Unsaturated silylated vinyl alcohol polymers

Unsaturated silylated vinyl alcohol polymers, derivatives thereof, and processes for their preparation.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to unsaturated silylated vinyl alcohol polymers, 
that is, polymers of conjugated polyenyloxysilanes and copolymers thereof 
with ethenyloxysilanes, and to their preparation. 
2. Background 
(1,3-Butadienyloxy)trialkylsilanes are known compounds or are prepared by 
known methods. For example, U.S. Pat. No. 3,472,888 discloses the 
preparation of (1,3-butadienyloxy)trihydrocarbylsilanes. Brun et al., 
Tetrahedron Lett., 24(4): 385 (1983) disclose 
(1,3-butadienyloxy)trimethylsilane and 1,3-butadienenyacetate. Makin et 
al., Kh. Org. Khim., 18(2): 287 (1982) disclose the preparation of 
(1,3-butadienyloxy)trimethylsilanes by silylating 
.alpha.,.beta.-unsaturated aldehydes with trimethylsilyl chloride and 
triethylamine. Jung et al., Tetrahedron Lett., 3791 (1977) disclose the 
preparation of ethenyloxysilanes from lithium enolates of aldehydes by 
reaction with trialkylsilyl chlorides. 
Polymers prepared from (1,3-butadienyloxy)trialkylsilanes are also known. 
Mukaiyama et al., Chem. Lett., 4: 319 (1975) disclose the formation of 
polymer in the titanium tetrachloride-catalyzed reaction of 
(1,3-butadienyloxy)trimethylsilane when methylene chloride or toluene were 
used as solvents. Polymer was not formed when a more strongly complexing 
solvent (THF) was employed or when titanium isopropoxide was added to the 
titanium tetrachloride. Makin et al., Zh. Org. Khim., 19(11): 2285 (1983) 
disclose reaction of 1,3-butadienyloxytrimethylsilanes with acetals 
catalyzed by zinc chloride without polymerization. Makarov et al., 
Vysokomol. Soedin. Ser. B, 13(3): 222 (1971) disclose copolymerization of 
1- and 2-acetoxy-1,3-butadiene with styrene and methyl methacrylate. USSR 
patent application No. 285,238-S discloses copolymerization of 
1,3-butadienyltrialkylsilanes with various vinyl monomers including 
styrene and methyl methacrylate using free radical catalysts. 
U.S. Pat. No. 3,491,068 discloses 1:1 alternating copolymers of maleic 
anhydride and diolefins, including 1- and 2-alkoxy-1,3-butadienes prepared 
by free radical polymerization. U.S. Pat. No. 3,458,491 discloses anionic 
(co)polymerization of various dienes, including 1- and 
2-alkoxy-1,3-butadienes. The catalyst was an alkali metal alkyl or aryl or 
complexed alkali metal. U.S. Pat. No. 1,963,108 discloses the preparation 
of 1- and 2-acyloxy-1,3-butadienes and their free-radical polymerization. 
U.S. Pat. No. 3,993,847 discloses adhesives comprising copolymers of 
conjugated dienes including 1- and 2-alkoxy-1,3-butadienes. U.S. Pat. No. 
3,418,293 discloses polymerization of vinyloxysilanes of the formula 
CH.sub.2 .dbd.CHOSi(R.sup.1)(R.sup.2)(R.sup.3) wherein R.sup.1-3 are the 
same or different, and each is a hydrocarbon radical which can include 
alkyl, cycloalkyl, aryl, aralkyl, and alkaryl, in the presence of an ionic 
catalyst of the Friedel-Crafts or Ziegler type, at a temperature in the 
range -80.degree. C. to 0.degree. C., in an anhydrous organic solvent. The 
product was a poly[(ethenyloxy)triorganosilane] which can be converted to 
poly(vinyl alcohol) by alcoholysis. 
Murahashi et al., Polymer Letters, 3: 245 (1965) and 4: 59, 65 and 187 
(1966), disclose the preparation of poly(vinyltrimethylsilyl ethers) by 
radical and cation-initiated polymerization of vinyloxy trimethylsilane 
and conversion thereof to stereoregular poly(vinyl alcohol). Also 
disclosed is the radical-initiated copolymerization of vinyloxy 
trimethylsilane ([ethenyloxy]trimethylsilane) with vinyl comonomers. 
Cationic initiators employed were SnCl.sub.4 or ethyl aluminum chlorides. 
Nozakura et al., J. Polymer Sci., Polymer Chem. Ed., 11: 1053 (1973), 
disclose the polymerization of several ethenyloxy trialkylsilanes 
initiated by cationic compounds SnCl.sub.4 or ethyl aluminum chlorides, 
and conversion of the poly(vinyltrialkylsilyl ethers) to poly(vinyl 
alcohol) with aqueous hydrofluoric acid. Runge et al., Makromol. Chem., 
120: 148 (1968), disclose the free radical-initiated copolymerization of 
ethenyloxytrimethylsilane with vinyl comonomers. Japanese published, 
unexamined application No. JA 22299/69 discloses a process of 
copolymerizing ethenyloxytrialkylsilanes with vinyl comonomers in the 
presence of radical catalysts such as azo-bis(isobutyronitrile). Colvin, 
"Silicon in Organic Synthesis", Butterworths, 1981, pages 219-220, 
discloses the reaction of alicyclic silyl enol ethers with aldehydes in 
the presence of a fluoride ion catalyst, for example, 
##STR1## 
Colvin, ibid, page 227, discloses the reaction of aromatic aldehydes with 
silyl ketene acetals in the presence of TiCl.sub.4 ; the silyl group in 
the product is subsequently removed by hydrolysis, for example, 
##STR2## 
Colvin, ibid, pages 221 and 222, discloses the alkylation of silyl enol 
ethers with certain alkyl and aralkyl halides in the presence of 
TiCl.sub.4 or ZnBr.sub.2, for example, 
##STR3## 
Colvin, ibid, pages 232-236, discloses the reaction of silyl enol ethers 
with acyl halides, halogenated acid anhydrides and ketones in the presence 
of Lewis acids. 
U.S. Pat. No. 4,544,724 discloses the polymerization of ethenyloxysilanes 
initiated by aldehydes or precursors thereof, and catalyzed by selected 
Lewis acids, including zinc halides. The polymers are aldehyde-terminated 
poly(ethenyloxysilanes), hydrolyzable to poly(vinyl alcohol), and 
copolymers thereof. 
The conversion of pendant siloxy groups, such as --OSi(CH.sub.3).sub.3, to 
hydroxyl groups in polymers by a variety of methods is disclosed in the 
aforesaid publications of Murahashi and Colvin and in the Japanese 
publication. 
U.S. Pat. No. 2,165,962 and Hoaglin et al., J. Am. Chem. Soc., 71: 3468 
(1949) describe the polymerization of alkyl vinyl ethers in the presence 
of acetals such as acetaldehyde acetal and a Lewis acid such as BF.sub.3 
to form acetal-capped polyvinyl ethers; for example, 
##STR4## 
Acetal-initiated polymerization of trialkylsilylvinyl ethers is not 
disclosed. Formation of unsaturated aldehydes by hydrolysis of a 1,1,3 
trialkoxy product formed by the condensation of an acetal with a vinyl 
ether is disclosed by Fishman et al., Synthesis Comm., 137 (1981); for 
example, 
##STR5## 
SUMMARY OF THE INVENTION 
The present invention provides a polymer (1), and derivatives thereof, said 
polymer (1) consisting essentially of 2 to 100 mole percent of a first 
recurring unit of the formula 
EQU --CH(R.sup.9)--C(R.sup.9).dbd.C(R.sup.9)--.sub.n CH[OSi(R.sup.1).sub.3 ]-- 
and 0 to 98 mole percent of a second recurring unit of the formula 
EQU --CH.sub.2 CH[OSi(R.sup.1).sub.3 ]-- 
wherein, 
R.sup.1 is independently selected from the group consisting of alkyl 
radicals having 1 to 10 carbon atoms, alkenyl radicals having 2 or 4-10 
carbon atoms, and aryl, aralkyl, and alkaryl radicals having 6 to 10 
carbon atoms; 
R.sup.9 is independently selected from the group consisting of H and alkyl 
radicals having 1 to 6 carbon atoms, provided that adjacent R.sup.9 groups 
are not both alkyl radicals; and 
n is an integer from 1 to 5, inclusive. 
DETAILED DESCRIPTION OF THE INVENTION 
This invention provides the following: 
1(a). Polymer (1) as defined above. 
1(b). Polymer (2) consisting essentially of polymer (1), wherein each 
polymeric chain is terminated at one end by a --CHO group. 
1(c). Polymer (3) consisting essentially of polymer (2), wherein each 
CHO-terminated polymeric chain is capped by a capping agent which is an 
aldehyde-reactive compound, said agent optionally containing at least one 
functional substituent that is unreactive under capping conditions. 
1(d). Polymer (4) prepared by hydrogenating polymer 1. 
1(e). Polymer (5) prepared by hydrolyzing polymer 1. 
2(a). A process for preparing polymer (1) comprising contacting one or more 
monomers of the formula 
EQU CH(R.sup.9).dbd.C(R.sup.9)--C(R.sup.9).dbd.C(R.sup.9)--.sub.n-1 
C(R.sup.9).dbd.CHOSi(R.sup.1).sub.3 
and, optionally, one or more monomers of the formula 
EQU CH.sub.2 .dbd.CHOSi(R.sup.1).sub.3 
under polymerizing conditions with a catalyst which is a Lewis acid, 
wherein R.sup.1, R.sup.9 and n are as defined above. 
2(b). A process for preparing polymer (2) comprising contacting one or more 
monomers of the formula 
EQU CH(R.sup.9).dbd.C(R.sup.9)--C(R.sup.9).dbd.C(R.sup.9)--.sub.n-1 
C(R.sup.9).dbd.CHOSi(R.sup.1).sub.3 
and, optionally, one or more monomers of the formula 
EQU CH.sub.2 .dbd.CHOSi(R.sup.1).sub.3 
under polymerizing conditions with a catalyst which is a Lewis acid and an 
initiator which is an aldehyde or an aldehyde precursor compound wherein 
R.sup.1, R.sup.9 and n are defined as above. 
2(c). A process for preparing polymer (3) comprising contacting and 
reacting polymer (2) with a capping agent which is an aldehyde-reactive 
compound optionally containing at least one functional substituent that is 
unreactive under capping conditions. 
3(a). A process for polymerizing one or more monomers of the formula 
EQU CH(R.sup.9).dbd.C(R.sup.9)--C(R.sup.9).dbd.C(R.sup.9)--.sub.n-1 
C(R.sup.9).dbd.CHOSi(R.sup.1).sub.3 
and optionally one or more monomers of the formula 
EQU CH.sub.2 .dbd.CHOSi(R.sup.1).sub.3 
wherein R.sup.1, R.sup.9, and n are as defined above, said process 
comprising contacting the monomer or mixture of monomers under 
polymerizing conditions with a catalyst comprising a Lewis acid, and 
preferably an initiator comprising an aldehyde or a aldehyde precursor 
compound. 
3(b). Polymer (6) prepared according to the process defined in 3(a). 
By "initiator" is meant an aldehyde or aldehyde precursor compound which, 
in the polymerization processes of the invention, initiates growth of 
polymer chains and, in conjunction with monomer, essentially controls 
M.sub.n of the polymer product, such that M.sub.n is approximately equal 
to 
##EQU1## 
wherein N.sub.m and N.sub.I, respectively, are the number of moles of 
monomer and initiator, and M.sub.m and M.sub.I, respectively, are the 
molecular weights of monomer and initiator. 
Aldehydes which are useful initiators in the invention for preparing the 
polymer of formula 2 or the polymer from the process of 3a include, but 
are not limited to, aliphatic, aromatic and polymeric aldehydes. Preferred 
aldehyde initiators are those of the formula 
EQU R.sub.H (Y.sup.2 CHO).sub.x ; 
wherein, in the formula: 
R.sub.H is H or a hydrocarbyl radical of valence x which may be an alkyl, 
cycloalkyl, aryl, alkaryl or aralkyl radical having up to 20 carbon atoms, 
or a polymeric radical having at least 20 carbon atoms, and which, 
optionally, may contain ether oxygen and/or one or more functional 
substituents which are unreactive under polymerizing conditions; 
x is an integer and is at least 1, preferably 1 to 10, most preferably 1; 
Y.sup.2 is Y.sup.3 (C[R.sup.4 ].sub.2).sub.y ; 
Y.sup.3 is a connecting bond or a divalent radical selected from --C(O)--, 
--R.sup.2 --, --N(R.sup.3)CH.sub.2 --, --CH(L.sup.1)--, 
--CH(L.sup.2)CH.sub.2 --, --CH(L.sup.3)--(CH.sub.2).sub.a --C(O)-- and 
##STR6## 
wherein 
R.sup.2 is an alkylene radical having 1 to 10 carbon atoms or an aralkylene 
radical having 7 to 20 carbon atoms; 
R.sup.3 is an alkyl radical having 1 to 4 carbon atoms; each R.sup.4 is 
independently selected from H, C.sub.1-10 alkyl and C.sub.6-10 aryl, 
aralkyl or alkaryl; 
L.sup.1 is --OR.sup.5, --OR.sup.6 OSi(R.sup.1).sub.3 or 
--OSi(R.sup.1).sub.3 ; 
R.sup.5 is an alkyl radical having 1 to 4 carbon atoms and R.sup.6 is an 
alkylene radical having 1 to 4 carbon atoms; 
L.sup.2 is --OSi(R.sup.1).sub.3 ; L.sup.3 is --(CH.sub.2).sub.b 
--C(O)OSi(R.sup.1).sub.3 ; L.sup.4 is --C(O)OSi(R.sup.1).sub.3 ; 
each of a and b, independently, is 0, 1 or 2; y is 0 or 1; and 
each R.sup.1 is independently selected from the group consisting of alkyl 
radicals having 1 to 10 carbon atoms, alkenyl radicals having 2 or 4-10 
carbon atoms, and aryl, aralkyl and alkaryl radicals having 6 to 10 carbon 
atoms. Most preferred aldehyde initiators are selected from the group 
consisting of acetaldehyde, isobutyraldehyde, neopentaldehyde, 
3-(dimethylamino)propionaldehyde, 
3,3',3"-(1,3,5-benzenetriyl)tris(propionaldehyde), benzaldehyde, 
terephthaldehyde and acrolein homo- and copolymers. 
By "aldehyde precursor compound" is meant the compound which, when 
contacted with a silyl enol ether under polymerizing conditions, forms an 
aldehyde initiator. The silyl enol ether may be a monomer used in the 
invention for preparing the polymer of formula 2. Aldehyde precursor 
compounds include, but are not limited to, those of the formula 
EQU R.sub.H (Y.sup.1 X.sup.1).sub.x 
wherein X.sup.1 is --OH, --Cl, --Br, --H, --R.sup.5, --OR.sup.5, 
Cl.crclbar., Br.crclbar., I.crclbar., O.crclbar.R.sup.5, 
O.crclbar.COR.sup.5, or CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 .crclbar., 
wherein R.sup.5 is an alkyl radical having 1 to 4 carbon atoms; 
preferably, X.sup.1 is --OH, --Cl, --Br, or --OR.sup.5 ; 
Y.sup.1 is a connecting bond or a divalent radical selected from --C(O)--, 
--R.sup.2 --, --CH[OSi(R.sup.1).sub.3 ]--, --CH(OR.sup.5)-- and 
--N.sym.(R.sup.3).dbd.CH.sub.2, wherein R.sup.1, R.sup.2, R.sup.3 and 
R.sup.5 are as defined above; preferably, Y.sup.1 is a connecting bond, 
--C(O)--, --CH(OR.sup.5)-- or --R.sup.2 --; and 
Y.sup.1 and X1 taken together is 
##STR7## 
or 
##STR8## 
wherein R.sup.6 is an alkylene radical having 1 to 4 carbon atoms, R.sup.8 
is a connecting bond or an alkylene radical having 1 to 10 carbon atoms, 
and R.sup.7 is an alkyl radical having 1 to 10 carbon atoms or an aryl 
radical having 6 to 10 carbon atoms, or 
R.sup.8 and R.sup.7 taken together is 
##STR9## 
wherein a and b are as defined above; with the provisos that: 
(i) when Y.sup.1 is a connecting bond, X.sup.1 is --OH; 
(ii) when Y.sup.1 is --C(O)--, X.sup.1 is --Cl, --Br, --H, or --R.sup.5 ; 
(iii) when Y.sup.1 is --R.sup.2 --, X.sup.1 is --Cl or --Br; and 
(iv) when Y.sup.1 is --N.sym.(R.sup.3).dbd.CH.sub.2, X.sup.1 is 
O.crclbar.R.sup.5, O.crclbar.COR.sup.5, Cl.crclbar., Br.crclbar., 
I.crclbar., or CH.sub.3 C.sub.6 H.sub.4 SO.sub.3 .crclbar.. Representative 
aldehyde precursor compounds are: water; alkanols; aliphatic, aromatic and 
polymeric primary and secondary bromides and chlorides, for example, 
n-hexyl bromide and chloride, a,a'-dibromo- and dichloroxylenes, 
poly(p-chloromethylstyrene); aldehyde acetals, including cyclic acetals; 
acyl bromides and chlorides; oxiranes; aliphatic and aromatic ketones, for 
example, diethylketone, cyclohexanone and benzophenone; and aliphatic and 
aromatic imino esters and their salts. All are known compounds or are 
readily prepared by known methods. 
Haloaromatic compounds, such as bromobenzene, should be avoided unless 
suitably activated by substituents which are themselves inert under 
polymerizing conditions. 
The in-situ reaction between the aldehyde precursor compound and a silyl 
enol ether requires at least one mole of silyl enol ether per mole of 
precursor compound. When the silyl enol ether is not a monomer, the 
reaction is usually equimolar (1:1). 
Preferably, the process of preparing the polymer of formula 2 is carried 
out in the presence of an aromatic aldehyde. Preferred embodiments of the 
processes of preparing the polymers of the invention include the 
additional steps wherein unsaturation is removed by hydrogenation and/or 
silyl ether groups in the polymers are hydrolyzed to --OH, particularly in 
the presence of fluoride or bifluoride ions. 
Catalysts which are useful in the invention process for preparing polymer 
(1) are Lewis acids, including but not limited to zinc iodide, zinc 
bromide, zinc chloride, mercuric iodide, stannic chloride, stannous 
chloride, ferric iodide, ferric bromide, ferric chloride, zeolites which 
are at least partially in their hydrogen form, boron trifluoride etherate, 
zirconium chloride, and dialkyl aluminium halides. Preferably, the 
catalysts are zinc halides, and most preferably zinc iodide. 
The process for preparing polymer (1) is carried out at about -100.degree. 
C. to about 120.degree. C., preferably at about 0.degree. C. to about 
70.degree. C., and most preferably at about 20.degree. C. to about 
40.degree. C. When boron trifluoride etherate or a dialkyl aluminum halide 
is used as the catalyst, the polymerization is carried out above about 
0.degree. C. By "polymerizing conditions" is meant an inert medium in the 
temperature range specified above. A solvent is desirable but not 
essential. 
Suitable solvents are aprotic liquids in which the monomer(s), initiator or 
initiator precursor, and catalyst are sufficiently dispersible and/or 
soluble for reaction (polymerization) to occur. A partial list of suitable 
solvents includes aromatic hydrocarbons, such as toluene or xylene, 
aliphatic hydrocarbons or chlorinated hydrocarbons. Preferred solvents are 
toluene, dichloromethane, and 1,2-dichloromethane. 
The polyenyloxysilane monomers which are preferred for use in the invention 
process are those wherein each R.sup.9 group is H and each R.sup.1 group 
is alkyl and the total number of carbon atoms in all of the R groups is at 
least six; more preferably, at least one of these alkyl groups is 
branched. It has been discovered that use of such monomers can provide 
polymers of formula (1) having significantly higher molecular weight. 
While lower molecular weight polymers of formula (1) are useful, 
especially as intermediates for block copolymers, and in blends with other 
polymers, the ability to attain higher molecular weight when desired is a 
preferred feature. 
The polyenyloxysilane monomers which are liquids can be polymerized without 
a solvent, although a solvent is beneficial in controlling exothermic 
temperature rise during polymerization. When a solvent is used, the 
monomer can be dispersed in the solvent at concentrations of at least 1 
weight percent; preferably, at least 10 weight percent; and most 
preferably, at about 50 weight percent. The initiator, if used, is 
employed at a concentration such that the monomer/initiator molar ratio is 
greater than one and, preferably, greater than 5. The amount of initiator 
can be varied to control the molecular weight of the polymeric product, in 
accordance with known polymerization procedures. The catalyst is normally 
present in such amount that the monomer/catalyst molar ratio is at least 
10; preferably, at least 50; and most preferably, at least 100. 
In the process for preparing polymer (1), it is preferable to charge the 
catalyst, initiator, if any, and solvent, if any, to a polymerization 
vessel before adding the monomer(s), especially if polymeric product of 
relatively narrow molecular weight distribution, that is, Mw/Mn is between 
1 and about 2, are desired. Although it is preferable to charge the 
catalyst, initiator, and solvent to the polymerization vessel before 
adding monomer(s), subsequent polymerization rate being controlled by 
monomer addition, further additions of catalyst can be necessary to 
sustain polymerization. 
The invention polymer (2) is prepared in the presence of an initiator which 
is an aldehyde or aldehyde precursor compound and contains active terminal 
--CHO groups until contacted with a reagent which is active towards 
aldehydes. The --CHO terminated polymer is "living" in the sense that it 
will polymerize further in the presence of monomer(s) and catalyst, 
permitting the preparation of "tailored" copolymers, such as block 
copolymers having highly desirable properties. The non-carbaldehyde 
portion of the initiating aldehyde is found, by analysis, to be attached 
to the inactive (non-carbaldehyde) ends of polymeric chains. 
The process for preparing the capped polymer (3) is carried out by reacting 
polymer (2) with an aldehyde-reactive capping agent. Preferred capping 
agents are silicon compounds, including silyl ketene acetals, silyl enol 
ethers, silyl ketene imines or the keto forms thereof, having the general 
formula (R.sup.1).sub.3 SiQ.sup.1 R.sub.p wherein R.sup.1 is defined as 
above; Q.sup.1 is an enoxy or enimino diradical, or keto form thereof, and 
R.sub.p is H, an alkyl radical having 1 to 4 carbon atoms, or a 
methacrylic and/or acrylic polymeric radical. Polymer (2) is reacted with 
the above-defined silicon compound in the manner described in U.S. Pat. 
No. 4,544,724. Preferably, the reagent (R.sup.1).sub.3 SiQ.sup.1 R.sub.p 
is the "living"0 polymer disclosed in U.S. Pat. Nos. 4,417,034 and 
4,508,880 and EPO Publication No. 0068,887 wherein R.sub.p is a polymeric 
material. The relevant disclosures of U.S. Pat. Nos. 4,417,034, 4,508,880, 
and 4,544,724 are incorporated herein by reference. When such "living" 
polymers are employed, the polymer of formula (2) comprises 
polyenyloxy-acrylic block polymers which may be linear or branched, the 
latter having, for example, star or comb configurations. 
Other preferred capping agents include those of the formula R.sub.p.sup.1 
X.sup.2 wherein R.sub.p.sup.1 is selected from the group consisting of H, 
alkyl, alkenyl, and alkadienyl radicals having 1 to 20 carbon atoms, 
cycloalkyl aryl, alkaryl, and aralkyl radicals having 6 to 20 carbon 
atoms, and polymeric radicals containing at least 20 carbon atoms; any of 
said radicals optionally containing one or more ether oxygen atoms within 
aliphatic segments thereof; and any of all the aforesaid radicals, 
optionally, containing one or more functional substituents that are 
unreactive under capping conditions; and X.sup.2 is a monovalent radical 
selected from --OH, --CN, --SO.sub.3 M, --NH.sub.2, --ONH.sub.2, 
--NHNH.sub.2, --NHC(O)NH.sub.2, --NHC(NH)NH.sub.2, --NHNHC(O)NH.sub.2 and 
--G where G is the halometal portion of a Grignard reagent and M is H, an 
alkalimetal or ammonium. Polymer (2) is reacted with the reagent 
R.sub.p.sup.1 in the manner described in U.S. Pat. No. 4,544,724, the 
relevant disclosures of which are incorporated herein by reference. 
The invention polymer (1) contains unsaturation and pendant 
--OSi(R.sup.1).sub.3 groups. Unsaturation can be eliminated by reductive 
hydrogenation employing known methods such as homogeneous hydrogenation in 
the presence of tris(triphenylphosphine)rhodium chloride. The polymer is 
dissolved in a suitable aprotic solvent such as toluene, and the reaction 
is carried out at a temperature of about 10.degree. C. to about 
100.degree. C., under positive hydrogen pressures of at least 20 psi (138 
kPa). Catalytic hydrogenation with heterogeneous catalysts such as Raney 
nickel or palladium/carbon has not been successful. 
Pendant --OSi(R.sup.1).sub.3 groups which can be present in polymers of the 
invention can be converted to --OH groups by known methods, such as 
hydrolysis, for example, by treatment with a source of fluoride ion, such 
as tetraalkylammonium fluoride, dissolved in THF-methanol mixture. The 
pendant --OH functions are useful reactive sites for cross-linking or 
other chemical modifications. 
It will be understood that invention polymer (1), after reduction and 
hydrolysis, consists essentially of recurring units of polyalkylene, 
--[CH(R.sup.9)CH(R.sup.9)].sub.p --, and hydroxyalkylene, 
--CH(R.sup.9)CH(OH)--, wherein p can vary from a minimum of about 0.02 per 
unit of hydroxyethelene to a maximum of about 5 per unit of 
hydroxyalklene. Preferably, R.sup.9 is H (i.e. polyalkylene is 
polyethylene and hydroxyalkylene is hydroxyethylene). These preferred 
polymers, referred to in the art as vinyl alcohol/ethylene copolymers, are 
melt-processible into shaped articles having excellent moisture and oxygen 
barrier properties.

In the following examples of specific embodiments of the invention, all 
parts and percentages are by weight and degrees are Celsius unless 
otherwise specified. The polydispersity (D) of the polymer products 
prepared in the examples is defined by D=Mw/Mn and the molecular weights 
were determined by gel permeation chromatography (GPC) in which methyl 
methacrylate standards were used. Unless otherwise specified, molecular 
weights were measured on the polymer of formula 1 before the polymer was 
hydrogenated and/or silyl groups were removed. 
EXAMPLE 1 
A. Preparation of (1,3-Butadienyloxy)phenyldimethylsilane 
##STR10## 
A 250 mL flask, fitted with a magnetic stirrer, a reflux condenser and an 
addition funnel, was charged with zinc chloride (0.25 g, 1.83 mmol, 
anhydrous), triethylamine (36.2 mL, 0.260M, distilled from CaH.sub.2), 
crotonaldehyde (21.0 mL, 0.257M, dried over MgSO.sub.4 and distilled), and 
toluene (35 mL, distilled from sodium). 42 mL of phenyldimethyl 
chlorosilane (0.254M) were added dropwise via the addition funnel over one 
hour with stirring. The resulting mixture was heated slowly to about 
65.degree. and maintained at 65.degree.-75.degree. for a total of 6.5 
hours with stirring. The mixture was cooled to ambient temperature and 
filtered to remove precipitated triethylamine hydrochloride (32 g, 92%) 
which was rinsed on the filter with 35 mL of dry toluene. The resulting 
filtrate and rinse were combined and distilled on a water pump at about 
110 mm to remove solvent and unreacted starting materials. The resulting 
residue was distilled on an oil pump to give 
(1,3-butadienyloxy)phenyldimethylsilane (30.9 g, 59%) as a colorless 
liquid boiling at 57.8.degree.-59.0.degree./0.10 mm (13 Pa). 
The .sup.1 H nmr spectrum of the liquid contained resonances at 
.delta.=7.14-7.60 ppm (C.sub.6 H.sub.5 --), at .delta.=4.57-6.54 ppm 
(multi-line pattern corresponding to the CH.sub.2 .dbd.CHCH.dbd.CH--group) 
and at .delta.=0.36 ppm (CH.sub.3 --Si) with relative intensities 
consistent with the (1,3-butadienyloxy)phenyldimethylsilane structure. 
B. Polymerization of (1,3-Butadienyloxy)phenyldimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
A 50 ml flask, fitted with a magnetic stirrer, a dropping funnel, a syringe 
septum, a thermocouple well and a reflux condenser capped with nitrogen 
bubbler, was charged with zinc iodide (0.25 g, 0.78 mmol), benzaldehyde 
(0.22 mL, 2.2 mmol), and methylene chloride (15 mL). The resulting mixture 
was cooled in a water bath at ambient temperatures. Then, with stirring 12 
mL of (1,3-butadienyloxy)phenyldimethylsilane (about 10.0 g, 49 mmol) were 
added dropwise via the dropping funnel over a period of 30 minutes. A mild 
exothermic reaction was evident. The reaction mixture was stirred at 
ambient temperature for about 16 hours. The reaction mixture was filtered 
to remove suspended undissolved zinc iodide which was washed on the filter 
with 10 mL of methylene chloride. The resulting filtrate and rinse were 
combined and distilled on a water pump to remove solvent. The resulting 
residue was dried under an oil pump vacuum at 50.degree. to give a viscous 
liquid polymer (10.4 g, 100%) with an inherent viscosity (1.5% in methyl 
isobutylketone at 25.degree.) of 0.064. Molecular weight (Mn) and 
polydispersity (D) were determined by gel permeation chromatography (GPC) 
to be 5290 and 1.93, respectively. 
EXAMPLE 2 
A. Preparation of (1,3-Butadienyloxy)n-propyldimethylsilane 
(1,3-Butadienyloxy)n-propyldimethylsilane (b.p. of 
61.6.degree.-62.2.degree./13 mm, 1.7 kPa) was prepared in a 65% yield from 
n-propyldimethylchlorosilane using a procedure similar to that described 
in Example 1A. The .sup.1 H nmr spectrum contained resonances at 
.delta.=5.71-6.80 ppm (the CH.sub.2 .dbd.CHCH.dbd.CH-- group) at 
.delta.=0.58-1.63 ppm (n--C.sub.3 H.sub.7 group) and at .delta.=0.21 ppm 
(CH.sub.3 --Si) with relative intensities consistent with the title 
structure. 
B. Polymerization of (1,3-Butadienyloxy)n-propyldimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol) benzaldehyde (0.22 mL, 2.2 mmol, 
distilled from calcium hydride), and methylene chloride (15 mL) which had 
been dried over and distilled from phosporus pentoxide. 10.0 mL of 
1,3-butadienyloxy)n-propyldimethylsilane (about 8.0 g, 47 mmol), prepared 
as described in Part A above, were added dropwise via the dropping funnel 
over a period of 23 minutes. The ensuing reaction was accompanied by a 
temperature rise of the reaction mixture of from 17.degree. to 
37.2.degree.. The mixture was stirred for about 16 hours at ambient 
temperature. 
The reaction mixture was worked up according to a procedure similar to that 
disclosed in Example 1B to give a viscous liquid polymer (4.57 g, yield 
not calculated because of loss on transfer) with the inherent viscosity of 
0.060. Molecular weight (Mn) and polydispersity (D) were determined by GPC 
to be 3550 and 1.8, respectively. 
EXAMPLE 3 
A. Preparation of (1,3-Butadienyloxy)ethenyldimethylsilane 
(1,3-butadienyloxy)ethenyldimethylsilane (b.p. 
43.0.degree.-46.4.degree./10.0 mm, 1.3 kPa) was prepared in a 68% yield 
from ethenyldimethylchlorosilane using a procedure similar to that 
described in Example 1A. The .sup.1 H nmr spectrum contained resonances at 
.delta.=4.69-6.67 ppm (multiline pattern corresponding to the CH.sub.2 
.dbd.CHCH--CH-- and the CH.sub.2 .dbd.CH-- groups) and at .delta.=0.29 ppm 
(CH.sub.3 --Si) with relative intensities consistent with the 
(1,3-butadienyloxy)ethenyldimethylsilane structure. 
B. Polymerization of (1,3-Butadienyloxy)ethenyldimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol), benzaldehyde (0.22 mL, 2.2 
mmol), and methylene chloride (15 mL). 9.0 mL of 
(1,3-butadienyloxy)ethenyldimethylsilane (about 7.0 g, 45 mmol), prepared 
as described in Part A above, were added dropwise via the dropping funnel 
over a period of 23 minutes. The ensuing reaction was accompanied by a 
temperature rise of the reaction mixture of from 21.2.degree. to 
35.8.degree.. The mixture was stirred for about 16 hours at ambient 
temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (6.15 g, about 
83%) with an inherent viscosity of 0.050. Molecular weight (Mn) and 
polydispersity (D) were determined to be 2620 and 2.78, respectively. 
Proton nmr spectrum indicated that there were about 18 diene units for 
each phenyl end group and that the vinyl group on the silicon of the diene 
monomer did not take part in polymerization. 
EXAMPLE 4 
A. Preparation of (1,3-Butadienyloxy)isopropyldimethylsilane 
1,3-Butadienyloxy)isopropyldimethylsilane (b.p. 
58.8.degree.-60.2.degree./11.0 mm, 1.5 kPa) was prepared in a 55% yield 
from isopropyldimethylchlorosilane using a procedure similar to that 
described in Example 1A. The .sup.1 H nmr spectrum contained resonances at 
.delta.=4.67-6.81 ppm (the CH.sub.2 .dbd.CHCH.dbd.CH-- group) at 
.delta.=0.67-1.27 ppm (--CH of isopropyl group), at 0.96 ppm (CH.sub.3 
--C), and at .delta..dbd.0.14 ppm (CH.sub.3 --Si) with relative 
intensities consistent with the (1,3-butadienyloxy)isopropyldimethylsilane 
structure. 
B. Polymerization of (1,3-Butadienyloxy)isopropyldimethylsilane initiated 
by benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol), benzaldehyde (0.22 mL, 2.2 
mmol), and methylene chloride (15 mL). 10.0 mL (about 47 mmol) of 
(1,3-butadienyloxy)isopropyldimethylsilane, prepared as described in Part 
A above, were added dropwise via the dropping funnel over a period of 17 
minutes. The ensuing exothermic reaction was accompanied by a temperature 
rise of the reaction mixture of from 21.degree. to 29.degree.. The mixture 
was stirred for about 19 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (7.67 g, 96%) 
with an inherent viscosity of 0.064. Molecular weight (Mn) and 
polydispersity were determined to be 3680 and 1.64, respectively. Proton 
nmr spectrum indicated that there were about 16 diene units for each 
phenyl end group. 
EXAMPLE 5 
A. Preparation of (1,3-Butadienyloxy)t-butyldimethylsilane 
##STR11## 
A 1 L flask equipped with a magnetic stirrer, a reflux condenser, a syringe 
adapter and a thermocouple was charged with anhydrous zinc chloride (10.87 
g, 79.8 mmol) t-butyldimethylchlorosilane (195.49 g, 1.297 mol), 
crotonaldehyde (108 mL, 1.32 mole, dried and distilled), triethylamine 
(190 mL, 1.36 mole, distilled from CaH.sub.2) and toluene (180 mL, 
distilled from Na). The resulting mixture was refluxed for about 18 hours. 
The ensuing reaction was accompanied by a temperature rise of the mixture 
of from 101.degree. to 107.degree.. The mixture was cooled to ambient 
temperature and filtered. The resulting solid was rinsed on the filter 
with toluene. The resulting filtrate and rinse were combined and distilled 
on a water pump at about 50 mm (6.7 kPa) to remove solvent and unreacted 
starting materials. The resulting residue was filtered to remove 
additional precipitate and distilled on an oil pump at about 2 mm (0.27 
kPa) to give (1,3-butadienyloxy)t-butyldimethylsilane (50.27 g, 21%, 
distilling at 26.2.degree./2.6 mm (0.35 kPa)-48.2.degree./3.0 mm (0.40 
kPa)). Redistillation of this material through an 18" spinning band still 
gave the title compound as a colorless liquid boiling at 42.2.degree./4.0 
mm (0.53 kPa)-54.6.degree./5.2 mm (0.69 kPa). The .sup.1 H nmr spectrum 
contained resonances at .delta.=4.62-6.67 ppm (CH.sub.2 .dbd.CHCH.dbd.CH-- 
group), at .delta.=0.87 ppm (C--CH.sub.3), at .delta.=0.11 ppm 
(Si--CH.sub.3) with relative intensities consistent with the 
(1,3-butadienyloxy)t-butyldimethylsilane structure. 
B. Polymerization of (1,3-Butadienyloxy)t-butyldimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.055 g, 1.7 mmol), benzaldehyde (0.060 mL, 0.59 
mmol), and methylene chloride (15 mL). 12.0 mL of 
(1,3-butadienyloxy)t-butyldimethylsilane (about 9.6 g, 52 mmol), prepared 
as described in Part A above, were added dropwise via the dropping funnel 
over a period of 33 minutes. The ensuing reaction was accompanied by a 
temperature rise of from 20.2.degree. to 27.0.degree.. The mixture was 
stirred for about 20 hours at ambient temperature. 
The reaction mixture was filtered and the resulting filtrate was distilled 
on a water pump to remove solvent. The resulting residue was dried under 
an oil pump vacuum to give a tough semi-solid colorless polymer (10.01 g, 
100%) having an inherent viscosity of 0.106. Proton nmr spectrum indicated 
that there were about 99 diene units for each phenyl end group. Molecular 
weight and polydispersity (D) were determined by GPC to be 11,600 and 
2.30, respectively. 
EXAMPLE 6 
A. Preparation of (1,3-Butadienyloxy)(2-phenylethyl)dimethylsilane 
(1,3-Butadienyloxy)(2-phenylethyl)dimethylsilane (b.p. of 
76.6.degree.-81.8.degree./0.05 mm, 6.7 Pa) was prepared in a 62% yield 
from (2-phenylethyl)dimethylchlorosilane using a procedure similar to that 
described in Example 1A. The .sup.1 H nmr spectrum contained resonances at 
.delta.=4.63-6.57 ppm (CH.sub.2 .dbd.CHCH.dbd.CH-- group, at .delta.=7.08 
ppm (C.sub.6 H.sub.5), and at .delta.=0.09 ppm (Si--CH.sub.3), with 
relative intensities consistent with the 
(1,3-butadienyloxy)(2-phenylethyl)dimethylsilane structure. 
B. Polymerization of (1,3-Butadienyloxy)(2-Phenylethyl)dimethylsilane 
initiated by benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol), benzaldehyde (0.22 mL, 2.2 
mmol) and methylene chloride (15 mL). 14.0 mL of 
(1,3-butadienyloxy)(2-phenylethyl)dimethylsilane (about 12.6 g, 54 mmol) 
prepared as described in Part A above, were added dropwise via the 
dropping funnel over a period of 35 minutes. The ensuing reaction was 
accompanied by a temperature rise of the reaction mixture of from 
20.2.degree. to 32.6.degree.. The mixture was stirred at ambient 
temperatures for about 19 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (12.18 g, about 
95%) with an inherent viscosity of 0.063. Molecular weight (Mn) and 
polydispersity (D) of the major component of the product were determined 
by GPC to be 5180 and 2.13 respectively. A small amount of a relatively 
low molecular weight fraction was also present in the product. 
EXAMPLE 7 
Polymerization of (1,3-Butadienyloxy)trimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 0.69 
g (2.2 mmol) of reagent grade zinc iodide. The flask was evacuated to a 
pressure of less then 1 mm (0.13 kPa) and heated with a heat gun for a 
period of 10 minutes to completely dry the zinc iodide. The flask was 
brought back to atmospheric pressure with dry nitrogen and charged with 
benzaldehyde (0.22 mL, 2.2 mmol) and methylene chloride (15 mL). 16.5 mL 
(136.5 mmol) of (1,3-butadienyloxy)trimethylsilane were added via the 
dropping funnel over a period of 42 minutes. The reaction mixture was 
stirred for about 20 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (11.85 g, 87%) 
with an inherent viscosity of 0.067. Molecular weight (Mn) and 
polydispersity were determined to be 4020 and 6.30, respectively. Proton 
nmr spectrum indicated that there were about 23 diene units for each 
phenyl end group. The infrared spectrum contained bands at 2950, 2900 and 
2860 cm.sup.-1 (sat CH), 3030 cm.sup.-1 (.dbd.CH), 1660 cm.sup.-1 (conj. 
aldehyde C.dbd.O), 1250, 840 and 750 cm.sup.-1 (Si--CH.sub.3) and at 970 
cm.sup.-1 which is the C--H out of plane deformation frequency diagnostic 
of an internal trans--CH.dbd.CH. 
EXAMPLE 8 
Polymerization of (1,3-Butadienyloxy)trimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 1.37 
g (4.3 mmol) of reagent grade zinc iodide. The flask was evacuated, 
heated, and brought back to atmospheric pressure according to a method 
similar to that described in Example 7. The flask was charged with 
benzaldehyde (0.44 mL, 4.4 mmol) and methylene chloride (15 mL). 16.5 mL 
of (1,3-butadienyloxy)trimethylsilane (13.4 g, 136.5 mmol) were added 
dropwise via the dropping funnel over a period of 27 minutes. The ensuing 
exothermic reaction was accompanied by a temperature rise of the reaction 
mixture of from 22.6.degree. to 36.8.degree.. The mixture was stirred for 
about 20 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (11.39 g, 82%) 
with an inherent viscosity of 0.051. Molecular weight (Mn) and 
polydispersity were determined to be 4290 and 7.52, respectively. The 
.sup.1 H nmr spectrum of the isolated polymer contained major resonances 
at .delta.=0.10 ppm (Si--CH.sub.3), 2.16 ppm (--CH.sub.2 --), 4.02 ppm 
(--CH--OSi) and at 5.48 ppm (.dbd.CH). A comparison of the relative 
intensities of these resonances indicated that there are two .dbd.CH 
protons which is consistent with a linear arrangement in the polymer 
backbone of the 4 carbon atoms of the butadiene units. There are also 
other nmr resonances which could arise from the pressure of small amounts 
of isomeric structures. 
EXAMPLE 9 
Polymerization of (1,3-Butadienyloxy)trimethylsilane initiated by 
benzaldehyde in the presence of zinc bromide 
A 250 mL flask, fitted with a magnetic stirrer, a dropping funnel, a 
syringe septum, a thermocouple well and a reflux condenser capped with a 
nitrogen bubbler was charged with anhydrous zinc bromide (0.71 g, 5.2 
mmol), benzaldehyde (0.44 mL, 4.4 mmol), and methylene chloride (50 mL). 
58.5 mL of (1,3-butadienyloxy)trimethylsilane (47.4 g, 333.5 mmol) were 
added dropwise via the dropping funnel over a period of 54 minutes. The 
mixture was stirred for about 16 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (38.35 g, 80%) 
with an inherent viscosity of 0.072. Molecular weight (Mn) and 
polydispersity were determined to be 5060 and 2.30, respectively. Proton 
nmr spectrum indicated that there were about 47 diene units for each 
phenyl end group. 
EXAMPLE 10 
Copolymerization of (1,3-Butadienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane 
An apparatus similar to that described in Example 1B was charged with 0.15 
g of reagent grade zinc iodide. The flask was evacuated, heated, and 
brought back to atmospheric pressure according to a procedure similar to 
that described in Example 7. The flask was charged with benzaldehyde (0.22 
mL, 2.2 mmol) and methylene chloride (15 mL). A well mixed mixture of 11.3 
mL of (ethenyloxy)t-butyldimethylsilane (8.98 g, 56.8 mmol) and 5.1 mL 
(4.14 g, 42.2 mmol) of (1,3-butadienyloxy)trimethylsilane was added 
dropwise via the dropping funnel over a period of 39 minutes. The ensuing 
exothermic reation was accompanied by a temperature rise of the reaction 
mixture of from 24.6.degree. to 33.2.degree.. The mixture was stirred for 
about 20 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (10.73 g, 79%) 
with an inherent viscosity of 0.037. Molecular weight (Mn) and 
polydispersity were determined to be 1970 and 1.80, respectively. Proton 
nmr spectrum indicated that there were about 16 diene units for each 
phenyl end group. The .sup.1 H nmr spectrum indicated that the ratio of 
monomers in the copolymer was close to 2 vinyl ether units for each diene 
unit. 
The monomodal molecular weight distribution curve indicated that the 
product was a true copolymer. 
EXAMPLE 11 
Reduction of a Copolymer of (1,3-Butadienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane 
A stainless steel pressure vessel which had been flushed with dry nitrogen 
was charged with 1.00 g of tris(triphenylphosphine)rhodium chloride and a 
solution of 5.53 g of the copolymer prepared in Example 10 dissolved in 
100 mL of anhydrous toluene. The vessel was cooled in dry ice, evacuated, 
pressured with hydrogen and heated at 60.degree. for 24 hours while the 
hydrogen pressure was maintained at 200 psi (1.38 MPa). 
An .sup.1 H nmr spectrum on a sample of the product obtained by evaporating 
the solvent showed that the polymer contained little if any carbon-carbon 
unsaturation. 
EXAMPLE 12 
Reduction of a Polymer of (1,3-Butadienyloxy)trimethylsilane 
A mixture of 1.00 g of tris(triphenylphosphine)rhodium chloride and a 
solution of 6.71 g of a (1,3-butadienyloxy)trimethylsilane polymer, 
prepared according to a procedure similar to that described in Examples 
7-9, in 100 ml of anhydrous toluene was reduced at 60.degree. and 200 psi 
(1.38 MPa) hydrogen pressure for a period of 24 hours according to a 
procedure similar to that described in Example 12. 
An .sup.1 H nmr spectrum of a sample of the product obtained by evaporating 
the solvent showed that it contained just a little unsaturated CH. The 
reduction was estimated to be 90-95% complete. 
EXAMPLE 13 
Copolymerization of (1,3-Butadienyloxy)t-butyldimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol), benzaldehyde (0.22 mL, 2.2 
mmol), and methylene chloride (15 mL). A well mixed mixture of 
(1,3-butadienyloxy)t-butyldimethylsilane (7.0 mL, about 5.6 g, 30.4 mmol) 
and (ethenyloxy)t-butyldimethylsilane (6.0 mL, 4.8 g, 30.4 mmol) was added 
dropwise via the dropping funnel over a period of 35 minutes. The ensuing 
exothermic reaction was accompanied by a temperature rise of the reaction 
mixture of from 19.6.degree. to 25.2.degree.. The mixture was stirred for 
about 18 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (9.78 g, 95%) 
with an inherent viscosity of 0.052. Molecular weight (Mn) and 
polydispersity were determined to be 4660 and 1.68, respectively. Proton 
nmr spectrum indicated that there were about 16 diene units for each 
phenyl end group. The relative intensities of appropriate resonances in 
the .sup.1 H nmr spectrum indicated that the polymeric product contained 
approximately equimolar quantities of the two monomers. The monomodal 
molecular weight distribution curve indicates that the product was a true 
copolymer. 
EXAMPLE 14 
Preparation of a Block Copolymer of (1,3-Butadienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 0.69 
g (2.2 mmol) of reagent grade zinc iodide. The flask was evacuated, 
heated, and brought back to atmospheric pressure according to a procedure 
similar to that described in Example 7. The flask was charged with 
benzaldehyde (0.22 mL, 2.2 mmol) and methylene chloride (15 mL). 8.3 mL of 
(1,3-butadienyloxy)trimethylsilane (6.7 g, 47.1 mmol) were added dropwise 
via the dropping funnel over a period of 29 minutes. The ensuing 
exothermic reaction was accompanied by a temperature rise of the reaction 
mixture from 21.6.degree. to 29.2.degree.. After the exothermic reaction 
appeared to be over, 6.2 mL of (ethenyloxy)t-butyldimethylsilane (4.9 g) 
were added dropwise via the dropping funnel over a period of 37 minutes. 
The mixture was stirred for a period of about 16 hours at ambient 
temperature. The reaction mixture was worked up according to a procedure 
similar to that described in Example 1B to give a viscous liquid polymer 
(11.01 g, 95%) with an inherent viscosity of 0.049. Molecular weight (Mn) 
and polydispersity were determined to be 2400 and 1.94, respectively. 
A comparison of the intensities of appropriate resonances in the .sup.1 H 
nmr spectrum indicated that the ratio of monomers in the copolymer was 
1.29 diene units for each ethenyloxy unit. The monomodal molecular weight 
distribution curve indicates that the product was a true copolymer. 
EXAMPLE 15 
Preparation of a Block Copolymer of (1,3-Butadienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane initiated by benzylaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 1B was charged with 0.69 
g of reagent grade zinc iodide. The flask was evacuated, heated, and 
brought back to atmospheric pressure according to a procedure similar to 
that described in Example 7. The flask was charged with benzaldehyde (0.22 
mL, 2.2 mmol) and methylene chloride (15 mL). 9.2 mL of 
(ethenyloxy)t-butyldimethylsilane (7.3 g, 46.2 mmol) were added dropwise 
via the dropping funnel over a period of 34 minutes. The ensuing 
exothermic reaction was accompanied by a temperature rise of the reaction 
mixture of from 21.6.degree. to 36.8.degree.. After the exothermic 
reaction appeared to be over, 8.3 mL (1.30 mmol) of 
(1,3-butadienyloxy)t-butyldimethylsilane were added dropwise via the 
dropping funnel over a period of 23 minutes. The resulting mixture was 
stirred for a period of about 15 hours at ambient temperature. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (12.13 g, 84%) 
with an inherent viscosity of 0.048. Molecular weight (Mn) and 
polydispersity were determined to be 3010 and 1.86, respectively. A 
comparison of the intensities of appropriate resonances in the .sup.1 H 
nmr spectrum indicated that the ratio of monomers in the copolymer was 
1.26 vinyl ether units for each diene unit. The monomodal molecular weight 
distribution curve indicates that the product was a true copolymer. 
EXAMPLE 16 
Polymerization of (1,3-Butadienyloxy)trimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
A 250 mL flask, fitted with a magnetic stirrer, a dropping funnel, a 
syringe septum, a thermocouple well and a reflux condenser capped with a 
nitrogen bubbler, was charged with anhydrous zinc iodide (0.50 g, 1.57 
mmol), benzaldehdye (0.44 mL, 4.4 mmol) and methylene chloride (60 mL). 59 
mL of (1,3-butadienyloxy)trimethylsilane (47.8 g, 336 mmol) were added 
dropwise via the dropping funnel over a period of 40 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (38.29 g, 79%) 
with an inherent viscosity of 0.080. Molecular weight (Mn) and 
polydispersity (D) were determined by GPC to be 6220 and 2.45, 
respectively. Proton nmr spectrum indicated that there were about 60 diene 
units for each phenyl end group. 
EXAMPLES 17 AND 18 
Polymerization of (1,3-Butadienyloxy)t-butyldimethylsilane in the presence 
of zinc iodide 
An apparatus similar to that described in Example 1B was charged with zinc 
iodide (0.50 g, 1.57 mmol) and methylene chloride (15 mL). 11.0 mL of 
(1,3-butadienyloxy)t-butyldimethylsilane (about 8.8 g, 10.2 mmol) were 
added dropwise via the dropping funnel over a period of 15 minutes. The 
ensuing mild exothermic reaction began about 30 minutes after the addition 
was completed. The reaction mixture was stirred at ambient temperature for 
about 16 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a viscous liquid polymer (8.22 g, 93%) 
with an inherent viscosity of 0.073. Molecular weight (Mn) and 
polydispersity (D) were determined by GPC to be 8530 and 1.97, 
respectively. 
Another run was carried out according to a procedure similar to that 
described above except that benzaldehyde (0.050 mL, 0.50 mmol) was added 
to the apparatus as described in Example 1B. The reaction mixture was 
worked up as described above to give a viscous liquid polymer (8.21 g, 
93%) with an inherent viscosity of 0.063. Molecular weight (Mn) and 
polydispersity were determined by GPC to be 5970 and 1.68, respectively. 
The polymers prepared above were compared by infrared spectroscopy. The 
polymers generated spectra which were essentially identical except that 
the polymer prepared with benzaldehyde initiator contained a weak band at 
1700 cm.sup.-1, whereas the spectrum of the polymer prepared without 
benzaldehyde had no such band. The band is believed to represent the 
C.dbd.O frequency for an aldehyde end group. 
EXAMPLE 19 
Removal of Silyl Groups from a Polymer of 
(1,3-Butadienyloxy)t-butyldimethylsilane 
A mixture of 4.84 g of a polymer of 
(1,3-butadienyloxy)t-butyldimethylsilane prepared according to a method 
similar to that described in Example 17 with an inherent viscosity of 
0.070, 20 mL of anhydrous tetrahydrofuran, 4 mL of reagent grade methanol, 
and 53 mL of 1M tetrabutylammonium fluoride in tetrahyrofuran was refluxed 
for about 4 hours. 
A sample of the resulting mixture was withdrawn and added to a large excess 
of water. The resulting solid, tan, powdery precipitate was filtered and 
dried on the filter. An infrared spectrum of the precipitate showed that 
it was primarily a polymeric unsaturated alcohol: 3390 cm.sup.-1 (--OH), 
2920+2850 cm.sup.-1 (sat CH), 1050 cm.sup.-1 (C--O), and 970 cm.sup.-1 
(trans internal (C.dbd.C)). Thus the spectrum is consistent with 
##STR12## 
Weak absorbtion at 1255 cm and 835 cm.sup.-1 indicates a small amount of 
residual Si--CH.sub.3 groups. The polymer was pressed at 150.degree. to a 
translucent self-supporting film. 
EXAMPLE 20 
Polymerization of (1,3-Butadienyloxy)trimethylsilane in the Presence of 
Stannic Chloride 
An apparatus similar to that described in Example 1B was charged with 15 mL 
of methylene chloride and 15 mL (85.4 mmol) of 
(1,3-butadienyloxy)trimethylsilane. A solution of 0.25 g (0.96 mmol) of 
anhydrous stannic chloride in 5 mL of methylene chloride was added 
dropwise via the dropping funnel over a period of 21 minutes. The 
resulting mixture was stirred for a period of about 16 hours at ambient 
temperature. 
The solid reaction mixture was broken up under methanol and the resulting 
polymer was isolated, further washed with methanol, and dried in a vacuum 
oven. The resulting product weighed 6.05 g (100%) and was shown by 
infrared spectroscopy to be essentially the same as the polymeric 
unsaturated alcohol obtained in Example 19. 
EXAMPLE 21 
Copolymerization of (1,3-Butadienyloxy)isopropyldimethylsilane and 
(Ethenyloxy)-t-butyldimethylsilane in the Presence of Zinc Iodide 
An apparatus similar to that described in Example 1B was charged with 0.058 
g (0.18 mmol) of anhydrous zinc iodide and 15 mL of methylene chloride. A 
well mixed mixture of 10.0 mL of 
(1,3-butadienyloxy)isopropyldimethylsilane (about 8.09 g, 47.6 mmol) and 
9.3 mL (46.7 mmol) of (ethenyloxy)-t-butyldimethylsilane was added 
dropwise via the dropping funnel over a period of 30 minutes. The ensuing 
exothermic reaction was accompanied by a temperature rise of the reaction 
mixture of from 21.0.degree. to 39.8.degree.. The mixture was stirred at 
ambient temperature for about 15 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 1B to give a colorless viscous semi-solid polymer 
(14.03 g, 91%) with an inherent viscosity of 0.090. Molecular weight (Mn) 
and polydispersity (D) were determined by GPC to be 7.670 and 3.06, 
respectively. 
EXAMPLE 22 
A. Preparation of (1,3,5-Hexatrienyloxy)trimethylsilane 
A 500 mL flask, fitted with a magnetic stirrer, an addition funnel, a 
thermocouple, and a reflux condenser connected to a nitrogen bubbler was 
charged with zinc chloride (0.50 g, 3.67 mmol), 72.4 mL of triethylamine 
(52.6 g, 0.519M, distilled from CaH.sub.2), 56.8 mL of freshly distilled 
2,4-hexadienal (49.5 g, 0.515M, b.p.=53.2.degree.-53.6.degree./10 mm, 1.3 
kPa), and 70 mL of toluene (distilled from Na). 64.4 mL of 
trimethylchlorosilane (55.1 g, 0.507M) were added dropwise via the 
addition funnel over a period of 68 minutes with stirring. The resulting 
mixture was heated to 63.degree. and maintained at about this temperature 
for 6 hour and 50 minutes. The mixture was cooled to ambient temperature 
and filtered to remove precipitated triethylamine hydrochloride. The 
resulting solid was rinsed on the filter with 70 mL of dry toluene. The 
resulting filtrate and rinse were combined and distilled on a water pump, 
first at about 100 mm (13.3 kPa) to remove solvent and unreacted starting 
materials and then at about 13 mm (1.7 kPa). Examination of the forerun 
indicated that it contained additional product. The total yield was 
estimated to be about 55%. For polymerization, the material was 
redistilled through an 18-inch spinning band still: b.p.=56.4.degree./3.0 
mm (0.40 kPa); 62.2.degree./5.0 mm (0.67 kPa). 
The .sup.1 H NMR spectrum (90 mHz) of the material contained a multi-line 
pattern for the hexatriene portion of the molecule at a=4.8-6.7 ppm. The 
high field portion of this pattern consists of a pair of overlapping 
doublets at a=4.99 ppm (J=9 Hz) and at a=5.12 ppm (J=15 Hz) which 
corresponds to the terminal CH.sub.2 of the hexatriene moiety. The rest of 
the hexatriene protons are represented by a very complicated series of 
lines at a=5.58-6.70 ppm. The methyl-on-silicon resonance is a singlet at 
a=0.23 ppm. The relative intensities of these three groups of resonances 
are consistent with the (1,3,5-hexatrienyloxy)trimethylsilane structure. 
B. Polymerization of (1,3,5-Hexatrienyloxy)trimethylsilane initiated by 
benzaldehyde in the presence of zinc iodide 
A 50 mL flask, fitted with a magnetic stirrer, a dropping funnel, a syringe 
septum, a thermocouple well and a reflux condenser capped with a nitrogen 
bubbler, was charged with anhydrous zinc iodide (0.084 g, 0.26 mmol), 15 
mL of methylene chloride, and benzaldehyde (0.080 mL, 0.80 mmol.). The 
reaction flask was cooled in a water bath at ambient temperature while 10 
mL of 1,3,5-hexatrienyloxy)trimethylsilane (8.0 g, 47.6 mmol) were added 
dropwise via the dropping funnel over a period of 25 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours 
and then filtered to remove some suspended solid. The resulting filtrate 
was distilled on a water pump to remove solvent, and the resulting residue 
was dried under an oil pump vacuum at 50.degree. C. to give a viscous 
liquid polymer (5.81 g, 73%). The liquid polymer became a tough, hard 
solid under nitrogen. 
The infrared spectrum (KBr) of the solid polymer contained bands at 3020 
cm.sup.-1 (.dbd.CH), 2960 and 2900 cm.sup.-1 (sat. CH), 1695 cm.sup.-1 
(conj. aldehyde (C.dbd.O), 1660 and 1620 cm.sup.-1 (conj. C.dbd.C), and at 
1255 and 840 cm.sup.-1 (Si--CH.sub.3). This spectrum is consistent with a 
linear polymer structure. A self-supporting film was pressed at 
150.degree.. 
EXAMPLE 23 
Polymerization of (1,3,5-Hexatrienyloxy)trimethylsilane in the presence of 
zinc iodide 
(1,3,5-hexatrienyloxy)trimethylsilane was polymerized according to a 
procedure similar to that described in Example 22 except that no 
benzaldehyde was used. The time period for adding the monomer was 27 
minutes and the reaction mixture was stirred at ambient temperature for 
about 16 hours after the monomer was added. After standing for three days 
under nitrogen, the reaction mixture was filtered and rinsed on the filter 
with fresh methylene chloride. The resulting residue was dried in a vacuum 
at 50.degree. to give 7.36 g of poly-(1,3,5-hexatrienyoxy)trimethylsilane 
(92%) as an amber-colored, hard solid. The polymer was insoluble in 
tetrahydrofuran, methylene chloride, and dimethyl-formamide, but could be 
pressed to an opaque, self-supporting film at 150.degree.. 
EXAMPLE 24 
Copolymerization of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane (1:1) initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.10 g, 0.31 mmol), methylene chloride (15 mL), and 
benzaldehyde (0.10 mL, 1.0 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)trimethylsilane (12.0 mL, 9.6 g, 57.1 mmol) and 
(ethenyloxy)t-butyldimethylsilane (11.4 mL, 9.1 g, 57.6 mmol) was added 
dropwise via the dropping funnel over a period of 34 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 22B to give a hard, yellow product (14.78 g, 79%). 
The product was somewhat soluble in tetrahydrofuran and could be cast to a 
clear film from the solvent. 
EXAMPLE 25 
Copolymerization of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane (1:3) initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.050 g, 0.16 mmol), methylene chloride (25 mL), 
and benzaldehyde (0.050 mL, 0.50 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)trimethylsilane (8.8 mL, 7.0 g, 41.6 mmol) and 
(ethenyloxy)t-butyldimethylsilane (25.0 mL, 19.9 g, 126 mmol) was added 
dropwise via the dropping funnel over a period of 35 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The resulting viscous reaction mixture was dripped slowly into 500 mL of 
methanol with rapid stirring. The resulting polymer was isolated, rinsed 
with fresh methanol and dried in a vacuum oven at 55.degree.-60.degree. to 
give a hard pale yellow product (22.5 g, 83%). The product was somewhat 
soluble in tetrahydrofuran and toluene. The polymer was plasticized with 
acetone to give a sticky, gelatinous material. A translucent, 
self-supporting film was pressed at 100.degree.. The product had an 
inherent viscosity of 0.151 (0.10% in toluene at 25.degree.). 
EXAMPLE 26 
Copolymerization of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(ethenyloxy)t-butyldimethylsilane (1:5) initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.050 g, 0.16 mmol), methylene chloride (25 mL), 
and benzaldehyde (0.050 mL, 0.50 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)trimethylsilane (5.3 mL, 4.2 g, 25.0 mmol) and 
(ethenyloxy)t-butyldimethylsilane (25.0 mL, 19.9 g, 126 mmol) was added 
dropwise via the dropping funnel over a period of 31 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The resulting viscous reaction mixture was worked up according to a 
procedure similar to that described in Example 25 to give a hard, 
colorless product (20.90 g, 86%) with an inherent viscosity of 0.076. A 
comparison of the intensities of appropriate resonances in the .sup.1 H 
NMR spectrum indicated that the ratio of monomers in the product was about 
5 ethenyloxy units for each triene unit. Molecular weight (Mn) and 
polydispersity (P) were determined by GPC to be 6,810 and 3.77, 
respectively. 
EXAMPLE 27 
Copolymerization of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(1,3-Butadienyloxy)trimethylsilane (1:2) initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.25 g, 0.78 mmol), methylene chloride (15 mL), and 
benzaldehyde (0.22 mL, 2.2 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)trimethylsilane (5.0 mL, 4.0 g, 23.8 mmol) and 
(1,3-butadienyloxy)trimethylsilane (8.5 mL, 6.9 g, 48.6 mmol) was added 
dropwise via the dropping funnel over a period of 30 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 22B to give a very viscous liquid polymer (9.78 g, 
88%) with an inherent viscosity of 0.140. Molecular weight (Mn) and 
polydispersity (D) were determined by GPC to be 7,800 and 6.12, 
respectively. 
EXAMPLE 28 
Copolymerization of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(1,3-Butadienyloxy)t-butyldimethylsilane (1:2) initiated by benzaldehyde 
in the presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.50 g, 1.57 mmol), methylene chloride (25 mL), and 
benzaldehyde (0.050 mL, 0.50 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)trimethylsilane (11.4 mL, 9.1 g, 54.1 mmol) and 
(1,3-butadienyloxy)t-butyldimethylsilane (25 mL, 20 g, 108.6 mmol) was 
added dropwise via the dropping funnel over a period of 29 minutes. The 
resulting mixture was stirred at ambient temperature for about 16 hours. 
The resulting viscous reaction mixture was worked up according to a 
procedure similar to that described in Example 27 to give a colorless, 
tough semi-solid product (20.76 g, 76%). A comparison of intensities of 
appropriate resonances in the .sup.1 H NMR spectrum indicated that the 
ratio of monomers in the product was about 2.3 diene units for each triene 
unit. Molecular weight (Mn) and polydispersity (D) were determined by GPC 
to be 9,930 and 4.39, respectively. A film was pressed at 100.degree.. 
EXAMPLE 29 
Removal of Silyl Groups from a Copolymer of 
(1,3,5-Hexatrienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane 
A mixture of 5.06 g of copolymer of (1,3,5-hexatrienyloxy)trimethylsilane 
and (ethenyloxy)t-butyldimethylsilane with an inherent viscosity of 0.090, 
prepared according to a method similar to that described in Example 26 
above, 20 mL of anhydrous tetrahydrofuran, 4 mL of reagent grade methanol, 
and 50 mL of 1M tetrabutylammonium fluoride in tetrahydrofuran was 
refluxed for 4 hours. The mixture was cooled to ambient temperature, 
filtered, and dripped slowly into 500 mL of distilled water with stirring. 
The resulting tan precipitate was filtered, rinsed on the filter with 
distilled water, and dried in a vacuum oven at 50.degree.-60.degree. to 
give a hard, tan product (1.69 g, 100%). The infrared spectrum indicated 
that the product was an unsaturated alcohol: 3400 cm.sup.-1 (--OH), 3020 
cm.sup.-1 (unsat. CH), 2960, 2930 and 2860 cm.sup.-1 (sat. CH), and 1075 
cm.sup.-1 (C--O). Weak absorption at 1255, 840 and 780 cm.sup.- 1 
indicated that the product had a small amount of residual Si--CH.sub.3 
groups. An opaque, self-supporting film was pressed at 150.degree.. 
EXAMPLE 30 
Reduction of a Copolymer of (1,3,5-Hexatrienyloxy)trimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane 
A mixture of 1.00 g of tris(triphenylphosphine)rhodium chloride and a 
solution of 7.00 g of a copolymer of (1,3,5-hexatrienyloxy)trimethylsilane 
and (ethenyloxy)t-butyldimethylsilane, prepared according to a method 
similar to that described in Example 26 above, in 100 mL of anhydrous 
toluene was reduced at 100.degree. and 300 psi (2.1 MPa) for a period of 
10 hours in a stainless steel pressure vessel. 
A .sup.1 H NMR spectrum of a sample of the resulting product obtained by 
evaporating the solvent indicated that most of the unsaturated CH had been 
converted to saturated CH. 
EXAMPLE 31 
A. Preparation of (1,3,5-Hexatrienyloxy)isopropyldimethylsilane 
A 500 mL flask, fitted with a magnetic stirrer, an addition funnel, a 
thermocouple, and a reflux condenser connected to a nitrogen bubbler was 
charged with 0.50 g of zinc chloride, 72.4 mL of triethylamine (52.6 g, 
0.51M, distilled from CaH.sub.2), 58.6 mL of distilled 2,4-hexadienal 
(51.0 g, 0.531M), and 70 mL of toluene (distilled from Na). 79.0 mL of 
isopropyldimethylchlorosilane (69.0 g, 0.504M) was added via the addition 
funnel and the resulting reaction mixture was heated slowly to 63.degree. 
and maintained at about this temperature for 6 hours and 50 minutes. 
The reaction mixture was worked up according to a procedure similar to that 
described in Example 22A to give 45.52 g of 
(1,3,5-hexatrienyloxy)isopropyldimethylsilane (44%) distilling at 
56.8.degree.-/0.30 mm (40 Pa) to 64.6.degree.-/0.65 mm (87 Pa). The .sup.1 
H NMR spectrum (90 mHz) of this material was essentially the same as that 
of (1,3,5-hexatrienyloxy)trimethylsilane described in Example 22, except 
that it contained resonances peculiar to the isopropyldimethylsilyl group 
instead of the trimethylsilyl resonance. The infrared spectrum (KBr) 
contained bands at 3080 and 3030 cm.sup.-1 (.dbd.CH), 2960, 2890 and 2870 
cm.sup.-1 (sat. CH), 1640 and 1585 cm.sup.-1 (conj. C.dbd.C), 1255 and 
840 cm.sup.-1 (Si--CH.sub.3), and 1185 cm.sup.-1 (unsat. Si--O--C), and is 
consistent with the hexatrienyloxysilane structure. 
B. Copolymerization of (1,3,5-Hexatrienyloxy)isopropyldimethylsilane and 
(Ethenyloxy)t-butyldimethylsilane (1:3) initiated by benzaldehyde in the 
presence of zinc iodide 
An apparatus similar to that described in Example 22B was charged with 
anhydrous zinc iodide (0.10 g, 0.31 mmol), methylene chloride (25 mL), and 
benzaldehyde (0.10 mL, 1.0 mmol). A well-mixed solution of 
(1,3,5-hexatrienyloxy)isopropyldimethylsilane (10.3 mL, 8.2 g, 48.8 mmol) 
and (ethenyloxy)t-butyldimethylsilane (25.0 mL, 19.9 g, 126 mmol) was 
added dropwise via the dropping funnel over a period of 31 minutes. The 
resulting mixture was stirred at ambient temperature for about 2.5 days. 
The resulting viscous reaction mixture was worked up according to a 
procedure similar to that described in Example 25 to give a solid 
colorless polymer. The polymer was isolated, rinsed with fresh methanol 
and dried in a vacuum at 35.degree.-40.degree. oven to give 27.5 g of 
product (97%). 
The infrared spectrum (KBr) of the product contained bands at 3020 
cm.sup.-1 (.dbd.CH), 2960, 2930, 2900 and 2860 cm.sup.-1 (sat. CH), 1660 
and 1620 cm.sup.-1 (weak-in the conj. C.dbd.C region), 1255 and 835 
cm.sup.-1 (Si--CH.sub.3), and 1075 cm.sup.-1 (sat. Si--O--C). The .sup.1 H 
NMR spectrum (CDCl.sub.3) contained resonances in the unsaturated CH 
region due to the hexatriene residues in the polymer, and a comparison of 
the intensities of these resonances to those of other resonances in the 
spectrum suggested that there are about 2.7 ethenyl residues for each 
hexatriene residue in the polymer.