CERTAIN DIUNSATURATED SILANES
ROBERT WILLIAM STACKMAN
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
ACDKcXW LED GEMENT$
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.
TABLE OP CONTENTS
ACKNOWLEDGEMENTS * * ,. .
LIST OF TABLES . . . . .
1. INTRODUCTION . .
A. Literature Review *
B. Statement of Problem
II. PREPARATION OF ONOMERS .
A. Materials . *
B. Equipment and Data .
0 a 0 o 0 0 0 0 0 0 0 0 ii
. . . .. . . .
* 6 9 0 0 *
* . .
* 0 0
* 0 0 0 .
C. Preparation of Intermediates .
1. Allyl Grignard reagent o
2. Methallyl Grignard reagent
D. Preparation of Monomers .
0 e o i i * a
1. Diallyldimethylsilane IC2i*CCH2 2)i(CH3)2.
2. Diallyldiphenylstilane F(CH,-M2CHC2) Si(C)2
KM2CH *CR2)2Si(CR)C6EC ] * * * .
r5(a2ud-c2) 2i(Cu2)C l . . . . .
CR2C 2 2Sc2 ****... *... ....
CH2C(C3CH2)2Si(C3>. 2 .*
JCH27(C3)CH2z) iS2(C3)C . . .
[(C C(cH3)ca2)2s(c2)]. ..........
10. AllyldtethylvinylsllanesMC2CCH2l (CH3) 2CH.C2.
Il. POLYMERIZATIONS a b , . . .
A* Materials ,* . . . .
*0C ..* Ct C
B. Equipment and Data . ., , ,
C. General Polymerization Procedures .
1. Ziegler catalyst polymerization
2. Free radical polymerization .
D. Polymerization of Monomers . . .
DiallyldimethylsLlane . . .
Diallyldiphenylaulane . . .
Dimethallyldimethylsilane . .
Dimethallyldiphenylsilane . ,
Allyldimethylvinylsilane 0 * *.
C CCC *C~ 0*
* a. .me...
CC C C0CC.~
0 0tb 0*
mm.. .4. t
. C 0 0 0 0
, m. ..
XV. DISCUSSION . . . . . . . . .
V. SUMMARY . . . . . . . . . . . ..
BIBLIOGRAPHY . . . . . . . . . . . . . .
BIOGRAPHICAL ITEMS . . ...... ..............
LIST OF TABLES
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
Z-CHn- 2 CH CH Z-CH2 CH CH-
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
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-
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
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,
b. polymerizing these monomeric silanes, and
c. studying the resulting polymers.
PRIPArATION OF ::?:D:~1rS
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.
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,
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
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
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
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,
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
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
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.
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
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);
Anal. Calcd. for (C18H20Si)n: C, 81,78; H, 7.63; Si, 10,60.
Found: C, 80.74; II, 7.60; Si, 10.40.
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.
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.
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.
Attempts to polymerize this monomer with the Zieoglr catalyst gave
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.
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.
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);
Anal. Calcd. for (C15H24Si)n: C, 78.18; H, 9.62; Si, 12.18.
Found: C, 76.31; H, 9.38; Si, 12.76.
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.
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
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,
ZIEGLER CATALYST POLYMERIZATION OF DIALLYLDIMETHYLSILANE
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.
EFfMCT OF CATALYST AGING UPON THE POLYMERIZATION OF
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
performed using 50 ml. heptane solvent and
run at 85 for 24 hours.
3.5 g. diallyldimethylsilane.
FREE RADICAL POLYHERIZATION OF DIALLYWIMTHlYLSILANB
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.
ZIEGLER CATALYST POLYMERIZATION OF DIALLYLDIPIIENYLSILANE
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 ----
CReaction temperature 700.
dReaction temperature 850.
eCatalyst aged one hour at 85o before addition of monomer.
FREE RADICAL POLY fllZAT1011 OF DIALLYWIPHENYLILANE
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.
POLYMERIZATION OF DIALLYLMETHYLPHENYLSILANE
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.
POLYMERIZATION OF DIALLYLCYCLOTETRAMETHYLENESILANB
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 .
POLYMERIZATION OF DIALLYLCYCLOPEMTAIIETIIYLENESILANE
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.
POLYM&RIZATIONq OF DIMETHALLYLSILANES
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
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-
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
Since these polymers are soluble and contain no residual unsatu-
racion, it is fairly certain that they contain cyclic recurring units as
A2 2 2
S 2 2 2,1
R A S, C65 n 4 or 5
* * CU3, C6 5
"-- -CB^C" "ca
R CBC H
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
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
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
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
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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
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
at .i^ ^:i'
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TITLE: Preparation and polymerization of certain diunsaturated silanes. (record
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