphorus. They were absent in

compounds with a phosphorus-oxygen-phenyl linkage, for
20
instance.2 One absorption in particular was used to esti-

mate the purity of the compounds obtained. The phosphoryl

linkage gives a strong absorption at 1180 cm.*1. The phos-

phonium compounds studied were said to be free of phosphine

oxide impurity when this band was absent from their spectra.

Absorptions corresponding to olefinic unsaturation were

found at 1640, 985, 930 and 870 cm."-1 The absorptions at

1640 and 930 cm.-1 were found to be absent in the spectra

obtained from the polymers produced. The 930 cm."1 absorption

was particularly useful due to its sensitivity to small

amounts of unsaturation except in the case of methylphos-

phonium derivatives. The methylphosphonium compounds give

an absorption at 915 cm.-l which interferes with the olefinic

absorption. This absorption at 915 cm."I is believed to be










associated in some way with the methylphosphonium group, as

it was found only in compounds containing this grouping.

Due to this interference it was necessary to use the ole-

finic absorptions at 985 and 870 cm.I^ to estimate residual

unsaturation. Both of these olefinic absorptions were

absent from spectra of polymers obtained from monomers con-

taining the methylphosphonium group. Two other absorptions

appear in the spectra of methylphosphonium compounds which

may be assigned to this group. They are found at 1300 and

1280 cm."1.


E. Poly-phosphine oxides


Quaternary phosphonium halides will react with sodium

hydroxide to yield tertiary phosphine oxides. The reaction

has been said to proceed by the following route:

-OH
R4P+ + -0H--- RP-OH ---> R P-O-


R + R3P-~0


VanderWerf has stated that the radical which is eliminated

is the most stable anion when a choice is possible.23 This

conversion of a phosphonium halide to a phosphine oxide was

carried out with two of the poly-phosphonium compounds which

had been prepared. When poly-(diallyldiphenylphosphonium

bromide) was treated, a phonyl anion was lost. The product










of the reaction was poly-(diallylphenylphosphine oxide)*

No reliable analysis could be obtained for this product.

Poly-(diallylphenylphosphine oxide) had been prepared by

the free radical polymerization of diallylphenylphosphine

oxide.20 It was found that it also was difficult to obtain

an acceptable analysis on the polymer obtained in this

manner.31 The infrared spectrum of the poly-phosphine

oxide prepared by hydroxide degradation was identical with

the spectrum obtained by Berlin.20

1When poly-(diallylphenylethylphosphonium bromide) was

degraded by this method, the product was found to be poly-

(diallylethylphosphine oxide)* The phenyl radical was

eliminated rather than the ethyl radical due to its greater

stability.32 Again, analyses obtained for the product were

inconclusive* An examination of the infrared spectrum showed

a strong absorption at 1180 cm."1 for the phosphoryl group.

No absorptions appeared in the spectrum which could be

assigned to the phenyl group. The spectrum was very similar

in other respects to the spectrum of poly-(diallylphenyl-

phosphine oxide).

The intrinsic viscosities of the polyphosphine oxides

were considerably larger than the intrinsic viscosities of

the poly-phosphonium bromides from which they were prepared,

as was mentioned earlier. The intrinsic viscosity found for

poly-(diallylphenylphosphine oxide) prepared by degradation










20
was 0,109. Berlin2 reported an intrinsic viscosity of 0.026

for the same polymer produced by the polymerization of diallyl-

phenylphosphine oxide. It appears that the phosphonium bromide

polymerized to give a product having a considerably greater

degree of polymerization.

The poly-phosphine oxides produced by both methods appear

to be identical except for chain length. This is considered

to constitute an alternate synthesis of this cyclic polymer

and lends support, along with other evidence presented, to

the theory of cyclic polymerization of 1,6-diolefinic phos-

phonium bromides.















CHAPTER VII

SUMMARY


Several 1,6-diunsaturated phosphonium bromides were

synthesized by the reaction of the desired phosphine with

an alkyl bromide. These materials were polymerized in

solution using free radical initiators. The polymers

obtained were soluble in ethanol and dimethylformamide

in every case. The infrared spectra of the polymers in-

dicated that they were free of unsaturation. This evidence

supports the theory of intramolecular-intermolecular poly-

merization which was proposed to account for the production

of linear polymers to the exclusion of cross-linked polymers

from other 1,6-diene compounds. Two of the phosphonium

bromide polymers were converted to phosphine oxide polymers

by the action of sodium hydroxide. These phosphine oxide

polymers were found to be identical with phosphine oxide

polymers obtained by an alternate route. Intrinsic viscosity

data obtained for both polyelectrolyte polymers and non-

electrolyte polymers indicated that intrinsic viscosity

gave very little indication as to the nature of the electro-

lyte polymers*














BIBLIOGRAPHY


1. G. B. Butler and R. L. Bunch, J. Am. Chem. Soc., 71,
3120 (1949).

2, G. B. Butler and F. L. Ingley, J. Am. Chem. Soc, 73,
895 (1951).

3, H. Staudinger and W. Heurer, Ber., 6* 1159 (1934).

4, G. B. Butler and R. J. Angelo, J. Am. Chem* Soc*, 72,
3128 (1957).

5, C. S. Marvel and R, D. Vest, J. Am. Chem. Soc., 7 2
5771 (1957).

6. C. S. Marvel and J. K. Still, J. Am. Chem. Soc., 80,
1740 (1958).

7, A. Crawshaw and G. B. Butler, J. Am. Chem. Soc., 80,
5464 (1958).

8. J. F. Jonesi J. Polymer Sci., 2 15 (1958).

9. G. B. Butler, D. L. Skinner and R. W. Stackman,
Conference on High Temperature Polymer and Fluid
Research, WADD, Dayton, Ohio, May, 1959.

10. 'W L. Millers Ph.D. Dissertations University of Florida,
January, 1961.

11, J. F. Jones, J. Polymer Sci., 32, 7 (1958).

12. N. D. Field, J. Org Chem., 25, 1006 (1960).

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81, 4737 (1959).
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Soc., 80, 3615 (1958).

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









16. O. Grummitt, E. P. Budewitz and C. C. Chudd, 0r. Syn.,
26, 61 (1956).
17. G. M. Kosolapoff, Organophosphorus Compounds, John Wiley
and Sons, Inc., New York, 1950, Chapter 5.

18. R. M. Fuoss and U. P. Strauss, Ann. N. Y. Acad. Scit.
51, 836 (1949).
19. I. Kagawa and R. M. Fuoss, J. Polymer Sci., 18, 535
(1955).

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

21. L. Horner, H. Hoffmann, H. G. 1ippel and G. Hassel,
Ber., 9.., 52 (1958).

22. K. F. Kumli W McEwen and C. A. VanderWerf, J. Am.
Chem. Soc., 81, 3805 (1959).

23. M. Zanber, C. A. VanderWerf and E. W. McEwen, J. Am.
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24. M. Tamele, C. J. Ott, K. E. Marble and G. Hearne, Ind.
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25. G. M. Kosolapoff, Organophosphorus Compounds, John Wiley
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26. L. J. Bellamy, The Infra-red Spectra of Complex Molecules,
John Wiley and Sons, Inc., New York, 1958, P. 312.

27. J, K. Still, Chem. Revs., 58, 5 41 (1958).

28. R. C. Laible, Chem. Revss., 8, 809 (1958).

29. G. B. Butler, The International Symposium on Macromole-
cular Chemistry, Moscow, U.S.S.R., June, 19'0.

30. C. Walling, Free Radical Reactions in Solution, John
Wiley and Sons, Inc., New York, 1957, P. 432.

31* Ko D. Berlin, private communication*

32. R. C. Fuson, Advanced Organic Chemistry, John Wiley and
Sons, Inc., New York, 1950, P. 304.















BIOGRAPHICAL SKETCH


David Lloyd Skinner was born May 8, 1933, in Akron,

Ohio. He attended both elementary school and high school

at Kent State University School at Kent, Ohio. He entered

Kent State University in September 1951 and was graduated

in June 1955 with the degree of Bachelor of Science.

Upon graduation he joined the research staff of The

Lubrizol Corporation at Wickliffe, Ohio. During his employ-

ment he was a part-time graduate student at Western Reserve

University.

He entered the Graduate School of the University of

Florida in September 1957. He served as a graduate assist-

ant in the Department of Chemistry from September 1957 until

June 1958. From June 1958 until the present he has served

as a research assistant on contracts supported by the Wright

Air Development Division.of the United States Air Force.












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.


January 28, 1961.



Dean, College of Arts 'afd Sciences



Dean, Graduate School


Supervisory Committee:


Chairman




hIf? [ fc

'^M p.^^

u^L..^~










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AUTHOR: Skinner, David
TITLE: The preparation and polymerization of some diallyl- and
dimethallylphosphonium bromides. (record number: 430040)
PUBLICATION DATE: 1961


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