Title Page
 Table of Contents
 List of Tables
 Preparation of monomers
 Biographical items

Title: Preparation and polymerization of certain diunsaturated silanes.
Full Citation
Permanent Link: http://ufdc.ufl.edu/UF00091621/00001
 Material Information
Title: Preparation and polymerization of certain diunsaturated silanes.
Series Title: Preparation and polymerization of certain diunsaturated silanes.
Physical Description: Book
Creator: Stackman, Robert William,
 Record Information
Bibliographic ID: UF00091621
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000427152
oclc - 11111321


This item has the following downloads:

Binder1 ( PDF )

Table of Contents
    Title Page
        Page i
        Page ii
    Table of Contents
        Page iii
        Page iv
    List of Tables
        Page v
        Page 1
        Page 2
        Page 3
        Page 4
        Page 5
        Page 6
    Preparation of monomers
        Page 7
        Page 8
        Page 9
        Page 10
        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
        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
    Biographical items
        Page 48
        Page 49
Full Text






January, 1961


The author wishes to express his gratitude to Dr. George B.

Butler for his guidance and encouragement during this work, and to

Dr. 1. D. Berlin and the members of his Supervisory Committee for their

advice and suggestions. He wishes to express his appreciation to the

many graduate students, who through their assistance, suggestions, and

encouragement, contributed much to this work, and Mrs. Geraldine Houck

who typed the manuscript.

The work described in this dissertation was performed under the

sponsorship of the United States Air Force through the Materials Central

of the Wright Air Development Division.



LIST OF TABLES . . . . .


A. Literature Review *

B. Statement of Problem


A. Materials . *

B. Equipment and Data .


0 a 0 o 0 0 0 0 0 0 0 0 ii

. . . .. . . .

* 6 9 0 0 *

0 00
* . .

* 0 0

* 0 0 0 .


* SO



C. Preparation of Intermediates .

1. Allyl Grignard reagent o

2. Methallyl Grignard reagent

D. Preparation of Monomers .


* 0

* 0


* 0


* 0


0 e o i i * a



* 0*














1. Diallyldimethylsilane IC2i*CCH2 2)i(CH3)2.

2. Diallyldiphenylstilane F(CH,-M2CHC2) Si(C)2

3. Diallylmethylphenylsilane
KM2CH *CR2)2Si(CR)C6EC ] * * * .
4. Diallylcyclotetramethylenesilane
r5(a2ud-c2) 2i(Cu2)C l . . . . .
5. Diallylcyclopentamethylenesilane
CR2C 2 2Sc2 ****... *... ....

6. Dimethallyldimethyluilane
CH2C(C3CH2)2Si(C3>. 2 .*
7. Dimethallyldiphenylsilane

8. Dimethallylmethylphenylsilane

JCH27(C3)CH2z) iS2(C3)C . . .








9. Dtmethallylcyclopentamethylenestlane
[(C C(cH3)ca2)2s(c2)]. ..........
10. AllyldtethylvinylsllanesMC2CCH2l (CH3) 2CH.C2.


A* Materials ,* . . . .

*0C ..* Ct C

Ce...... .

B. Equipment and Data . ., , ,

C. General Polymerization Procedures .

1. Ziegler catalyst polymerization
2. Free radical polymerization .

D. Polymerization of Monomers . . .

DiallyldimethylsLlane . . .
Diallyldiphenylaulane . . .
Diallylmethylphanylsilane *
Diallylcyclotetramethylenesilane ,
Diallylcyelopentamethylenestilane .
Dimethallyldimethylsilane . .
Dimethallyldiphenylsilane . ,
Dimethallylmethylphenylsilane. .
Dimethallylcyclopentame thylenesilane
Allyldimethylvinylsilane 0 * *.

C CCC *C~ 0*

* a. .me...

meem.m.m .

0 0tb 0*
mm.. .4. t

. C 0 0 0 0

, m. ..

XV. DISCUSSION . . . . . . . . .

V. SUMMARY . . . . . . . . . . . ..

BIBLIOGRAPHY . . . . . . . . . . . . . .

BIOGRAPHICAL ITEMS . . ...... ..............


Table Page

1. Ziegler Catalyst Polymerisation of DiallyldimethylsLlane . 26

2. Effect of Catalyst Aging Upon the Polymeriation of
Diallyldimethylsilan6e , , , '. 0 . . 27

3. Free Radical Polymeri.tatiotl of Diallyldimethylsilane I . 28

4. 'Ziegler Catalyst Polymerization of Diallyldiphenylilane .. 129

5. Free Radical Polymerization of Diallyldiphenylsilane . .30

6. Polymerization of Diallylmethylphenylsilane . . . . 31

7. Polymerization of Diallyleyclotetramethyleneetlane . . 32

8. Polymerization of Diallylcyclopentamethylenestlane . . 33

7. Polymerization of ,Dimethallylsilanes ,* . . ,. ... .*. 34



A. Literature Review

Previous work in these and in other laboratories has shown that

many non-conjugated diene systems may be polymerized to linear, soluble,

saturated polymers containing a cyclic repeating unit.

Butler and Ingley,1 and Butler and Angelo2 reported that diallyl

quaternary ammonium salts polymerized to yield water soluble, linear

polymers which contained little or no residual unsaturation,,. An alter-

nating intramolecular-intermolecular chain propagation mechanism was

proposed to account for the polymers produced.2 According to this mecha-

nism, diene monomers capable of forming six--iembered ring systems by an

intramolecular attack on the terminal methylene of the second double bond

within the same molecule can result in linear saturated polymers, as

indicated below:


2 2 P2 2

The process consumes two double bonds per molecule, each molecule being

converted to a six-membered ring.

Considerable evidence for such a mechanism can be found in the

literature. Walling3 has commented on the fact that observed gel-points

in polymerizing systems, capable of crosslinking, should occur slightly

later than calculated by use of the gel-point equation of Stocknaycr4 due

to the occasional formation of cyclic structures. Studies were made on

systems of methyl methacrylate and ethylene dimethacrylate, and vinyl

acetate and divinyl adipate. The observed gel-point to calculated

gel-point ratio was often as high as 15-20. Simpson, Holt, and Zeite5

studied the polymer of diallyl phthalate at that gel-point and found

that about 40 per cent of the reacted monomer had been used up in the

formation of cyclic structures, Haward6 calculated from probability con-

siderations that 31 per cent of the reacted monomer in polymerizing

diallyl phthalate should be used up in cyclization of some hind. The

expcrinental results obtained by Simpsonet al.. are in good agrecncat

with this calculation. Simpson and Holt and Hlavard and Simpson have

e::tcnded their 'ork along these lines. More recently Oiwa and Ogata9

have shoxa that as high as 81 per cent cyclization occurs when diallyl

phthalate is polymerized in solution.

Butler, Cra'Ushnu, and Miller10 degraded representative polymers

of diallyl quaternary ammonium salts and proved the presence of piperi-

dinium rings in the polymer chain.

Polymerization by this mechanism has been extended by Marvel and

Vest who polymerized apz'-dimethylene pimelate derivatives to essen-

tially saturated linear polymers. Marvel and Stille described essen-

tially saturated linear polymers from 1,5-hexadiene and 1,6-heptadiene

by use of the trialkyl aluminum-titanium tetrachloride catalyst, although

some crosslinking occurred in the case of 1,5-hexadiene. Polymerization

of 1,6-heptadiene gave no crosslinking although the soluble polymer

contained 4-10 per cent of monomer unite which had not cyclized and each
13 14,15
contained one double bond. Crawehaw and Butler and Jones inde-

pendently described polymerization of acrylic anhydride, under a variety

of conditions to a soluble polymer. In an attempt to synthesize

diacrylylmethane by a Claisen condensation of methyl vinyl ketone with

ethyl acrylate, Jones16 isolated poly-(diacrylylmethane) which he at-

tributed to anionic polymerization of the monomer as it formed. Jones

has also prepared a cyclic 'polymer from allo'ocimene, 1arvcl, Kiener,

and Vessel, however, have described a linear, unsaturated polymer from

this monomer by Ziegler catalysis, tarvel and Vest19 have described

soluble polymers by polymerisation of a,' -dimethylenepimelonLtrilc as

well'as copolymers of this lonomer with other well-kLown' ionomer.e .

Marvel and Gall described the preparation of 2, 6diphenyll,6*hepia-
21 L
diene and Field has described the polymerisation of this monomer by all

the known general types of initiation, free radical, Ziegler type,

cationic and anionic, to give a polymer having cyclic units. Marvel and

Gall22 polymerized this monomer and also Z,5-diphenyl-l,5-hic:adieno and

Z,7-diphenyl-l,7-octadiene to yield polymers with cyclic recurring units.

They found that the five- and seven-membered rings form less readily than

does the six-membered ring in such polymerization reactions.

Price23 has described soluble copolymers of diallylalkylamine

oxides with acrylonitrile and other monomers. These copolymers were

assumed to possess one double bond for each molecule of diallylamine

oxide entering'the chain, however, in view of the polymerization mecha-

nism under consideration, copolymerization has probably occurred according

to this mechanism to produce saturated copolymers. Schuller, Price,

Moore, and Thomas24 have described a number of soluble copolymers in-

volving several diallyl monomers and several conventional monomers, and

have postulated that these copolymorizations follow the mechanism under

discussion. Friedlander25 reported the cyclization of allyl ether and

allyl sulfide to substituted tetrahydropyrans and tetrahydrothiopyrans

respectively when attempts were made to add various reagents under free

radical conditions.

Berlin and Butler26 have described soluble polymers from diallyl-

phenylphosphine oxide and dimethallylphenylphosphine oxide, and Skinner27

has described soluble polymers from diallylalkylarylphosphonium salts.

Marvel and Woolford28 and Butler and Stackman29 have reported linear

polyL.ers from diallyldimethylsilane.

Marvel and Garrison30 obtained varying ratios of soluble polymer

from higher diolefins in which the terminal double bonds were separated

by from four to eighteen methylene groups. Cyclization in these poly-

merizations can give rise to rings of from seven to twenty-one members.

Still 31 has described polymerization of 1,6-diynes, by use of

the Kiwilr catalyst, to linear, cyclic polymers in which the polymer

backbone consists of a continuous conjugated system of double bonds.

Barnett, Crawshaw, and Butler32 studied the polymerization of

unsaturated esters of maleic and fumaric acid and obtained soluble

polymers which contained cyclic units.

Butler33 has shown that 1,4-dienes will undergo copolymerization

with certain olefins to produce polymers containing a csi-ncrbered ring

formed during the process. Other copolymerizations were studied which


involved 1,5-dienes and molecules which are capable of inserting one atom

into the propagating chain, such as sulfur dioxide.

Delmonte and Hays 34have described the cyclization of a diole-

finic monomer which is accompanied by chain transfer. They studied

copolymerizations with vinyl acrylate as one of the monomers, and

cyclization of the vinyl acrylate followed by chain transfer stopped the


There are many references in the literature to certain dienes in

which cyclization may have occurred during polymerization. Blout and

Ostberg35 and Cohen, Ostberg, Sparrow, and Blout36 studied the polymeri-

zation of allylmethacrylate at both low and high temperatures. At

elevated temperatures gelation occurred at 6 per cent conversion while at

10 gelation did not occur until 39 per cent conversion. Evidence was

presented indicating that cyclization may have occurred but the results

were not attributed to this.

In an attempt to explain the strong polymerization tendencies of

1,6-dienes relative to their monoolefinic counterparts, it has been sug-

gested that there exists some kind of intramolecular electronic inter-
action between the two double bonds. A simple, well-known example of

this type of interaction is found in the case of the Claisen rearrange-

ment, in which 1,6-dienes rearrange through an intramolecular mechanism.37

The proposed interaction is also supported by the work of Marvel and

Stille,2 Schuller, et al.,24 Price,23 Miller,38 and Mikulasova and

Hvirik.39 Miller studied the shifts in the infrared spectra band for the

in-the-plane-deformation vibration of the terminal methylene group for a

series of diallyl compounds. Mikulasova and Hvirik39 have shown that


the total activation energy of radical polymerization for diallyldimethyl-

silane is about 9 kilocalories per mole double bond less than that for

allyltrimethylsilane. All of this evidence along with many other pub-

lished articles strongly supports this idea of an interaction between

the double bonds in 1,6-dienes.

B. Statement of Problem

The purpose of this research is to investigate the scope of the

intramo lecular-intermolecular polymerization ccichinis. by:

a. preparing a series of diunsaturated silanes, Ihich are

functionally capable of undergoing a cyclization, as a

part of the polymerization reaction, to give linear,

saturated polymers,

b. polymerizing these monomeric silanes, and

c. studying the resulting polymers.



In order to study the polymerization of diunsaturated silanes it

was decided to prepare a series of diallyl- and dimethallylsilanes. The

other groups attached to the central silicon atom were varied to study

any effect that they might have upon the polymerization. It was thought

that the polymers of compounds, in which the central silicon atom was

contained in a ring, might give polymers possessing interesting proper-

ties. Cyclic organosilicon compounds have been prepared by West.40
Tamborski and Rosenberg have reported a series of dialkylcyclopenta-

methylenesilanes. In addition to the diallyl- and dimethallylsilanes

allyldimethylvinylsilane was prepared in which the two unsaturated

groups were of different lengths.

Several diallyl- and dimethallyl silanes have been prepared.424344

Nasiak and Post44 prepared a series of these compounds by the action of

allyl or methallyl Grignard reagents.upon the appropriate chlorosilane.

This method was used for the preparations in this investigation.

A, Materials

The chlorosilanes, vinyldimethylethoxysilane, allyl bromide and

methallyl chloride were purchased from Peninsular ChemResearch Inc.,

Gainesville, Florida, and were distilled before using. The vinyl

Grignard reagent was also purchased from this company and was used as

received. The ether was obtained from stock and was dried over sodium

ribbon before use.

B. -quipme9t and Data

Temperatures reported nto this work are uncorrected. Distillation

pressures wtre read on a Zinmerli gauge.
Infrared data were determined with either a PerklU-Slaer Model 21

spectrophotometer or a Perktin-1Ber Infracord spectrophotometer.

The gas-liquid chromatographic analyses were performed with a
Vilkins Aerograph Model A-110-C gas chromstographic instrument, using

helium as the carrier gas and a five foot column packed with G. E. SF-96

silicone on C-22 fire brick.

Refractive indices were determined with a Bausch and Lomb Abbe 34
refractometer fitted with an achroaatic compensating prism.

Densities were determined on approximately 5 ml. samples nd all

weighings were made on an analytic balance.
Microanalyaes were performed by Clark Microanalytical Laboratory,
Urbana, Illinois.

C. Preparation of *aermediatee

to a fveliter, three-necked flask, equipped with a reflux con-
denser, addition funnel and mechanical stirrer, were added 85 0s

(3.5 ge-atoms) of magnesium turnings and 1.75 1. of absolute ether. The

flask we flushed with dry nitrogen. Two hundred and twelve grams (1.75

moles) of allyl bromide were weighed and a few ailliliters were 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. Throughout 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 with standard

base. The solution was found to contain 1.65 equivalents of the allyl

Grignard reagent; yield; 94 per cent.

2. Methallyl Grignard reagent

Into a two-liter, three-necked flask, equipped as above, were

added 36 g. (1.5 g.-atoms) of magnesium turnings and 500 ml. of absolute

ether. The reaction was started by the addition of a few milliliters of

allyl bromide. The flask was cooled with an ice bath and 91 g. (1.0 mole)

of methallyl chloride were added dropwise over a period of three hours.

After the addition was completed the mixture was stirred for an addi-

tional three hours. The Grignard reagent was a smooth suspension in the

ether and was too thick to analyze by titration.

D. Preparation of Monomers

1. Diallyldimethylsilane U2CH2 CHH2) 2Si(CH3) 2]

To 2.3 1. (2.3 equivalents) of allyl Grignard reagent were added

129 g. (1.0 mole) of dimethyldichlorosilane over a period of four hours.

The mixture was stirred for twenty hours at room temperature. Hydrolysis

was accomplished by pouring the contents of the reaction flask into a

chilled, 10 per cent hydrochloric acid solution. The ether layer and

one 100 ml. ether extract of the aqueous phase were dried over calcium
chloride; removal of the solvent by distillation left an oil which, when
fractionated, gave 106 g. (76.5 per cent) of diallyldimethylsilane,
b.p. 135o, nD 1.4405 reportedd4 b.p. 135-1360, n20 1.4402_]. Gas-
liquid chromatography indicated that the compound was pure. An infrared
spectrum of the compound exhibited the following bands (cm. ): 3050,
2950, 2900 (C-1); 1635 (C1I2=C'H-); 1423, 1390, 1298, 992, 894 (CH and Ci2
deformations); 1255, 830 (-Si(CH3)2-).

2. Diallyldiphenylsilane [CH2t=CCH2 2S(C 5) 2

To a solution of 1.5 equivalents of allyl Grignard reagent were

added 126 g. (0.5 mole) of dichlorodiphenylsilane, over a period of two
hours. The mixture was stirred for twenty-four hours and was then
treated in the same manner as was the above preparation to give 91 g.

(71 per cent) of diallyldiphenylsilane, b.p. 1340 (1 Bm.), p 1.5738
reportedd4 b.p. 140.50 (2 =m.), n20 1.5750J The infrared spectrum of
this compound exhibited the following bands (cm. ): 3050, 2970, 2950,
2900 (C-H); 1960, 1880, 1800 (phenyl);'1633 (CI12=CI-); 1425, 1350, 990,
900 (CH and CH2 deformations); 1428, 1111 (Si-phenyl); 1190 (Si-C).

3. Diallylmethylphenylsilane (CH212C iCR2) 2Si(CH3)CHO5

To a solution of 1.2 equivalents of allyl Grignard reagent were

added 100 g. (0.52 mole) of dichloromethylphenylsilane. The mixture was
stirred for twenty-four hours and was then treated in the same manner as
was the previous preparation to give 80.3 g. (75 per cent) of diallyl-
methylphenylsilane, b.p. 124 (15 mm.), 20 1.5200 Lreported-

b.p. 123.5-124.4o (20.5 u.m.), 20 1.522 An infrared spectrum of this

compound exhibited the following bands (cm. 1) 3060, 2970, 2950, 2575

(C-I1); 1960, 1880, 1800 (phenyl); 1635 (CI2=iCi-); 1485, 1390, 1300, 987,

893 (CHI and C12 deformations); 1426, 1112 (Si-phenyl); 1250, 830

4. Diallylcyclotetramethylenesilane E(CH12 cMIC2)2Si(CH2)4

To a solution of 1.05 equivalents of allyl Grignard reagent were

added 67 g. (0.43 mole) of dichlorocyclotetramethylenesilane over a

period of two hours. The mixture was stirred for an additional eight

hours and was then treated in the same manner as were the previous prepa-

rations, to give 56 g. (79 per cent) of diallylcyclotetramethylenesilane,

b.p. 98*101 (35 =m.), n 1.4857 d4 0.8825, MD 54.3 called. 54.9.

Gas-liquid chromatography indicated that the compound was pure. An infra-

red spectrum of this compound exhibited the following bands (cm.o- ): 3050,

2930, 2850 (C-R); 1635 (CeI2MCH-); 1450, 1415, 1400, 1380, 1290, 990, 894

(CH and CH2 deformations); 1245, 855 (Si-R).

Anal. Calcd. for C oH18Si: C, 72.20; H, 10.90; Si, 16.88.

Found: C, 69.80; H, 11.64; Si, 17.33,

5. Diallylcyclopentamethylenesilane [(C2=-CHCH2)2Si(C12)5]

To a solution of 1.48 equivalents of allyl Grignard reagent were

added 100 g. (0.59 mole) of dichlorocyclopentamethylenesilane, over a

period of three hours. The mixture was stirred for an additional eight

hours and was then treated in the same manner as was the previous prepa-

ration to give 72 g. (68 per cent) of diallylcyclopentamethylenesilane,


b.p. 104 (24 rm.), nD- 1.438S, d24 0.8779, M1D 59.9 calcd. 60.6.45 G-

liquid chromatography indicated that this compound was pure. An infrared

spectrum of this compound exhibited the following bands (c." ): 3030,

3030, 2900, 2850, 2800 (C-l); 1635 (CG2=CH1-); 1450, 1420, 1400, 1300, 990,

900 (C1 and CH2 deformations); 915 (cyclopentamethylene silicon ring).46
Anal. Calcd. for C H120Si: C, 73.28; II, 11.18; Si, 15.54.
Found: C, 72.07; I, 10.82; Si, 15.06.

6. Dimethallyldimethylsilane [(CH2C(CH3)CH2 2Si(C3) 2

To a suspension of the methallyl Grignard reagent, prepared with

1.0 mole of methallyl chloride, were added 25 g. (0.2 mole) of dimethyl-
dichlorosilane over a period of one hour. After the mixture was stirred
for twelve hours at room temperature, the mixture was treated in the

same manner as were the previous preparations to give 24 g, (71.5 per

cent) of dimethallyldimethylsilane, b.p. 75-79 (25 zm.), nD 1,4525

reportedd4 b.p. 71-71.6o (22 mm.), n20 1.4538]1. Gas-liquid chroma-
tography indicated that this compound was pure. An infrared spectrum of

this compound exhibited the following bands (cm." ): 3030, 2850, 2770
(C-lI); 1640 (C02=CII-); 1450, 1440, 1370, 1276, 997, 870 (CII and CH2

deformations); 1247, 830 (-Si(CH3)2-).

7. Dimethallyldiphenylsilano (C72_C(C3)CH2)2 Si(C6H5)2]

To a suspension of the methallyl Grignard reagent, prepared from

1,0 mole of methallyl chloride, were added 63 g. (0.25 mole) of dichloro-
diphenyloilane over a period of one hour. The mixture was stirred for an
additional t:canty-four hours and was then treated in the same manner as


were the previous preparations to ivo 41, g. (55 per cent) of dinethallyl-
0 22 44
diphenylsilane, b.p. 148o (0.5 mm.), n22 1.5650 [reported b.p. 193.8-

194.1 (14.5 s.), n2 1.5693 An infrared spectrum of this compound
exhibited the following bands (cm. ): 3050, 2980, 2910, 2720 (C-H);

1960, 13,0, 1800 (phenyl); 1635 (CHI2=C-); 1450, 1370, 1300, 1280, 975,

875 (CI and CH2 deformations); 1430, 1110 (Si-phenyl); 1190 (Si-R),

8. Dimethallylmethylphenylsilane E(CH2=C(CH3)CH2 2Si(CH 3)C6H5]

To the suspension of the methallyl Grignard reagent, prepared

from 1.5 moles of methallyl chloride, were added 70 g, (0.37 mole) of

dichloromethylphenylsilane over a period of one hour. The mixture %was

stirred for an additional twenty-four hours and was then treated in the

same manner as were the previous preparations to give 43 g. (51 per cent)

of dirothallylmethylphenylsilane, b.p. 1338 (12 r .), n2 1.5180 [repor-

ted b.p. 142143 (20 mm), n20 1.5221] An infrared spectrum of this

compound exhibited the following bands (cm."1): 3050, 2980, 2910, 2850,

2720 (C-iH); 1960, 1880, 1800 (phenyl); 1635 (CH2=CHI-); 1450, 1400, 1370,

1305, 1280, 980, 875 (CII and CH2 deformations); 1430, 1120 (Si-phenyl);

1255, 835 (Si-R).

9. Dimethallylcyclopentamiethylenesilane 1(CH12C(3)CHG2) 2Si(CH2)5-]

To the suspension of the methallyl Grignard rea3ent, prepared

from 1.8 moles of methallyl chloride, were added 82 g. (0.45 mole) of

dichlorocyclopentamethylenesilane over a period of one hour. The mixture

was stirred for an additional twenty-four hours and then was treated in

the same manner as were the previous preparations, to give 58 g.


(59.5 per cent) of dimethallylcyclopentamethylenesilane, b.p. 950 (2 mr.),
24 d4 08
nD 1.4907, d 0,8770, MRD 68.8 calcd. 68.9.45 Gas-liquid chromatography

indicated that this compound was pure. An infrared spectrum of this com-

pound exhibited the following bands (cm.1l): 3100, 2970,2900, 2300 (C-7);

1640 (CH2=CHl-); 1450, 1400, 1380, 1345, 1280, 993, 875, (CH and C12 defor-

mations); 915 (cyclopentarethylene silicon ring),46

Anal. Calcd. for C1U2Si: C, 74.94; 1, 11.61; Si, 13.45.

Found: C, 74.01; H, 11.36; Si, 13.77.

10. Allyldimethylvinylsilane [CI2=C2CSi(2I()2CI=CH2]

a. To a solution of 1.8 equivalents of vinyl Grignard reagent

in tetrahydrofuran were added 134 g. (1.0 mole) of allyldimethylchloro-

silane, dropwise over a period of five hours. The mixture was stirred

for an additional twenty hours and was then treated in the same manner as

were the previous preparations to give 64 g. (51 per cent) of allyldi-

methylvinylsilane, b.p. 111 (760 mm.), n2 1.4315, d4 0.7540, HR 43.39

calcd. 44.23.45 Gas-liquid chromatography indicated that this compound

was pure.

b. To a solution of 1.0 equivalent of allyl Grignard reagent

were added 130 g. (1.0 mole) of vinyldimethylethoxysilane over a period

of one hour. The mixture was then stirred at reflux temperature (40 )

for forty-eight hours. At the end of this period no reaction had occurred.

To the reaction flask was then added 500 ml. of benzene, and 500 ml. of

ether were removed by distillation. The mixture was stirred at 700 for

twenty-four hours. At the end of this period a large amount of salts

had formed in the mixture. The mixture was then treated in the same


manner as were the previous preparations to yield 35 g. (28 per cent) of

allyldimethylvinylsilane, b.p. Ill0 (760 =m.). The refractive indes: and

gas-liquid chromatography retention time for this compound were the same

as those for the product in the first preparation of this compound abovo.

Both products also possessed identical infrared spectra. The

spectrum exhibited the following bands (cm. ): 3030, 3000, 2950 (C-H);

1635, 1600 (CH2= C-); 1450, 1425, 1390, 1300, 1010, 990, 950, 895 (CH and

CH2 deformations); 1255, 850 (-Si(CH3)2-).

Anal. Calcd. for C7I14Si: C, 66.57; I, 11.17; Si, 22.24.

Found: C, 66.61; H, 10.95; Si, not determined.



It was expected that the silanes, described previously, would

undergo homopolymerization by the intra-intermolecular polymerization

mechanism. The work of Marvelet al. 12,1822 has shown that six-mem-

bered cyclic units form more readily than do five-membered rings and

therefore some difficulty might be encountered in the polymerization of

allyldimethylvinylsilane. Also in view of the larger size of silicon

compared to carbon and the known tendency of silicon to form eight-mem-
bered rings in the siloxane series, one is led to the conclusion that

the five-membered ring may be difficult to form.

Attempts have been made previously to polymerize a few diallyl-

and dimethallylsilanes with free radical initiators at high pressures. 449

These attempts have led to low molecular weight oils and cross-linked,

infusible solids. A kinetic study of the free radical initiated poly-

merization of diallyldimethylsilane and allyltirmethylsilane has been

made39 and low molecular weight polymers were reported. Polymerization

of diallyldimethylsilane and diallyldiethylsilane by use of a triethyl

aluminum-titanium tetrachloride complex catalyst has been reported50 in

which both liquid and solid polymers were obtained. From the liquids

could be isolated trimers, tetramers, and pentamers, however, the solid

polymers were insoluble in benzene, ether, and carbon tetrachloride but

swelled in heptane. These solids were obviously cross-linked.


Marvel and Woolford28 obtained soluble polymers containing cyclic

units from diallyldimethylsilane with Ziegler-type catalysts. Butler and

Stackman29 polymerized diallyldimethylsilane and diallyldiphenylsilane

with Ziegler catalysts to yield soluble, saturated polymers.

It was decided to attempt the polymerization of the diunsaturated

silanes with both Ziegler catalysts and with free radical initiators. Due

to "degradative chain transfer" most free radical initiated allylic poly-

merizations tend to give relatively low degrees of polymerization.51 The

Ziegler catalysts might be expected to give higher molecular weight poly-

mers. A great deal of work has been published concerning polymerizations

by use of these complex metal catalysts in the past five years.52'53

With these catalyst systems it is possible to obtain high molecular

weight polymers of a-olefins which could not be polymerized with free

radical initiators. There are, however, some types of a-olefins which

cannot be polymerized with conventional Ziegler catalysts. It has been

reported that -olefins with branching closer than the 3- or 4-position

to the double bond cannot be polymerized by this method. In view of this

evidence it would be unlikely that the dimethallylsilanes and possibly

the vinylsilanes would polymerize with the Ziegler catalysts. If these

findings hold true for these compounds it will be necessary to poly-

merize them by means of free radical initiators.

The Ziegler catalyst system chosen for the polymerizations was

triethyl aluminum-titanium tetrachloride. This is a common catalyst

system and both of these materials are readily obtainable. The free

radical initiator chosen was di-t-butyl peroxide. This initiator was

chosen because it is readily obtainable and is soluble in the non-polar

systems which will be used in the polymerizations.

Intrinsic viscosity measurements will be made on samples of the

polymers obtained in order to get an approximation to the relative degree

of polymerization.

A. Materials

The triethyl aluminum was obtained from the Hercules Powder Co.

Inc., Wilmington, Delaware, as a 25 per cent by weight solution in hep-

tane. Titanium tetrachloride was purchased from the Fisher Chemical Co.,

Fairlawn, New Jersey. Di-t-butyl peroxide was obtained from the Shell

Chemical Corp., New York, New York. The dicyclopentadienyltitanium

dichloride was provided by the National Lead Co., New York, New York.

Benzoyl peroxide was purchased from the Cadel Chemical Corp., Burt, New

York, and the aoa'-azobisisobutrronitrile was purchased from the Eastman

Organic Chemicals Division of Eastman Kodak Co., Rochester, New York.

The heptane used in the polymerizations was obtained from stock and was

distilled from sodium cubes and stored over sodium wire. Benzene, used

for intrinsic viscosity measurements was reagent grade obtained from

Fisher Chemical Co., New York, New York, The benzene, methanol, and

other solvents used in this work were obtained from stock and were used

as received.

B. Equipment and Data

Intrinsic viscosity determinations were performed using either a

Cannon-Fenske-Ostwald or Cannon-Fenske Semi-Micro Dilution type viscometer,


Melting points were determined in open capillary tubes in a melt-

ing point block.

Infrared data were determined with either a Perkin-Elmer Model 21

spectrophotometer or a Perkin-Elmer Infracord spectrophotometer.

licroanalyses were performed by Clark Microanalytical Laboratory,

Urbana, Illinois.

C. General Polymerization Procedures

1. Ziegler catalyst polymerization

Into a 50 or 100 ml. reaction flask, equipped with a reflux con-

denser, mechanical stirrer, gas addition tube, and rubber injection gasket,

was injected a measured amount of dry heptane. The flask was swept with

dry nitrogen. Measured amounts of triethyl aluminum and titanium tetra-

chloride were then injected into the flask. The dark brown catalyst

suspension was heated and stirred for a definite period to age the cata-

lyst, After this period the m=cnomer was added and the mixture was allowed

to react for various periods of time. At the end of the polymerization

period the mixture was hydrolyzed by pouring it into methanol. The poly-

imer was removed from the mixture by filtration, washed with a 10 per cent

hydrochloric acid solution, and dissolved in benzene. The solution was

filtered to remove any insoluble polymer and then the soluble polymer was

reprecipitated by adding the solution to rapidly stirred methanol. The

polymers were further purified by repeated reprecipitations from benzene

solution. The solvent was then removed by storing the polymers in a

vacuum desiccator.

2., Free radical polymerization

In a 20 amm test tube, equipped with a reflux condenser, was

placed a solution of the monomer and the free radical initiator (di-t-butyl

peroxide). The solution was heated by placing the tube in a bath maintained

at 135' by refluxing xylene. At the end of the polymerization period the

heat was removed. The polymers were removed from the tube and purified

in the same manner as were the polymers obtained with the Ziegler catalyst,

D Polymerization of Monomers

1l Diallyldimethylsilane

This monomer was polymerized by both free radical and Ziegler

catalyst initiation. The results of these polymerizations are summarized

in Tables 1, '2, and 3. From the Ziegler catalyst initiated polymeriza-

tions were obtained heavy, viscous liquids, gurney, semi-solids, and wilite

solids. All these fractions were soluble in benaene, heptane, and chloro-

form, A small amount of insoluble material was also found among the

products. A series of experiments was performed in which the catalyst

mixture, made up of various mole ratios of the co-catalyst compounds, was

aged for short periods. The results of this study are listed in Table 2.

The products of the free radical initiated polymerizations were either

heavy, viscous oils or gummy, semi-solids. Upon standing in closed

bottles for about two months, the soluble, radical initiated polymers

cross-linked to give insoluble, infusible solids,

The infrared spectra for these polymers were all very similar,

The free radical initiated polymers showed an appreciable absorption for

unsaturation. The infrared spectrum of a typical, Ziegler catalyst

initiated polymer exhibited the following bands (cma, ): 2980, 2900

(C-H); 1440, 1400 (CI2 and CH3 deformations); 1285, 830 (Si-(C 3)-).

Anal, (Ziegler catalyzed polymer) calcd, for (C8116Si)n C,

68.52; H, 11.50; Si, 19.98. Found: C, 65,84; 1, 10.91; Si, 19.73.

2. Diallyldiphenylsilane

This monomer was polymerized with both initiator systems. The

results of the polymerizations are summarized in Tables 4 and 5, The

polymers were all white solids and there was no apparent difference in

the polymers obtained with different initiators. Polymerization was also

attempted with a soluble Ziegler type catalyst using dicyclopentadienyl-

titanium dichloride in place of the titanium tetrachloride. In the

several polymerization attempts made, only trace amounts of solid polymer

were obtained.

The infrared spectra of the polymers were identical and exhibited
the following bands (cm.1): 3020, 2970, 8880 (C-IH); 1960, 1880, 1800

(phenyl); 1485, 1443, 1400 (CH2 deformations); 1428, 1111 (Si-phenyl);

1190 (Si-R).

Anal. Calcd. for (C18H20Si)n: C, 81,78; H, 7.63; Si, 10,60.

Found: C, 80.74; II, 7.60; Si, 10.40.

3. Diallylmethylphenylsilane

Polymerization of this monomer was accomplished by use of the

Ziegler catalyst to give heavy oils, gummy solids, and white solids. The

results of the polymerizations are shown in Table 6. The infrared

spectrum of one of the solid polymers exhibited the following bands


(cm.'1): 3000, 2950, 2875 (C-H); 1960, 1880, 1800 (phenyl); 1485, 1440,

1395 (CI2 and CH3 deformations); 1426, 1112 (Si-phenyl); 1250, 830


Anal. Calcd. for (Cl3 18Si)n: C, 77.15; H, 8,96; Si, 13.88.

Found: C, 71.60; H, 8.72; Si, 13.79.

4. Diallylcyclotetramethylenesilane

This monomer was polymerized with the Ziegler catalyst to give a

white, solid polymer as well as some lower molecular weight material.

The results of the polymerizations are shown in Table 7, The infrared

spectra of polymers exhibited the following bands (cm, ): 2950, 2900,

2830 (C-H); 1635 weak (CH2=CHl-); 1455, 1400 (CH2 deformation); 1250, 860


Anal. Calcd. for (C H Si)n: C, 72.20; H, 10.90; Si, 16.88.

Found: C, 69.80; I, 11.64; Si, 17.41.

5, Diallylcyclopentamethylenesilane

Polymerization of this monomer was accomplished by use of the

Ziegler catalyst to give white, solid polymers in addition to other lower

molecular weight compounds. The results of these polymerizations are

shown in Table 8. The infrared spectra of the polymers exhibit the fol-

lo.in2 bands (cm."1): 3030, 2300, 2800 (C-IH); 1635 weak (0C12=.1-); 1460,
1450, 1400 (CH2 deformations); 915 (cyclopentamethylene silicon ring).

Anal. Calcd. for (C iH20Si)n: C, 73.28; 1, 11.18; Si, 15.54.

Found: C, 69,07; IH, 10.58; Si, 15.95.

6. Dimethallyldimnethylsilane

Attempts to polymerize this monomer with the Zieoglr catalyst gave

no polymer.

Polymerization of this monomer was accomplished with di-t-butyl

peroxide as the initiator. The results of the polymerizations are shown

in Table 9. The polymers obtained were soft, sticky semi-solids, soluble

in benzene and heptane. The infrared spectra of the polymers exhibit the

following bands (cm."1): 3100, 3030, 2960, 2850 (C-1); 1640 very weak

(CH2=CH-); 1460, 1425, 1380, 1280, 980 weak, 880 weak (CH2 and CH3 defor-

mations); 1255, 825 (-Si(CH3)2-).

Anal. Calcd. for (C H120Si) : C, 71.34; H, 11.97; Si, 16.68.

Found: C, 71.04; U, 11.31; Si, 16.75.

7. Dimethallyldiphenyloilane

Polymerization of this monomer was accomplished with di-t-butyl

peroxide as the initiator. The polymers obtained were white solids which

were soluble in benzene. The results of the polymerizations are shown in

Table 9. The infrared spectra of the polymers exhibited the following

absorption bands (cm. 1): 3100, 3000, 2920 (C-H); 1960, 1880, 1800

(phenyl); 1460, 1380, 1300 (CH2 and CH3 deformations); 1425, 1120

(Si-phenyl); 1190 (Si-R).

Anal. Calcd. for (C20H24Si)n: C, 82.12; H, 8.27; Si, 9.60.

Found: C, 80.88; Si, 8.72; Si, 9.43.

8, Dimethallylmethylphenylsilane

Polymerization of this monomer with di-t-butyl peroxide gave a

white, benzene soluble, solid. The polymerization conditions and proper-

ties of the polymer obtained are listed in Table 9. An infrared spectrum

of this polymer exhibited the following absorption bands (cm," ): 3100,

3000, 2920 (C-H); 1960, 1880, 1800 (phenyl); 1640 very weak (CH2=CH-);

1450, 1375, 1300 (CH2 and. C3 deformations); 1425, 1120 (Si-phenyl);

1200 (Si-R).

Anal. Calcd. for (C15H24Si)n: C, 78.18; H, 9.62; Si, 12.18.

Found: C, 76.31; H, 9.38; Si, 12.76.

9, Dimethallylcyclopentamethylenesilane

This monomer was polymerized with the free radical initiator,

di-t-butyl peroxide. A white solid was obtained which was soluble in

benzene. The results of the polymerization are shown in Table 9. The

infrared spectrum of the polymer exhibited the following bands (cm. ):

3010, 2900, 2820 (C-H); 1640 very weak (CH2=CH-); 1450, 1400, 1380, 1350,
1290 (CHI2 and CH3 deformations); 915 (cyclopentamethylene silicon ring).

Anal. Calcd. for (C13H24Si) : C, 75.64; 0, 10.74; Si, 13.60.

Found: C, 73.68; H, 10.84; Si, 14.77.

10. Allyldimethylvinylsilane

Polymarization of this monomer was attempted with both Ziegler

catalysts and free radical initiators,

Ziegler catalyst polymerization gave heavy, brown oils which

could not be purified. The oils were non-volatile and would not solidify

at -700 The infrared spectra exhibited the following bands (cm." ):


3080, 2900, 2850 (C-H); 1635 veak, 1595 (CH2=CH-); 1450, 1380, 1350, 1010,

990, 950, 890 (CH, CII2, and CII3 deformations); 1255, 850 (-Si(C1I3)2-).

Polymerization vas also attempted by the same method used to

polymerize the dimethallyl monomers. With 2 per cent di-t-butyl.per-

oxide, an oil, similar to that obtained with the Ziegler catalyst, was

isolated after two days. After four days an insoluble solid was obtained.

The infrared spectra of these products were similar to those of the oils

described above.

Other polymerization attempts were made using benzoyl peroxide

and aa'-azobisisobutyronitrile. With benzoyl peroxide a heavy, brown

oil was obtained using 5 per cent of the initiator at 700 for one week.

The infrared spectrum of this oil was similar to that of the Ziegler

catalyst initiated polymer except that the bands for the allyl double

bond were much stronger. Attempted polymerization with 5 per cent

cz,a'-azobisisobutyronitrile at 700 for one week gave no appreciable

polymer. Only a very small amount of heavy, non-volatile oil was ob-


None of the products obtained could be purified to a sufficient

degree for analysis,



Reptane AEt TCEt3 Monomer Temp, Polymer Yield Melting Intrinsic
3 4 Moles Ti TimeRange Viscosity

go g. g. g. hrs. oC. g. % oC.

10 0.07 0.08 2.1 3.0 24-96a 30-60 0 ---- ----

10 0.11 0.10 2.5 2.0 30 60 0.3 15 110-123 ---

10 0.11 0.10 2.5 2.0 48 60 0.5 25 115-140 0.11

50 0.45 0.40 2.7 10.0 48 60 0.7 7 115-130 0.13

50 0.52 0.50 2.5 10.0 24 85 1.0 10 110-118 0.10

aPolymerizations run at several temperatures and for various periods.




Moles A1Et3
AlEt3 TLC Moles At Agg Time Yield Nonvola- Yield
3 4 Moles TiCl tile Liquid Solid Polymer

g8. g. hrs. g. % g. 7.

0.39 0.65 1.0 1 1.10 31 2.01 59

0.39 0.65 1.0 2 0.7 20 1.1 37

0.39 0.65 1.0 3 1.4 40 1.5 43

0.39 0.65 1.0 4 1.4 40 0.9 26

0.39 0.32 2.0 1 0.2 6 0.6 17

0.39 0.32 2.0 2 0.3 9 0.5 14

0.39 0.16 4.0 1 0.3 9 0.9 26

0.39 0.16 4.0 2 0.4 11 0.8 23

All experiments


performed using 50 ml. heptane solvent and

run at 85 for 24 hours.

3.5 g. diallyldimethylsilane.



Reaction Melting Descripion
Initiator Tme oonnoer Polymer Yield Range of Polymer

% hrs. g. g.o 7 C..

10 24 2 1.23 62 85-103 soft, gummy solid

5 48 2 .** ..--- insoluble solid

1.2 65 3 0.3 10 80-100 white solid

2.5 60 2 0.95 47 .... gummy solid

Polymerizations performed at 1350.



Moles A-t3 Reaction
Heptane AEt TiCl Holes AlEt3 Reaction Polymer Yield Melting Intrinsic
e3 T 4 oles T o eime Range Viscosity

ml. 8. g. g. hrs. g. % oC.

5 0.07 0.08 2.1 3 24a 1.5 50 135-152 ---
10 0.11 0.10 2.5 5 48b 1.5 30 130-140 0.06
10 0.11 0.10 2.5 3 48a 0.5 15 .... ..
50 0.45 0.40 2.7 8 46c 2.0 25 120-135 0.065
50 0.60 0.30 4.8 10 24d 5.6 56 142-180 0.08
50 0.30 0.30 2.4 10 68d 1.0 10 ... --
100 0.30 0.65 1.1 25 45de 13.5 54 120-140 ----



temperature 600.

temperature 65.

CReaction temperature 700.
dReaction temperature 850.

eCatalyst aged one hour at 85o before addition of monomer.



nitiato Reaction Melting Intrinsic
Initiator Time Monomer Polymer Yield Range Viscosity

% hrs. g. g. 0% C.

10 24 2.9 1.0 35 105-115 0.04

I 28 2.9 1,4 48 115-140 0.06

1 67 6.16 3.1 50 110-122 0.05

Polymerizations performed at 1350.



Reptane A1R C14s 3 esAeZt Reaction Polyme Yield Melting Intrinsic
eptane AlEt3 TiC4 Moles TiC onomer Time Polymr Yield Range Viscosity

ml. 8. g. g. hrs. g. 7 oC,

50 0.60 0.33 4.5 5.0 24 trace .. ..
50 0.68 0.40 3.7 10.0 24 0.4 4 90-110 0.12
50 0.60 0.33 4.5 10.0 48 1.0 10 95-120 ----
50 0.60 0.33 4.5 10.0 24 0.4 4 ... ---
50 0.60 0.33 4.5 10.0 24 0.6 6 90-115 0.07
50 0.60 0.30 4.9 9.0 48 0.5 56 87- 95 ..
25 0.60 0.33 4.5 10.0 48 2.6 26 98-112 0.09

Polymerizations performed- at 850.



Moles A1Et3 Reaction Melting Intinsic
Reptane A1Et3 TiC14 ...... 1 Monomer Te Polymer Yield Rang iscosity
3 4 Moles T1C14 Time Range Viscosity

ml. g. g, g. hrs. g. 7% C.

50 0.45 0.20 5.4 6.0 24 0.3 15 110-130
50 0.30 0.15 4.5 3.0 24 0.8 27 120-140 0.11
50 0.60 0.33 4,4 5.0 24 0.5 10 100-115 -
50 0.60 0.33 4.4 10.0 24 0 -- --.
25 0.30 Q.16 4.3 6.0 72 2.9 48 80-100 0.05

Polymerizations performed at 85 .



Holes Alt3ae
Reptane AlEt TC1 Mole Al Monomer Reaction Polymer Yield elting Intrinsic
3 4 Moles TiCl4 Time Range Viscosity

ml. g. g. g. hrzs g. % C

50 0.30 0.15 4.5 4.0 48 0.5 13 80-105
50 0.07 0.40 0.5 5.0 24 trace -- ---- ---
50 0.60 0.30 4.8 6.0 24 0-.. .-*
50 0.60 0.50 4.8 10.0 24 0.7 7 95-108 0.04
25 0.60 0.38 4.4 4.0 48 3.0 75 95-110 0*04

Polymerizations performed at 850.



Reaction e Melting Intrinsic
Monomer Initiator Time Monomer Polymer Yield Range Viscosity

% hr s g. g. % OC,

Dimethallyldimethyltilane 5 48 5.5 1.9 35 -.---o- 0.04
2.5 48 4.0 1.5 38 "" ..
5 24 3.0 0.5 17 ...

Dimethallyldiphanylsilane 5 48 4.0 3.0 75 110-125 0.026
3.5 66 11.0 7.0 64 115-120 0.03

Dimethallylphenylmethylsilane 3 48 5.0 2.0 40 65- 75 0.03

DimethallylcyclopentamethyLenesxliane 4 48 5,0 2.3 50 75- 90 0.04

Polymerizations performed at 135.



Diallyl- and dimethallylsilanes were prepared by reaction of

allyl or methallyl Grignard reagents with the appropriate dichloro*

silane. All but the cyclic silanes had been reported previously,

The reaction of allyl and methallyl Grignard reagents with cyclotetra-

methylenedichlorosilane and cyclopentamethylenedichlorosilane gave com*

pounds which could be identified as the expected products by analyses,

molar refraction, and infrared spectra, All of these methods gave

results which are consistent with the proposed structure, The prepara-

tion method has been used previously to yield analogous compounds,40'41

Allyldimethylvinylsilane was prepared both by the reaction of

vinyl Grignard reagent with allyldimethylchlorosilane and by the reaction

of allyl Grignard reagent with vinyldimethylethoxysilane. The products

of the two reactions were identical in their physical properties and

infrared spectra, providing a definite structure proof for this compound

in addition to the analysis and molar refraction. The infrared spectrum

of this compound exhibits two distinct peaks for the two carbon-carbon

double bonds at 1635 and 1595 cma*, The peak at 1595 cm." appears in

the spectra of other vinylsilanes and can be attributed to the vinyl
i -1
group attached to silicon. The peak at 1635 cm. appears in all of the

spectra of the allylsilanes and is assigned to the allyl double bond.

This shift indicated that the carbon-carbon double bond of the vinyl group

is of lower energy than is that of the allyl group. This suggects a

polarization of the vinyl double bond due to the presence of the silicon


The polymerization of the diallyl- and dimethallylsilanes was

accomplished by two different methods. The Ziegler catalyst was effective

for the polymerization of the diallylsilanes while free radical initiators

were effective for the polymerization of the dimethallylsilanes.

All of the diallylsilanes gave solid, benzene soluble polymers

when treated with the Ziegler catalyst. A wide variety of conditions were

used in some of the polymerizations in order to obtain the best conversion

of the monomer to polymer. The factors varied were: mole ratio of the

co-catalyst components, reaction time, temperature, and aging time of the


It is reported54 that the aluminum triethyl-titanium tetrachlo-

ride mole ratio should be 2 or 3 to I in order to obtain the most active

catalyst. It was found, in the polymerization of diallyldimethylsilane

(Table I), that when the catalyst was not aged, the best conversion was

obtained with a mole ratio of 2.5 to 1. It was found, as expected, that

the conversion was increased by raising the reaction temperature from

30 to 850, The reaction time seemed to have only a small effect upon the

yield of polymer obtained,

The effect of aging of the catalyst upon the conversion to poly-

mer was studied for the polymerization of diallyldimethylsilane (Table 2).

It is reported54 that the aging of the catalyst decreases its activity.

It was found that the aging of the catalyst actually increased the con-

version of this monomer to solid, linear polymer. The best conversion


was obtained with a co-catalyst mole ratio of I to I and a one hour aging

time for the catalyst. The conversion dropped off slowly as the catalyst

was aged for a longer period.

In the polymerization of diallyldiphenylsilane it was found that

the mole ratio of the co-catalyst components had a smaller effect upon

the conversion, between mole ratios of 2.2 and 4.4 to 1 (Table 4), Uith

this monomer the temperature and reaction time seem to have only a small

effect upon the conversion.

In some polymerizations of diallyldiphenylsilane, titanium tetra-

chloride was replaced in the catalyst by dicyclopentadienyltitanium

dichloride, to give a soluble Ziegler type catalyst. Diallyldiphenyl-

silane was chosen for these experiments due to the fact that good yields

of solid polymer had been obtained in previous polymerizations of this

monomer with the conventional Ziegler catalyst. Only small amounts of

solid polymer were obtained with the soluble catalyst mixture, Natta5

has reported that this soluble catalyst is less active than is the con-

ventional catalyst.

Polymerization of the remaining diallylsilanes was accomplished

with the conventional Ziegler catalyst. Conditions for these polymeriza-

tions were not significantly varied and no attempts were made to obtain

optimum conditions for the polymerizations.

Attempts were made to polymerize dimethallyldimethylsilane with

the Ziegler catalyst but no polymer was isolated. This was not surprising

in view of previously published reports of attempts to polymerize olefins
with branching close to the double bond*

Free radical polymerization of the dimethallylsilanes led to

soluble polymers (Table 9). Di-t-butyl peroxide was used as the initi-

ator for these polymerizations. Diallyldimethylsilane (Table 3) and

diallyldiphenylsilane (Table 5) were also polymerized with this initi-


Lower melting points and lower intrinsic viscosity values for

these free radical initiated polymers indicate that the polymers are of

lower molecular weight than are those obtained with the Ziegler catalyst.

The dimethallylsilanes all have very low intrinsic viscosities which

indicate that they have a low degree of polymerization. The low degree

of polymerization is probably due to "degradative chain transfer"

involving the allylic hydrogen atoms, In the dimethallylsilanes, this

effect should be more important due to the greater number of allylic

hydrogens. Diallylsilanes have four allylic hydrogens while the di-

methallylsilanes have ten. Comparison of the results of the free radical

polymerization of diallyldiphenylcilane (Table 5) and of dimethallyldi-

phenylsilane (Table 9) shows that although both have low intrinsic vis-

cosity values, those for the diallyl polymers are about twice those for

the dimethallyl polymers. Since these compounds are very similar it seems

likely that the molecular weights for these two polymers would be in

about the same ratio as are their intrinsic viscosities.

All of the diallyl- and dimethallylsilanes gave polymers which

were soluble in benzene although small fractions of a few polymers were

insoluble. These soluble polymers exhibited little or no residual

unsaturation in the infrared spectra. In most cases the absorption bands

for carbon-carbon double bond stretch and for terminal methylene defor-

mations could be removed from the spectra by further purification of the


The analytical results of the polymers are in many cases rather

far from the theoretical value for carbon. It is reported,56 that in the

analysis of silicon polymers, combustion of the sample may lead to the
formation of some silicon carbide which to not completely oxidised. The

formation of this compound would account for the low per cent of carbon

found in the analyses of these polymers. The per cent silicon would not

be affected by this due to the fact that the silicon analyses are per-
formed on a separate sample using vet oxidation methods. The silicon and

hydrogen analyses of these polymers are fairly close to the theoretical

values and it seems certain that the formulae assigned to the polymers
are correct.

Since these polymers are soluble and contain no residual unsatu-
racion, it is fairly certain that they contain cyclic recurring units as
represented below.

A2 2 2
S 2 2 2,1


R A S, C65 n 4 or 5

* * CU3, C6 5


"-- -CB^C" "ca
2 22

2 1 2,, x

R'c iCc C6% ....

In view of the properties of these polymers and the previous work

reported2'10'12'13 on the polymerization of 1,6-dienes, these structures

are the most likely ones for these polymers,

The polymerization of allyldimethylvinylsilane was attempted with

several catalysts but no solid, soluble polymer was obtained. The poly-

merization with free radical initiators gave varying results. With

di-t-butyl peroxide both an insoluble solid and a heavy oil were obtained.

The infrared spectra were very similar and showed absorption for both

allyl and vinyl groups. The allyl double bond absorption was decreased a

great deal in the two polymers however. Bensoyl peroxide gave a low

yield of heavy oil which had an infrared spectrum similar to that of the

polymers above. Use of aczl'-azobisisobutyronittile gave no polymeriza-


It has been reported that vinylsilanes do not polymerize with

bensoyl peroxide.57 The reason for this lack of polymerization can be

explained by consideration of the radical which would be formed by a free

radical attack on a vinylsilane.

Z* + CH 2T zc2
SR3 3

It has been mentioned earlier in this section that there is a polariza-

tion of the vinyl group attached to silicon. This polarization is due to

the "electron sink" effect of silicon. This "electron sink" effect would

stabilize the free radical formed above. This radical stability is

apparent in the free radical chlorination of tetraalkylsilanes. The

chlorination of tetraethyleilane gives the a-chloro compound exclusively,

This indicates that the radical on a carbon atom adjacent to a silicon

atom of a tetraalkylsilane is very stable. The stability of this radical

may account for lack of polymerization of allyldimethylvinylsilane. The

low molecular weight polymers which did result from this monomer were

probably formed by polymerization through the allylic double bonds. This

type of polymerization leaves a vinyl group on the chain which may, under

proper conditions, react to form a crosslink leading to insoluble poly-


Attempts to polymerize this monomer by use of Ziegler catalysts

gave results similar to those obtained with free radical initiators. In

this case the vinyl double bond does not take part in the polymerization

due to steric factors.52 The allyl double bond undergoes polymerization,

however, to give low molecular weight oils, It was not possible to

purify the polymers obtained with this monomer to any large extent due to

the fact that the polymers were non-volatile and liquid at even very low

temperatures. Infrared spectra, however, indicate that the only major

changes from the monomer is the decrease of allyl double bond content in

the polymer.



A series of diallyl- and dimethallylsilanes were prepared by the

reaction of allyl or methallyl Grignard reagents with the appropriate

dichlorosilanes. Three of these monomers had not been previously reported.

Allyldimethylvinylsilane was prepared by two different routes.

The diallylsilanes were converted to polymers by use of Ziegler

catalysts. The polymers were soluble in benzene, and shoved little or no

unsaturation in the infrared spectra. A study was made of the effect of

aging time of the catalyst upon the polymerization of diallyldimethylsi-

lane, It was found that increased yields of polymer were obtained when

the catalyst was aged for short periods before the addition of the imonmer.

The dimethallylsilanes were polymerized by use of the free radi-

cal initiator di-t-butyl peroxide' to give benzene soluble polymers con-

taining little residual unsaturation. Intrinsic viscosity measurements

indicate that the Ziegler catalyst initiated polymers' have a higher

degree of polymerization than do the free radical initiated polymers.

In view of the physical properties of these polymers it was con-

cluded that the monomers were polymerized by the intramolecular-inter-
molecular chain propagation mechanism to give polymers containing cyclic

recurring units.

Polymerization of allyldimethylvinylsilane gave low molecular

weight polymers with both Ziegler catalyst and free radical initiators.


The infrared spectra indicate that polymerization occurred through the

carbon-carbon double bond of the allyl group only leaving the unreacted

vinyl groups on the polymer chain.


1. Butler, G. B., and Ingley, 'F, T., to. g. ; S. 894 (1951).
2. Butler, G. B., and Angelo, R. J*' J, to Chem. S 3128 (1957)1
3. Walling, C., leAm. I em.* Loc., jO 441 (1945).
4. Burnetts G. ., Mechanism of Polymer Reactons, Interacience Publ-
lUshers Inc. New York, 1954, p. 436,
5, Simpson, W., Bolt, T., and Zeite, Rp., Polymr Sot. 10, 489
6. Havard, M., J. Polymer SA 14, 535 (1954).
7, Simpson, W., and Holt, T., Polyjmer SAc. 18 440 (1955).
8, Haward, N,, and Simpson, .,4 J. Polymer gUt.. .l 440 (1955).
9. OiW M, and Ogata, 3J, j Chem. Soc. Ja j 1506 (1958).
10, Butler, G. B., Cravshaw, A., and Miller, W sL. AM, .Ch. Soc.,
80s 3615 (1958).
11. Marvel, C. S., and Vests RI B, . -f. a. g Soc.$ 79, 5771 (1957).
12. Marvel, C. S., and Stillel J. K, .. M. Shm. Soc., .80 1740 (1958).
13. Crawshaw, A., and Butler, G. B., B &m. g Soc ., 80- 5464 (1958).
14. Jones, J ., Polymenr Set*, 15 (1958).
15. Jones, J, F., Italin Patent 563,941, June 7, 1957, to B. F. Good-
rich Company,

16. Jones, J. o,, J., Polymer et., "q 7 (1958).
17. Jones, J. It, I Polymer i.. 33, 513 (1958).
18. Marvel, C. S., Kiener, P. Es and Vessel, B., X, * t C Soc.
8., 4694 (1959),
19. Marvel, C. S., and Vest, R. D., J. &, ghem. Soc., 8, 984 (1959).
20, Marvels C. S., and Gall, E, J., J_. Or, Chem.s., 1494 (1959).

21. Field, N. Ds., J. gr. h.Cem., 1006 (1960).
22. Marvel, C. 8., and Gall, E. J., .. g.J ,Chem., J.2, 1784 (1960).
23. Price, J. A., A,. Patent 3,871,229 January 27, 1959, to American
Cyanamid Company.
24. Schuller, W. B., Price, J. A., Moore, S. T., and Thomas, W. M., J.
Shem. SS.*Data, 4 273 (1959).
25. Friedlander, W. 8., Paper No. 29, Div, of Org. Chemn., American Chemi-
cal Society Meeting, San Francisco, April, 1958, p. 184.

26. Berlin, K. D., and Butler,, G. B., l. Am. em So., 82, 2712 (1960).
27. Skinner, D. L., Ph.D. Dissertation, University of Florida, Januarys

28. Marvel, C. S., and Woolford, R. G., J. Og. Chm., 3., 1641 (1960).
29. Butler, G. B., and Stackman, R. We, go. g h ., 25 1643 (:960).
30. Marvel, C. SL and Garrison, W. B., Jr., J. A.Chm. Soc., 1
4737 (1959).
31. Still, J. 9., Paper No. 43, Div. of Polymer Chem., American Chemi-
cal Society Meeting, Boston, April, 1959, p. 174.
32. Barnett, H. D., Crawshaw, A., and Butler, G. B., J. Ae. hw. e2.,'
81. 5946 (1959).
33. Butler, G. B., Paper presented before the International Symposium on
Macromolecular Chemistry, Moscov, U. S. S. i., June, 1960.
34. Delmonte, D. W., and Hays, J. Ti, Paper presented at Delaware Science
Symposium, Newark, Delaware, February, 1959.

35. Blout, B. R., and Ostberg, B. S., j. Polneor Sei. j, 230 (1946).
36. Cohen, 8. Go, Ostberg, B. E., Sparrow, D. B., and Blout, E. R., J.
P2solymer Lea, 3 264 (1948).
37. Gould, E. S., Mechanism and Structure j Organic Chemistry, Henry
Holt and Company, NHew York, 1959, p. 644.

38. Miller, W. L., Ph.D. Dissertation, University of Florida, January,

39. Mikulasova, G., and Hvirik, A., Chem. Zvest. J1 641 (1957).

40. West, s., .. AM. Lea. Soc., 76 6012 (1954).
41. Tamborski, C., and Rosenberg, H., Or*r. Chem., 32, 246 (1960).
42. Petrov, A. D., Mironov, V. F.4 and Glukhoutsev, V. Go, Imt*. Akad.
Manc, 1123 (1954); _. Abltractse. 4,9 7510 (1955).
43. Petrov, A. D., and Mironov, V. F., Poklady Akad. HauE. S, S. .
8.0 7614 (1951); ;hg Abstracts. 46, 11102 (1952).
44. Nastak, L. D., and Post, N. W., *. Or' Chem. 490 (1959).
45. Warrick, B. L., 1. A. Che S 6. 2455 (1946).
46. Oshesky, G. D., and Benltey, F' F., a&# he. Soc., 729 2057
47. Rochov, B. C., An Introduction to the Chemistry of the Silicones,
John Wiley and Sons, Inc., New York, 1951, p. 80.

48. Polyakova, A. H., Korshok, V. V., Sakharova, A. A., Petrov, A. D.,
Mironov, V. F., and Nikishin 0, I ., Igvest Akad. Mauk, 8,. S.
.* Es, Otdel m* Hank. 999 (1956); AbcAtets 51, 4979
49. Petrov, A. D., Polyakova, A. M.N Sakharova, A. A., Korashok, V. V.,
Mironov, V. F., and Nikishin, G. I., Poklady Akad. a A., 8,.
8. 9* 9 29 785 (1954); Che. Abstracts, 49 15727 (1955).
50. Topchiev, A. V., Nametkin, N. S., Durgar'yan S. C., and Dyankov,
8., fhitm jL Prait. Primpenie groggeorg Soadinenit Tr udy
Sonp., Leningrad, No. 2, 118 (1958); Chem. Abstracts#, k 8686
51. Labiles R. C., 13. &a. 5.8, 807 (1958).
52. Stille, J. Ko, em# U-va., ^8, 541 (1958).
53. Gaylord; Go., and Mark, H. F', Linear and Steoeoregular Addition
Polymers lInterscience Publishers Inc., New York, 1959.
54. Gaylord, 0., and Mark, a. )., neal and Stereoregular Addition
Polymers, Interscience Publishers Inc., New York, 1959, p. 90.
55. Natta, 0., Pino, P., Massanti, G,, and Gionnini, U., j. Am. gCem.
Soc., 79 2975 (1956).

56. Rochow, E. C.,* A Introduction to t Chemistry of LIe Silicones,
John Wiley and Sons, Inc., 'New York, 1951, p. 162.


57. Post, BH W., Silicones and Other Organic Silicon Compunds, Reinhold
Publishing Corporation, New York, 1949, p. 39.

58. Walling, C., Free Radicals in Solution, John Wiley and Sons, Inc.,
New York, 1957, p. 369,


Robert W. Stackman was born in Dayton, Ohio, on June 29, 1935.

He entered the University of Dayton, Dayton, Ohio, in September 1953

and received the degree of Bachelor of Science, with a major in Chemistry

in June 1957.

In September of 1957 he entered the Graduate School of the Uni-

versity of Florida. He has been employed by the Chemistry Department of

the University of Florida as a graduate assistant, and as a research


He is a member of Alpha Chi Sigma fraternity and the American

Chemical Society.

This dissertation was prepared under the direction of the chair-

man 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 ap-

proved as partial fulfillment of the requirements for the degree of

Doctor of Philosophy.

January 28, 1961

Dean, College of Arts add sciences

Dean, Graduate School

Super.vsory Committee:


at .i^ ^:i'

Internet Distribution Consent Agreement

In reference to the following dissertation:

AUTHOR: Stackman, Robert
TITLE: Preparation and polymerization of certain diunsaturated silanes. (record
number: 427152)

I, _, as copyright holder for the
aforementioned dissertation, hereby grant specific and limited archive and distribution rights to
the Board of Trustees of the University of Florida and its agents. I authorize the University of
Florida to digitize and distribute the dissertation described above for nonprofit, educational
purposes via the Internet or successive technologies.

This is a non-exclusive grant of permissions for specific off-line and on-line uses for an
indefinite term. Off-line uses shall be limited to those specifically allowed by "Fair Use" as
prescribed by the terms of United States copyright legislation (cf, Title 17, U.S. Code) as well as
to the maintenance and preservation of a digital archive copy. Digitization allows the University
of Florida or its scanning vendor to generate image- and text-based versions as appropriate and
to provide and enhance access using search software.

This grant of per issions prohibits use of the digitized versions for commercial use or profit.

Signature of Copyright Holder

Printed or Typed Name of Copyright Holder/Licensee

Personal information blurred

Date of Signature

Please print, sign and return to:
Cathleen Martyniak
UF Dissertation Project
Preservation Department
University of Florida Libraries
P.O. Box 117008
Gainesville, FL 32611-7008

University of Florida Home Page
© 2004 - 2010 University of Florida George A. Smathers Libraries.
All rights reserved.

Acceptable Use, Copyright, and Disclaimer Statement
Last updated October 10, 2010 - - mvs