Silylated vinyl alcohol polymers

Silylated vinyl alcohol polymers and processes for their prepartion.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to silylated vinyl alcohol polymers, that is, 
polymers of ethenyloxysilanes, and to their preparation. 
2. Background 
Ethenyloxysilanes are known compounds or are prepared by known methods, for 
example, as described by Jung et al., Tetrahedron Lett., 3791 (1977); 
polymers prepared therefrom are also known. For example, U.S. Pat. No. 
3,418,293 discloses the polymerization of vinyloxysilanes of the formula 
CH.sub.2 .dbd.CHOSi(R.sup.1)(R.sup.2)(R.sup.3) wherein R.sup.1, R.sup.2 
and R.sup.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 polymerization product is a 
poly[(ethenyloxy)triorganosilane] which can be converted to poly(vinyl 
alcohol) by alcoholysis. Other processes for polymerizing silanes, 
employing free radicals or compounds such as SnCl.sub.4 or ethyl aluminum 
chlorides, but not aldehydes, as initiators, are disclosed in the art, for 
example, as follows. 
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 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 reaction of certain alkyl 
and aralkyl halides with silyl enol ethers 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. 
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## 
DETAILED DESCRIPTION OF THE INVENTION 
This invention provides the following: 
1(a). Process of preparing the polymer consisting essentially of the 
polymer of the formula 
EQU R.sub.H (Y.sup.2 --CH(OSi[R.sup.1 ].sub.3)CH.sub.2 --.sub.n CHO).sub.x ( 1) 
the process comprising contacting an ethenyloxysilane monomer, or mixture 
of such monomers, of the formula CH.sub.2 .dbd.CHOSi(R.sup.1).sub.3, under 
polymerizing conditions, with (i) an initiator which is an aldehyde of the 
formula 
EQU R.sub.H (Y.sup.2 CHO).sub.x ( 1a); 
or a precursor compound thereof of the formula 
EQU R.sub.H (Y.sup.1 X.sup.1).sub.x ( 1b) 
and (ii) a catalyst which is a suitable Lewis acid or a source of 
bifluoride ion, wherein, in the formulas: 
R.sub.H is H or a hydrocarbyl radical of valence x which may be alkyl, 
cycloalkyl, aryl, alkaryl or aralkyl, containing up to 20 carbon atoms, or 
a polymeric radical containing 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; 
n is an integer and is at least 5; 
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 
##STR6## 
wherein 
R.sup.2 is C.sub.1-10 alkylene or C.sub.7-20 aralkylene, R.sup.3 is 
C.sub.1-4 alkyl, L.sup.1 is --OR.sup.5, --OR.sup.6 OSi[R.sup.1 ].sub.3 or 
--OSi[R.sup.1 ].sub.3, wherein R.sup.5 is C.sub.1-4 alkyl and R.sup.6 is 
C.sub.1-4 alkylene, L.sup.2 is --OSi[R.sup.1 ].sup.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, and each of a and b, independently, is 0, 1 or 2; 
y is 0 or 1; 
each R.sup.1 is independently selected from C.sub.1-10 alkyl, alkenyl 
having 2 or 4-10 carbon atoms, and C.sub.6-10 aryl, alkaryl and aralkyl; 
each R.sup.4 is independently selected from H, C.sub.1-10 alkyl and 
C.sub.6-10 aryl, aralkyl or alkaryl; 
X.sup.1 is --OH, --Cl, --Br, --H, --R.sup.5, --OR.sup.5, Cl.sup..crclbar., 
Br.sup..crclbar., I.sup..crclbar., O.sup..crclbar. R.sup.5, 
O.sup..crclbar. COR.sup.5, or CH.sub.3 C.sub.6 H.sub.4 
SO.sub.3.sup..crclbar., wherein R.sup.5 is C.sub.1-4 alkyl; 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.sup..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 X.sup.1 taken together is 
##STR7## 
wherein 
R.sup.6 is C.sub.1-4 alkylene, R.sup.8 is a connecting bond or C.sub.1-10 
alkylene, and R.sup.7 is C.sub.1-10 alkyl or C.sub.6-10 aryl, or 
R.sup.8 and R.sup.7 taken together is 
##STR8## 
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.sup..sym. (R.sup.3).dbd.CH.sub.2, X.sup.1 is 
O.sup..crclbar. R.sup.5, O.sup..crclbar. COR.sup.5, Cl.sup..crclbar., 
Br.sup..crclbar., I.sup..crclbar., or CH.sub.3 C.sub.6 H.sub.4 
SO.sub.3.sup..crclbar.. 
Preferably, each R.sup.1 is alkyl and the total number of carbon atoms in 
all of the R.sup.1 groups is at least six; more preferably, at least one 
R.sup.1 alkyl is branched; most preferably, one R.sup.1 alkyl is t-butyl 
and two R.sup.1 alkyl groups are CH.sub.3. Preferably, at least one 
R.sup.4 is H or alkyl, preferably methyl; most preferably, each R.sup.4 is 
H. Also, preferably, Y.sup.3 is a connecting bond. --C(O)--, --R.sup.2 -- 
or --CH(L.sup.1)--. 
1(b). Process of 1(a) wherein the aldehyde initiator of formula 1a wherein 
y is 1 is produced in-situ by contacting an ethenyloxysilane of the 
formula C[R.sup.4 ].sub.2 .dbd.CHOSi[R.sup.1 ].sub.3, under polymerizing 
conditions, with the aldehyde precursor compound of formula 1b wherein 
R.sup.1 and R.sup.4 are defined as above; 
2. Process of preparing the polymer consisting essentially of the polymer 
of the formula 
EQU R.sub.H (Y.sup.2 --CH(OSi[R.sup.1 ].sub.3)CH.sub.2 --.sub.n CH (OSi[R.sup.1 
].sub.3 Q.sup.2 R.sub.p).sub.x ( 2) 
by reacting the polymer of formula 1, in the presence of a suitable Lewis 
acid or a source of bifluoride, fluoride, difluorotrimethylsilicate, 
cyano, or azido ions, with the compound of the formula (R.sup.1).sub.3 
SiQ.sup.1 R.sub.p, wherein, in the formulas: 
R.sub.H, Y.sup.2, n, x and R.sup.1 are defined as above; 
Q.sup.1 is a divalent radical selected from 
##STR9## 
and mixtures thereof; 
Q.sup.2 is a keto or cyano group-containing divalent radical selected from 
##STR10## 
and mixtures thereof; 
R.sub.p is H, C.sub.1-4 alkyl, or a polymeric radical of a methacrylic 
and/or acrylic living polymer prepared by the process disclosed in U.S. 
Pat. No. 4,417,034 and in EPO Publication No. 0 068 887; preferably, 
R.sub.p is a polymeric radical, more preferably, such a radical prepared 
from methyl methacrylate; 
X is --CN, --CH.dbd.CHC(O)X' or --C(O)X'; 
Y is --H, --CH.sub.3, --CN or --CO.sub.2 R, provided however, when X is 
CH.dbd.CHC(O)X', Y is --H or --CH.sub.3 ; 
X' is --OSi(R.sup.1).sub.3, --R, --OR or --NR'R"; 
R is C.sub.1-20 alkyl, alkenyl or alkadienyl; C.sub.6-20 cycloalkyl, aryl, 
alkaryl or aralkyl; any of said groups optionally containing one or more 
ether oxygen atoms within aliphatic segments thereof; and any of all the 
aforesaid groups optionally containing one or more functional substituents 
that are unreactive under its preparative polymerizing conditions; and 
each of R' and R" is independently selected from C.sub.1-4 alkyl. 
3. Process of preparing the polymer of the formula 
EQU R.sub.H (Y.sup.2 --CH(OSi[R.sup.1 ].sub.3)CH.sub.2 --.sub.n X.sup.3).sub.x 
( 3) 
by reacting the polymer of formula 1 with an aldehyde-active reagent other 
than the compound of the formula (R.sup.1).sub.3 SiQ.sup.1 R.sub.p, as 
defined above, preferably a conventional aldehyde-active reagent selected 
from an oxidizing agent, a reducing agent and an aldehyde-active compound 
of the formula R.sub.p.sup.1 X.sup.2 wherein: 
R.sub.H, R.sup.1, Y.sup.2, n and x are defined as above; 
R.sub.p.sup.1 is defined as for R.sub.H ; 
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 wherein G is the halometal 
portion of a Grignard reagent and M is H, an alkali metal or ammonium; and 
X.sup.3 is --CH.sub.2 OH, --CO.sub.2 M or --Q.sup.3 R.sub.p.sup.1 wherein 
R.sub.p.sup.1 is defined as for R.sub.H and Q.sup.3 is a di- or trivalent 
radical selected from 
##STR11## 
wherein M is H, an alkali metal or ammonium and G is the halometal portion 
of a Grignard reagent. 
4. Process of polymerizing an ethenyloxysilane monomer, or mixture of such 
monomers, of the formula CH.sub.2 .dbd.CHOSi(R.sup.1).sub.3, wherein each 
R.sup.1 is independently selected from C.sub.1-10 alkyl, alkenyl having 2 
or 4-10 carbon atoms, and C.sub.6-10 aryl, alkaryl and aralkyl, by 
contacting the monomer or mixture of monomers under polymerizing 
conditions with (i) an aldehyde initiator and (ii) a catalyst which is a 
suitable Lewis acid or a source of bifluoride ion. 
5. The polymer consisting essentially of the polymer of formula 1. 
6. The polymer consisting essentially of the polymer of formula 2. 
7. The polymer consisting essentially of the polymer of formula 3. 
8. The polymer prepared by hydrolyzing the polymer of formula 1. 
9. The polymer prepared by hydrolyzing the polymer of formula 2. 
10. The polymer prepared by hydrolyzing the polymer of formula 3. 
11. The polymer prepared by the process of 4. 
Preferred embodiments of the processes of preparing the polymers of 
formulas 1, 2 and 3 include the additional steps wherein the silyl ether 
groups in the polymers are hydrolyzed to --OH, particularly in the 
presence of fluoride or bifluoride ions. 
By "initiator" is meant the aldehyde 1a or aldehyde precursor compound 1b 
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. Aldehyde initiators include, 
but are not limited to, those of formula 1a. 
Aldehydes which are useful initiators in the invention for preparing the 
polymer of formula 1 or the polymer from the process of 4 include, but are 
not limited to, aliphatic, aromatic and polymeric aldehydes, for example, 
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 of formula 1b which, 
when contacted with an ethenyloxysilane of the formula C[R.sup.4 ].sub.2 
.dbd.CHOSi[R.sup.1 ].sub.3 under polymerizing conditions, forms an 
aldehyde of formula 1a. When the ethenyloxysilane is a monomer used in the 
invention for preparing the polymer of formula 1, i.e., each R.sup.4 group 
is H, polymerization of said monomer is initiated in the aldehyde-forming 
reaction between monomer and the aldehyde precursor compound. If one or 
both R.sup.4 groups is not H, the product is an aldehyde of formula 1a 
which is capable of initiating polymerization of ethenyloxysilane monomer. 
Aldehyde precursor compounds include, but are not limited to, those of the 
formula 1b, representative of which are: water; alkanols; aliphatic, 
aromatic and polymeric primary and secondary bromides and chlorides, for 
example, n-hexyl bromide and chloride, .alpha.,.alpha.'-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 an 
ethenyloxysilane of the formula C[R.sup.4 ].sub.2 .dbd.CHOSi[R.sup.1 
].sub.3 requires at least one mole of ethenyloxysilane per mole of 
precursor compound. When at least one R.sup.4 in the silane is not H, 
i.e., the silane is not a monomer, the reaction is usually equimolar 
(1:1). Ethenyloxysilanes which are preferred for use in the in-situ 
preparation of the aldehyde initiator 1a from the aldehyde precursor 
compound 1b include 2-substituted silanes wherein one or both of R.sup.4 
is alkyl, preferably methyl; most preferably, each R.sup.1 group is also 
alkyl. 
Catalysts which are useful in the invention process for preparing the 
polymer of formula 1 or the polymer from the process of 4 are known or are 
readily prepared by known methods. These catalysts either are sources of 
bifluoride ions, such as potassium bifluoride, tetrabutylammonium 
bifluoride, or tris(dimethylamino)sulfonium bifluoride, or are Lewis 
acids, such as zinc iodide, zinc bromide, zinc chloride, boron trifluoride 
etherate, or dialkyl aluminum halides. Bifluoride ion, zinc bromide, zinc 
chloride, and zinc iodide are preferred; zinc bromide is most preferred. 
The process of preparing the polymer of formula 1 is carried out at about 
-100.degree. C. to about 120.degree. C., preferably above about 0.degree. 
C. to 70.degree. C., most preferably 20.degree. C. to 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 liquid 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. When anionic species are 
employed as catalysts, suitable solvents are polar liquids and include 
tetrahydrofuran (THF), N,N-dimethylacetamide, acetonitrile, 
N-methylpyrrolidone, ethyl acetate, bromobenzene, diethoxyethane and 
Cellosolve acetate; THF and acetonitrile are preferred. When the catalyst 
is a zinc compound or other Lewis acid, suitable solvents are limited to 
aromatic hydrocarbons, such as toluene or xylene, aliphatic hydrocarbons 
or chlorinated hydrocarbons; toluene, dichloromethane and 
1,2-dichloroethane are preferred. Chlorinated solvents should be avoided 
when anionic catalysts are employed. 
The ethenyloxysilane monomers which are preferred for use in the invention 
process are those wherein each R.sup.1 group is alkyl and the total number 
of carbon atoms in all of the R.sup.1 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 weights than those which can be 
prepared from nonpreferred ethenyloxysilane monomers. While lower 
molecular weight polymers of formula 1 are useful, especially in blends 
with other polymers, the ability to attain higher molecular weight when 
desired is a preferred feature. 
The ethenyloxysilane monomers which are useful in the invention process for 
preparing the polymers of formula 1 are liquids and can be polymerized 
without a solvent, although a solvent is beneficial in controlling 
temperature during the polymerization which is exothermic. When a solvent 
is used, the monomer can be dispersed in the solvent at concentrations of 
at least 1 wt %; preferably, at least 10 wt %; more preferably, about 50 
wt %. The initiator is employed at a concentration such that the 
monomer/initator molar ratio is greater than 1; preferably, greater than 
5. The amount of initiator can be varied to control the molecular weight 
of the product, in accordance with known polymerization procedures. The 
catalyst is normally present in such an amount that the molar ratio of 
initiator to catalyst is in the range 0.1:1 to 200:1, preferably, 0.1:1 to 
1:1. 
In the invention polymerization process wherein the polymer of formula 1 is 
prepared, it is preferable to charge the initator, catalyst, and solvent, 
if a solvent is used, to the polymerization vessel before adding the 
monomer(s), especially if polymers of narrow molecular weight 
distribution, that is, M.sub.w /M.sub.n is about 1, are desired 
(monodisperse polymers). At higher values of M.sub.w /M.sub.n the polymer 
is said by the art to be polydisperse. 
Although it is preferable to charge the initiator, catalyst and solvent to 
the polymerization vessel before adding monomer(s), subsequent 
polymerization rate being controlled by monomer addition, further 
additions of catalyst may sometimes be necessary to sustain 
polymerization. 
The invention polymer of formula 1 contains terminal --CH.sub.2 CHO 
aldehydic groups and remains "living" unless contacted by a reagent which 
is active towards aldehydes, including compounds of the aforesaid formula 
(R.sup.1).sub.3 SiQ.sup.1 R.sub.p. By "living" is meant that the polymer 
is capable of polymerizing further in the presence of monomer(s) and 
catalyst, permitting the preparation of "tailored" copolymers, such as 
block copolymers having highly desirable properties. 
Although not intending to be bound by this explanation, in the process for 
preparing the polymer of formula 1, the ethenyloxysilane monomer is 
believed to be cleaved at the O--Si bond by the initiator of formula 1a or 
1b, the cleavage being catalyzed by bifluoride ion or selected Lewis 
acids. Polymerization proceeds by addition of further monomer units to the 
C.dbd.O bond of the aldehyde intermediate, yielding the polymer of formula 
1. 
The noncarbaldehyde portion of the initiating aldehyde of formula 1a, i.e., 
R.sub.H (Y.sup.2 --.sub.x, is found, by analysis, to be attached to the 
nonliving (noncarbaldehyde) end of the polymer. When the initiator is an 
aldehyde precursor compound of formula 1b, the aldehdye-forming, 1:1 
reaction with monomer results in a Si-containing adduct or by-product. 
Si-containing by-products are formed in Examples 9, 10 and 12 to 14 
wherein alcohol, water and aralkyl halides are employed as initiators, as 
shown in the following table: 
TABLE 
__________________________________________________________________________ 
Initiator 1:1 Adduct 
Ex. 
R.sub.H (Y.sup.1 X.sup.1).sub.x 
R.sub.H (Y.sup.2 CHO).sub.x 
By-Product 
__________________________________________________________________________ 
9 C.sub.2 H.sub.5 OH 
CH.sub.3 CHO (R.sup.1).sub.3 SiOC.sub.2 H.sub.5 
10 H.sub.2 O CH.sub.3 CHO [(R.sup.1).sub.3 Si].sub.2 O 
12 (C.sub.6 H.sub.5).sub.2 CHCl 
(C.sub.6 H.sub.5).sub.2 CHCH.sub.2 CHO 
(R.sup.1).sub.3 SiCl 
13 C.sub.6 H.sub.4 (CH.sub.2 Br).sub.2 
C.sub.6 H.sub.4 (CH.sub.2 CH.sub.2 CHO).sub.2 
(R.sup.1).sub.3 SiBr 
14 C.sub.6 H.sub.3 (CH.sub.2 Br).sub.3 
C.sub.6 H.sub.3 (CH.sub.2 CH.sub.2 CHO).sub.3 
(R.sup.1).sub.3 SiBr 
-- CH.sub.3 C(O)Cl 
CH.sub.3 C(O)CH.sub.2 CHO 
(R.sup.1).sub.3 SiCl 
-- 
##STR12## CH.sub.3 N(CH.sub.3)CH.sub.2 CH.sub.2 CHO 
(R.sup.1).sub.3 SiOC(O)CH.sub.3 
-- 
##STR13## (R.sup.1).sub.3 SiOCH.sub.2 CH.sub.2 CH.sub.2 CHO 
None 
-- 
##STR14## (R.sup.1).sub.3 SiOC(O)CH.sub.2 CH.sub.2 C(O)CH.sub.2 
None 
-- 
##STR15## (R.sup.1).sub.3 SiOCH.sub.2 CH.sub.2 OCH(CH.sub.3)CH.sub.2 
CHO None 
__________________________________________________________________________ 
In Example 14, the moiety R.sub.H is trivalent, i.e., x is 3, and in this 
case, the polymer formed is a 3-arm star. Other illustrations wherein x is 
greater than one are provided in subsequent examples. 
Terminal functions, such as --C(O)OSi(R.sup.1).sub.3, --OSi(R.sup.1).sub.3 
and substituted amino, can be introduced at the non-living end of the 
polymer chain by using oxiranes, anhydrides, cyclic acetals or amine salts 
as initiators. These and other functions which are unreactive under 
polymerizing conditions may also be introduced into the polymer via the 
initiator moiety R.sub.H, as described above. 
The process of preparing the polymer of formula 2 is carried out by 
reacting the polymer of formula 1 and the compound of the formula 
(R.sup.1).sub.3 SiQ.sup.1 R.sub.p, as defined above, in the presence of a 
catalyst, also defined above, at about -20.degree. C. to about 150.degree. 
C., preferably 0.degree. C. to 50.degree. C. A solvent is usually 
desirable, especially when R.sub.p is a polymeric radical as defined 
above. A solvent may not be required if the compound (R.sup.1).sub.3 
SiQ.sup.1 R.sub.p is liquid or gaseous. Suitable solvents include those 
described above for the preparation of the polymer of formula 1, with the 
same restrictions regarding the use of chlorinated hydrocarbons. 
Catalysts which are useful in the invention process for preparing the 
polymer of formula 2 include those recited above for preparing the polymer 
of formula 1. In addition, sources of fluoride, cyano or azido ions can be 
employed. Other useful catalysts include those which are disclosed as 
co-catalysts in the aforesaid U.S. Pat. No. 4,417,034 and EPO Publication 
No. 0 068 887. When cyano or azido ion sources are employed as catalysts, 
it is preferable to place the solvent, catalyst, and silyl compound of the 
formula (R.sup.1).sub.3 SiQ.sup.1 R.sub.p in the reactor prior to adding 
the polymer of formula 1. 
Preferred reagents (R.sup.1).sub.3 SiQ.sup.1 R.sub.p include the living 
polymer disclosed in the aforesaid U.S. Pat. No. 4,417,034 and EPO 
Publication No. 0 068 887, wherein R.sub.p is a polymeric radical. When 
such living polymers are employed, the polymer of formula 2 comprises 
ethenyloxy-acrylic block copolymers which may be linear or branched, the 
latter having, for example, star or comb configurations. As an 
illustration, a typical living poly(methyl methacrylate) of the formula 
##STR16## 
wherein b is the number of monomer repeat units in the polymer which, for 
simplicity, may be represented as 
##STR17## 
wherein PMMA represents the poly(methyl methacrylate) chain, can be 
reacted with the polymer of formula 1 to yield a block polymer of formula 
2, for example, in accordance with the following equation wherein n is an 
integer and is at least 5: 
##STR18## 
Using such a process, multi-block, linear or branched copolymers can be 
produced, depending on the structure of R.sub.p and Q.sup.1. Moreover, as 
discussed above, the reactant polymer of formula 1 may itself be a block, 
star-branched, comb and/or branched copolymer, depending on the structure 
of R.sub.H and the value of x. Thus, the polymer of formula 2 embraces a 
wide spectrum of copolymer structural configurations. 
In the process of preparing the polymer of formula 3, the polymer of 
formula 1 is reacted with an aldehyde-active reagent other than the 
compound of the formula (R.sup.1).sub.3 SiQ.sup.1 R.sub.p of the process 
of 2, preferably a conventional aldehyde-active reagent selected from an 
oxidizing agent, a reducing agent or an aldehyde-active compound of the 
formula R.sub.p.sup.1 X.sup.2, at a temperature of about -20.degree. C. to 
about 150.degree. C., preferably 0.degree. C. to 80.degree. C. Suitable 
oxidants include solutions of acidified potassium dichromate, ammoniacal 
silver nitrate, Fehling's solution (CaSO.sub.4 in an alkaline solution of 
a tartarate salt). Suitable reductants include catalytic hydrogenation 
catalysts, such as Raney nickel or platinum, zinc and sodium hydroxide, 
iron and acetic acid, and aluminum trialkoxides, such as aluminum 
tri(isopropoxide). Suitable R.sub.p.sup.1 X.sup.2 compounds include 
alcohols, hydrogen cyanide, amines, urea and substituted ureas, 
morpholine, hydrazine, hydroxylamine, ammonia and Grignard reagents, such 
as alkyl magnesium bromide or iodide. Such reactions are usually carried 
out in a solvent, particularly when the oxidizing or reducing agent or 
aldehyde-active compound is a solid. Suitable solvents include those 
described above for the preparation of the polymer of formula 1, without 
the restriction regarding chlorinated hydrocarbons. THF and chlorinated 
hydrocarbons are preferred solvents. The resulting polymers can have 
useful functionality. For example, polymers containing the terminal groups 
--CO.sub.2 M or --CH.sub.2 OH result from oxidation or reduction, 
respectively, of the --CHO group in the polymer of formula 1. Reaction of 
the polymer with alkali metal bisulfite, hydrogen cyanide or an alkanol 
ROH provides polymers having --CH(OH)X' functions wherein X' is, 
respectively, --SO.sub.3 M, --CN and --OR; acid hydrolysis of the 
cyanohydrin provides --CH(OH)CO.sub.2 H; and further reaction of the 
hemiacetal with alkanol provides --CH(OR).sub.2. Reaction of the polymer 
of formula 1 with ammonia, primary amines, hydroxylamine, hydrazine, urea, 
morpholine, semicarbazide, alkylhydrazines, or arylhydrazines provides 
terminal functions --CH.dbd.NX" where X" is, respectively, --H, --R, 
--OH, --NH.sub.2, --C(O)NH.sub.2, --C(NH)NH.sub.2, --NHCONH.sub.2 and 
--NHR (for the alkyl- and arylhydrazines), wherein R is as defined above. 
Pendant groups --OSi(R.sup.1).sub.3, which may be present in polymers of 
the invention, can be converted to --OH groups by known methods, such as 
by hydrolysis, for example, by treatment with a source of fluoride ion, 
such as tetraalkylammonium fluoride, dissolved in a THF-methanol mixture. 
The pendant --OH functions are useful reactive sites for cross-linking or 
other chemical modification.

In the following examples of specific embodiments of the invention, parts 
and percentages are by weight and temperatures are in degrees Celsius 
unless otherwise specified. The polydispersity (D) of the polymer products 
of the examples is defined by D=M.sub.w /M.sub.n, the molecular weights 
being determined by gel permeation chromatography (GPC). Unless otherwise 
specified, molecular weights were measured on the polymer of formula 1 
before silyl groups were removed, that is, on the polymers wherein X.sup.1 
in the formula is --Si(R.sup.1).sub.3. In the Examples: 
EBDS is (ethenyloxy)-t-butyldimethylsilane, 
TBAF is tetrabutylammonium fluoride, 
ETS is (ethenyloxy)trimethylsilane, 
TASHF.sub.2 is tri(dimethylamino)sulfonium bifluoride, 
MPTS is [(1-methoxy-2-methyl-1-propenyl)oxy]-trimethylsilane 
EXAMPLE 1 
Polymerization of (ethenyloxy)-t-butyldimethylsilane (EBDS) initiated by 
benzaldehyde in the presence of zinc chloride 
A 3-necked 50 mL flask, fitted with a stirrer, argon inlet and a 
thermocouple, was charged with zinc chloride (anhydrous, 0.035 g, 0.26 
mmol), dichloromethane (20 mL) and benzaldehyde (0.25 mL, 2.46 mmol). 
Then, (ethenyloxy)-t-butyldimethylsilane (EBDS) (7.41 g, 46.81 mmol) was 
added via a syringe pump at 0.5 mL/min. The ensuing reaction was 
accompanied by a temperature rise to 35.4.degree. from 26.0.degree.. The 
mixture was stirred for 3 h (or until the temperature had dropped to 
26.degree.) and evaporated. The residue (7.70 g) was dissolved in 
dichloromethane (10 mL) and added to methanol (1 L) to precipitate the 
polymer. The white precipitate was collected by filtration and dried at 
60.degree./0.1 mm Hg to give 7.50 g of white powdery material. Molecular 
weight was determined by gel permeation chromatography (GPC) (PMMA 
Lucite.RTM. standard) to be: M.sub.n 2180, M.sub.w 2800, D 1.28, intrinsic 
viscosity, [.eta.], 0.021 dlg.sup.-1 (THF, 25.degree.), M.sub.n (VPO) 4300 
(THF, 37.degree.), M.sub.n (calc.) 3112. .sup.1 H NMR (CDCL.sub.3, ppm): 
.delta.9.82 (--CHO, triplet, 1H), 7.20 (--C.sub.6 H.sub.5, singlet 5H), 
5.45 (Ar--CH, triplet, 1H), 3.87 (--HCOSi, broad, 16H), 1.58 (--CH.sub.2 
--, broad, 34H), 0.88 (--SiC(CH.sub.3).sub.3, singlet, 144H), 0.08 
(--Si(CH.sub.3).sub. 2, singlet, 96H). .sup.13 C NMR (CDCl.sub.3, ppm): 
.delta.-3.7 (--Si(CH.sub.3).sub.2), 18.1 (quaternary carbon of t-butyl 
group), 26.2 (t-butyl methyl carbon), 46.8 (chain methine carbon), 72.4 
(terminal methine carbon), 126.3 (orthoaromatic carbon), 127.0 
(para-aromatic carbon), 128.1 (meta-aromatic carbon), 202.1 (terminal 
aldehyde carbon). 
EXAMPLE 2 
A. Polymerization of EBDS initiated by benzaldehyde in the presence of zinc 
bromide 
The apparatus and procedure employed were as in EXAMPLE 1, except that 
anhydrous zinc bromide (0.056 g, 0.25 mmol) was substituted for zinc 
chloride, 7.60 g of polymer was isolated as a white powder. M.sub.n 2280, 
M.sub.w 3060, D 1.35 (GPC), [.eta.] 0.029 dlg.sup.-1 (THF, 25.degree.), 
M.sub.n (VPO) 2700 (THF, 37.degree.), M.sub.n (calc.) 3112. 
B. Polymerization at ZnBr.sub.2 /initiator mole ratio of 1:1 
A 3-necked 250 mL reactor, fitted with a stirrer, argon inlet and a 
thermocouple, was charged with anhydrous zinc bromide (0.023 g, 0.10 
mmol), dichloromethane (15 mL) and benzaldehyde (0.01 mL, 0.098 mmol) at 
25.degree.. Then, the monomer, EBDS (15.8 g), was added dropwise over a 
period of 30 minutes. The temperature of the reaction rose to 40.degree. 
accompanied by noticeable increase in the viscosity of the solution. The 
mixture was stirred until the exothermic reaction subsided completely. It 
was then poured into methanol (2 L) and the resulting precipitate was 
collected by suction filtration and dried at 60.degree./0.1 mm Hg; yield 
15.5 g; [.eta.] 0.076 dlg.sup.-1 (THF, 25.degree.) (indicates unusally 
high molecular weight), M.sub.n 79800, M.sub.w 121000, D 1.51. 
C. Polymerization at ZnBr.sub.2 /initiator mole ratio of 2:1 
Using a reactor similar to that of Example 4 which follows, EBDS (29.64 g, 
187 mmol) was polymerized in the presence of benzaldehyde (0.04 g, 0.39 
mmol) and zinc bromide (0.18 g, 0.80 mmol) in dichloromethane (40 mL). 
Upon precipitation from methanol (4 L), 29.70 g of polymer was isolated as 
a white powdery material. M.sub.n 13500, M.sub.w 24900, D 1.85. 
EXAMPLE 3 
Polymerization of EBDS initiated by benzaldehyde in the presence of 
titanium tetrachloride. 
To the reactor used for Example 1 were added dichloromethane (20 mL), 
titanium tetrachloride (0.50 mL, 0.5 M in CH.sub.2 Cl.sub.2), and 
benzaldehyde (0.25 mL, 2.46 mmol). Then, EBDS (7.41 g, 46.81 mmol) was 
added over a period of 10 minutes. The mixture was stirred for 3 h, 
evaporated and the viscous oily residue was dried; yield 0.70 g; M.sub.n 
476, M.sub.w 801, D 1.68, M.sub.n (VPO) 410 (THF, 37.degree.), M.sub.n 
(calc. from .sup.1 H NMR) 586, M.sub.n (calc.) 3112. 
EXAMPLE 4 
Conversion of poly [(ethenyloxy)-t-butyldimethylsilane](poly[EBDS]) into 
poly(vinyl alcohol) 
This example illustrates cleavage of trialkylsilyl groups. 
A 3-necked 100 mL reactor, fitted with a stirrer, reflux condenser, and an 
argon inlet was charged with tetrahydrofuran (20 mL), methanol (5 mL) and 
poly [EBDS] (10 g made by the process of Example 1). To the resultant 
solution was added tetrabutylammonium fluoride (TBAF, 20 mL, 1M in THF) 
containing water (5%) and the resulting mixture was heated to 70.degree.. 
It was allowed to reflux for 90 minutes and was then cooled to room 
temperature. The solvent was evaporated in vacuo and the residue was 
dissolved in boiling water (100 mL). Upon addition of the water solution 
to methanol (2 L) a precipitate formed; it was collected by filtration and 
dried; yield, 2.7 g; .sup.13 C NMR (DMSO-d.sub.6, ppm): 44-46 (multiplet, 
chain methine carbon), 65-67 (chain methylene carbon), 126-128 (aromatic 
carbon). Detailed analysis of the .sup.13 C NMR spectrum showed that the 
polyvinyl alcohol was 57% syndiotactic, 43% heterotactic (diads). 
EXAMPLE 5 
Polymerization of (ethenyloxy)trimethylsilane (ETS) initiated by 
benzaldehyde and conversion to a polyvinyl alcohol) 
A. To a solution of (ethenyloxy)trimethylsilane (ETS) (20.77 g, 0.18 mol) 
in THF (12 mL) in a reactor similar to that of Example 6 which follows was 
added benzaldehyde (1.0 mL, 9.85 mmol). Then, the catalyst, 
tris(dimethylamino)sulfonium bifluoride (TASHF.sub.2, 0.12 mL, 1M in 
acetonitrile), was added. The mixture was stirred for 16 h and then 
treated with tetrabutylammonium fluoride (2.0 mL, 1M in 95% THF/5% water) 
to hydrolyze pendant --OSi(CH.sub.3).sub.3 groups. After the ensuing 
exothermic reaction had subsided the mixture was poured into methanol (1 
L). The slightly yellowish precipitate was collected by filtration, dried 
and weighed; yield, 6.22 g; Dp was calculated from proton NMR to be 15, Dp 
(theory) 18, .sup.1 H NMR (D.sub.2 O), .delta. ppm: 1.25 (CH.sub.2, 30H), 
310 (OH, 15H), 4.0 (--CH--O, 15H), 7.1-7.6 (ArH, 5H), 9.50 (HC.dbd.O, 1H). 
B. A polymerization similar to that of Part A was performed except that the 
TASHF.sub.2 catalyst was replaced with a similar catalyst in which the 
bifluoride ions were deuterium-exchanged. Polymer having a Dp (NMR) of 20 
was obtained, Dp (theory) 15. The proton NMR spectrum was identical to 
that obtained in Part A. 
EXAMPLE 6 
Polymerization of ETS at low temperature 
A solution of TASHF.sub.2 (0.10 g, 0.50 mmol) in THF (5 mL) in a reactor 
identical to that used in Example 4 was cooled to -71.8.degree.. Then, ETS 
(0.79 g, 6.80 mmol) was added, followed by addition of benzaldehyde (0.51 
mL, 5.0 mmol). The temperature of the reaction mixture rose from 
-71.8.degree. to -62.2.degree.. After the exotherm had subsided 
completely, more monomer (ETS, 5.02 g, 43.3 mmol) was added. The mixture 
was stirred for 1 h at -71.degree. and then allowed to warm to 25.degree.. 
The reactor was then heated to 70.degree. and the contents was allowed to 
reflux for 1 h. The mixture was allowed to cool to 25.degree., then 
evaporated, and the residue was dried; yield, 1.98 g of a mixture of 
poly(vinyl alcohol) (PVA) and silylated PVA. Dp (NMR) 8, Dp (theory) 10. 
EXAMPLE 7 
Polymerization of EBDS initiated by benzaldehyde in the presence of 
TASHF.sub.2 
A 100 mL reactor similar to that used in Example 1 was charged with THF (30 
mL), benzaldehyde (0.26 g, 2.45 mmol) and TASHF.sub.2 (0.1 mL, 1M in 
acetonitrile). The reactor was cooled to -65.2.degree. while the contents 
were continuously stirred under argon. Then EBDS (7.41 g, 46.81 mmol) was 
added at approximately 1.0 mL/minutes via a syringe pump. The mixture was 
stirred at -60.degree. for 3 h, allowed to warm to 25.degree. and then 
evaporated. The residue was dried at 60.degree./0.1 mm Hg for 12 h; yield, 
7.60 g. 
EXAMPLE 8 
Polymerization of EBDS initiated by benzaldehyde in the presence of 
TASHF.sub.2 in THF at higher temperature 
A. The procedure of Example 7 was used, except that reaction was started at 
ambient temperature. EBDS was polymerized to give 7.70 g of polymer. The 
exothermic reaction caused the temperature to rise to 43.2.degree. (with 
boiling) during the course of monomer addition. 
B. The example of part A was repeated, except that toluene was substituted 
for THF as the solvent; 7.50 g of polymer was obtained. 
EXAMPLE 9 
Polymerization of EBDS in the presence of ethanol as the aldehyde initiator 
precursor, and zinc bromide 
This example illustrates aldehyde initiator-generation by a proton source 
and also demonstrates that the polymer is living. 
A reactor similar to that used in Example 1 was charged with zinc bromide 
(0.023 g, 0.10 mmol) and ethyl alcohol (0.03 mL, 0.51 mmol). Then, 
dichloromethane (10 mL) was added, followed by addition of the monomer, 
EBDS (3.93 g, 24.8 mmol). The temperature rose from 25.4.degree. to 
42.2.degree. with boiling. After the exotherm had subsided completely, the 
mixture was stirred at 25.degree. for 1 h. Then, a second portion of EBDS 
(1.96 g, 12.4 mmol) was added, whereupon the temperature rose to 
38.8.degree.. A third portion of monomer (1.96 g) was added and the 
temperature rose to 36.5.degree. from 26.degree. C. The mixture became 
noticeably viscous and stirring was continued until the exotherm subsided 
completely. Then, it was poured slowly into methanol (1 L) to precipitate 
the polymer which was filtered; the white powdery precipitate which was 
recovered was dried well; yield. 7.0 g, M.sub.n 6340, M.sub.w 15000, D 
2.37, M.sub.n (calc.) 15450. 
EXAMPLE 10 
Polymerization of EBDS in the presence of water as the aldehyde initiator 
precursor, and zine bromide 
The procedure of Example 9 was substantially repeated using the following 
reagents: EBDS (7.85 g, 49.6 mmol), zinc bromide (0.023 g, 0.10 mmol), 
dichloromethane (10 mL) and, instead of ethyl alcohol, distilled water 
(0.02 g, 1.10 mmol). Addition of the first batch of EBDS (3.93 g) was 
accompanied by a temperature rise to 41.6.degree.. The second addition of 
monomer (1.96 g) caused the temperature to rise to 35.degree., while on 
adding a third portion (1.96 g) it rose to 37.4.degree.. Each time the 
exotherm was allowed to subside completely before further monomer 
addition. Polymer was isolated by pouring the mixture into methanol (1 L), 
filtering the precipitate and drying it; yield, 7.20 g, M.sub.n 3420, 
M.sub.w 5620, D 1.64, M.sub.n (calc.) 3569. 
EXAMPLE 11 
Polymerization of EBDS initiated by terephthaldehyde in the presence of 
zinc bromide 
This example illustrates polymerization in two directions using a 
dialdehyde initiator, and subsequent conversion of the aldehyde end groups 
into ester end groups. 
A reactor similar to that used in Example 1 was charged with 
dichloromethane (20 mL), zinc bromide (0.56 g, 2.50 mmol), and 
terephthaldehyde (0.27 g, 2 mmol). With stirring under argon the monomer, 
EBDS (7.41 g, 46.81 mmol) was added dropwise over a 10 minute period. The 
temperature of the reaction rose to 40.6.degree. from 26.0.degree.. The 
mixture was stirred until the exothermic reaction subsided completely. 
Then, [(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane (MPTS, 1.0 mL, 
5.0 mmol) was added, whereupon, the temperature rose to 39.2.degree. from 
26.2.degree.. The mixture was stirred until the temperature dropped to 
26.0.degree.. It was then evaporated and the residue was dried; yield, 
8.60 g (white foam). This was dissolved in dichloromethane (20 mL) and 
poured into methanol (1 L). The precipitate was filtered off and dried; 
yield, 8.25 g, M.sub.n 4150, M.sub.w 5130, D 1.24, M.sub. n (VPO), 4000 
(THF, 37.degree.), M.sub.n (theory) 3840. 
EXAMPLE 12 
Polymerization of EBDS employing diphenylmethyl chloride as the aldehyde 
initiator precursor in the presence of zinc bromide 
A reactor similar to that used in Example 1 was charged with zinc bromide 
(0.06 g, 0.27 mmol), dichloromethane (10 mL) and diphenylmethyl chloride 
(0.20 g, 1.0 mmol). Then EBDS (7.86 g, 49.6 mmol) was added dropwise over 
10 minutes. The mixture was stirred at ambient temperature for 18 h and 
then poured into methanol (1 L). The precipitate was collected by suction 
filtration and dried; yield, 7.1 g, M.sub.n 6500, M.sub.w 8000, D 1.23; 
M.sub.n (theory) 7877. 
EXAMPLE 13 
Polymerization of EBDS employing 1,4-bis-(bromomethyl)-benzene as the 
aldehyde initiator precursor 
This example demonstrates growing of polymer chains in two directions using 
a difunctional alkyl halide as the aldehyde initiator precursor and 
preparation of a living polymer. 
A reactor similar to that used in Example 1 was charged with zinc bromide 
(0.06 g, 0.27 mmol), dichloromethane (10 mL) and 
1,4-bis(bromomethyl)benzene (0.13 g, 0.50 mmol). To the stirred mixture 
was added EBDS (3.93 g, 24.8 mmol) dropwise over 10 minutes. The 
temperature rose to 37.degree. from 24.degree.. The mixture was stirred 
until the exotherm subsided completely. Then, more EBDS (3.93 g) was 
added. The temperature rose to 36.5.degree. from 24.degree., accompanied 
by noticeable increase in the viscosity of the mixture. After the exotherm 
subsided completely, the mixture was poured into methanol (1 L). The 
resultant white precipitate was collected by filtration, dried, and 
weighed; yield, 6.67 g, M.sub.n 16500, M.sub.w 37900, D 2.29, M.sub.n 
(theory) 15808. 
EXAMPLE 14 
Polymerization of EBDS employing 1,3,5-tris-(bromomethyl)benzene as the 
aldehyde initiator precursor 
This Example illustrates preparation of a 3-arm star silylated poly(vinyl 
alcohol). 
The procedure of Example 12 was repeated using zinc bromide (0.045 g, 0.20 
mmol), 1,3,5-tris(bromomethyl)benzene (0.08 g, 0.22 mmol), dichloromethane 
(10 mL), and EBDS (3.93 g, 24.8 mmol); yield, 3.73 g, M.sub.n 13600, 
M.sub.w 30900, D 2.26. M.sub.n (theory) 17284, [.eta.] 0.13 dlg.sup.-1 
(THF, 25.degree.), glass transition temperature (Tg) 64.degree. 
(differential scanning calorimetry, DSC). 
EXAMPLE 15 
Polymerization of EBDS employing 1,2,4,5-tetrakis-(bromomethyl)benzene as 
the aldehyde initiator precursor 
This Example illustrates preparation of a 4-arm star polymer. 
The procedure of Example 12 was repeated using zinc bromide (0.06 g, 0.27 
mmol), dichloromethane (10 mL), 1,2,4,5-tetrakis(bromomethyl)benzene 
(0.067 g, 0.15 mmol), and EBDS (3.93 g, 24.8 mmol); yield, 3.85 g, M.sub.n 
15500, M.sub.w 35300, D 2.27, M.sub.n (theory) 25822, [.eta.] 0.16 
dlg.sup.-1 (THF, 25.degree.), Tg 72.degree. (DSC). 
EXAMPLE 16 
Preparation of block copolymer of poly(methyl methacrylate) and EBDS 
A. Polymerization of methyl methacrylate (MMA) initiated by MPTS in the 
presence of a bifluoride ion 
The procedure described in U.S. Pat. No. 4,417,034 and in EPO Publication 
No. 0 068 887 was followed using TASHF.sub.2 (0.05 mL, 0.1M in 
acetonitrile), THF (100 mL), MPTS (10 mL, 50 mmol) and methyl methacrylate 
(50 g, 0.50 mol). MMA was added over a 45 minute period and the mixture 
was evaporated in a moisture-free atmosphere to give 59 g of polymer. 
M.sub.n 1080, M.sub.w 1390, D 1.28, M.sub.n (theory) 1174. 
B. EBDS was polymerized according to the procedure of Example 1 using zinc 
bromide (0.45 g, 2.0 mmol), benzaldehyde (1.0 mL, 9.85 mmol), 
dichloromethane (20 mL) and EBDS (14.82 g, 93.6 mmol). After the 
exothermic reaction had completely subsided, a 19 mL-aliquot was removed 
with a syringe and evaporated, and the residue was dried to give 7.1 g of 
polymer. Upon purification by precipitation from methanol 6.84 g of 
polymer was obtained. M.sub.n 1080, M.sub.w 1300, D 1.21, M.sub.n (VPO) 
1300, M.sub.n (theory) 1610. To the balance of the reaction mixture was 
added the living poly(methyl methacrylate) (6 g) prepared in Part A, as a 
solution in 10 mL of dichloromethane. The resulting mixture was stirred 
for 1 h and evaporated and the residue was dried to give 13 g of polymer. 
The polymer was dissolved in dichloromethane (10 mL) and the solution was 
poured into methanol (1 L). The precipitate was filtered and dried; 
yield, 12.48 g, M.sub.n 1610, M.sub.w 1910, D 1.15, M.sub.n (theory) 2160. 
Examples 17 to 20 illustrate the use of ZnCl.sub.2, ZnBr.sub.2, ZnI.sub.2 
and BF.sub.3, respectively, as catalysts in the benzaldehyde-initiated 
polymerization of ETS. In each case pendant silyl groups were removed by 
washing the polymeric product with water. Yields of the recovered 
poly(vinyl alcohols) were low because of their high solubility in water. 
EXAMPLE 17 
Polymerization of ETS initiated by benzaldehyde in the presence of zinc 
chloride 
A reactor similar to that of Example 1 was charged with zinc chloride (0.15 
g) and the reactor was heated under vacuum to dry the zinc chloride well. 
After the reactor was allowed to cool, dichloromethane (10 mL) and 
benzaldehyde (0.1 mL, 0.98 mmol) were charged. Then, ETS (6 mL, 41.4 mmol) 
was added dropwise via a syringe pump. The mixture was stirred for 2 h and 
evaporated. The resultant residue was dissolved in ethyl acetate and 
washed successively with two 100 mL-portions of water and one 100 
mL-portion of saturated sodium chloride. The ethyl acetate layer was dried 
over MgSO.sub.4, filtered, evaporated and the resultant residue was dried; 
0.22 g of polymer was recovered. 
EXAMPLE 18 
The procedure of Example 17 was followed using ETS (6 mL), zinc bromide 
(0.25 g), dichloromethane (10 mL), benzaldehyde (0.1 mL), and MPTS (0.2 
mL); 0.20 g of polymer was recovered. 
EXAMPLE 19 
The procedure of Example 17 was followed using zinc iodide (3.19 g, 10 
mmol), benzaldehyde (0.2 mL), EBDS (10 mL), dichloromethane (10 mL) and 
MPTS (0.5 mL); 1.04 g of polymer was recovered. [.eta.] 0.033 dlg.sup.-1 
(THF, 25.degree.). 
EXAMPLE 20 
Polymerization of ETS catalyzed by boron trifluoride etherate 
The procedure of Example 17 was followed, except that the initial heating 
to dry catalyst was omitted. Reagents used were: benzaldehyde (0.1 mL), 
boron trifluoride etherate (0.15 g), ETS (6 mL), dichloromethane (10 mL), 
and MPTS (0.2 mL); 0.69 g of polymer was recovered. 
EXAMPLE 21 
Preparation and polymerization of (ethenyloxy)diphenylmethylsilane 
All equipment was dried at 135.degree. and allowed to cool under dry 
nitrogen. All operations were carried out under dry nitrogen. 
A. Preparation of lithium ethenoxide 
In a 1-L flask equipped with a glass paddle stirrer, a dropping funnel, a 
syringe septum, and a reflux condenser capped with a nitrogen bubbler, was 
placed 200 mL of anhydrous tetrahydrofuran. With stirring, 315 mL of 1.6N 
n-butyl lithium in hexane was added in 11/4 h. The reaction mixture was 
allowed to stir at room temperature for about 18 h. 
B. Reaction of lithium ethenoxide with diphenylmethylchlorosilane 
The dropping funnel from the n-butyl lithium addition was replaced with a 
clean dry funnel which was loaded with 114 mL (128.6 g, 0.552 mole) of 
chlorodiphenylmethylsilane. The reaction flask was cooled in an ice bath 
and, with stirring, the chlorosilane was added over about 40 minutes. 
Stirring was continued at ice bath temperature for 1 h and then at room 
temperature for about 2 h. The mixture was filtered, the solid residue was 
rinsed with 20 mL of anhydrous tetrahydrofuran, and the rinsings were 
added to the filtrate. Distillation of the filtrate through a small 
spinning band still, first at atmospheric pressure to remove the solvents, 
and then at reduced pressure, yielded 88.69 g (67% yield) of 
(ethenyloxy)diphenylmethylsilane distilling at 
86.2.degree.-88.6.degree./0.10 mm. The .sup.1 H NMR spectrum (Cl.sub.3 CD) 
exhibited resonances at .delta.=0.63 ppm (CH.sub.3), 4.11, 4.51 and 6.41 
ppm (vinyl hydrogens) and 7.2-7.7 ppm (C.sub.6 H.sub.5) with the relative 
intensities expected for (ethenyloxy)diphenylmethysilane. 
C. Polymerization of (ethenyloxy)diphenylmethylsilane 
All equipment was dried at 135.degree. and allowed to cool under dry 
nitrogen. All operations were carried out under dry nitrogen. 
In a 50 mL flask was placed 0.69 g of zinc iodide and a magnetic stirrer. 
The flask was evacuated to about 0.1 mm and then heated strongly with a 
heat gun for 10 minutes to dry the zinc iodide. After the flask had cooled 
to room temperature, it was brought back to atmospheric pressure with dry 
nitrogen and then fitted with a dropping funnel, a syringe septum and a 
reflux condenser capped with a nitrogen bubbler. The flask was then 
charged with 15 mL of methylene chloride, which had been distilled from 
phosphorus pentoxide, and 0.22 mL of benzaldehyde, which had been 
distilled from calcium hydride. 
The dropping funnel was charged with 11.3 mL of 
(ethenyloxy)phenylmethylsilane which was then added with stirring over a 
period of 19 minutes. The polymerization was exothermic from the start, 
the temperature rising to a high of 32.8.degree. from 24.degree. (as 
measured by a thermocouple inserted through the syringe septum). After the 
addition was completed, the mixture was allowed to stir for a period of 20 
h at room temperature. The mixture was then filtered to remove undissolved 
salt, and the filtrate was distilled on the water pump to remove the 
solvent. The viscous polymeric residue was further dried for several hours 
at about 0.5 mm under mild heating (up to 50.degree.); wt. 11.6 g 
(.about.100% yield). The .sup.1 H NMR spectrum (Cl.sub.3 CD) showed that 
no vinyl hydrogen resonances remained, but have been replaced with broad 
resonances at .delta.=3-4.2 ppm and 0.8-2.0 ppm, that is, in the regions 
expected for saturated CH (with an adjacent siloxy group) and CH.sub.2 
groups, respectively. The resonances expected for CH.sub.3 -Si and C.sub.6 
H.sub.5 groups occur at .delta.=0.46 and .delta.=6.8-7.7 ppm, 
respectively. M.sub.n 3960, M.sub.w 11800, D 2.97. 
EXAMPLE 22 
Copolymerization of ETS and EBDS 
This polymerization was carried out as described in Example 21C with the 
following quantities of materials: 
Zinc iodide: 1.37 g 
Benzaldehyde: 0.44 mL 
Methylene chloride: 15 mL 
ETS: 6.2 mL 
EBDS: 8.4 mL. The mixture of silanes was added to the stirred mixture of 
zinc iodide, benzaldehyde and methylene chloride during 1/2 h. The 
temperature rose to 45.degree. from 22.degree. during the addition. The 
reaction mixture was allowed to stir at room temperature for several hours 
after the addition was completed. After filtration, removal of solvent, 
and drying under vacuum as described in Example 21C, there was obtained 
8.15 g (66% yield) of a very viscous substantially colorless material. The 
.sup.1 H NMR spectrum (Cl.sub.3 CD) exhibited, in addition to broad 
resonances for the CH.sub.2 and CH groups of the polymer backbone, 
resonances for CH.sub.3 Si--, (CH.sub.3).sub.3 C-- and C.sub.6 H.sub.5 
--C-- group at .delta.=0.08 ppm, .delta.=0.85 ppm and at .delta.=7.22 ppm, 
respectively. From the relative intensities of these resonances it was 
determined that the ratio of the two monomers in the polymer=56 units of 
EBDS/44 units of ETS, and that there are about 11 monomer units for each 
benzaldehyde molecule. 
EXAMPLE 23 
Preparation and polymerization of (ethenyloxy)vinylmethylphenylsilane 
All equipment was dried at 135.degree. and allowed to cool under dry 
nitrogen. All operations were carried out under dry nitrogen. 
A. Preparation of lithium ethenoxide 
This step was carried out in the manner and on the same scale as described 
in Example 21A. 
B. Reaction of lithium ethenoxide with (chloro)vinylmethylphenylsilane 
Following the procedure of Example 21B, 98 mL (101.33 g, 0.555 mole) of 
(chloro)vinylmethylphenylsilane was added to the cooled lithium ethenoxide 
solution prepared in Part A. After work-up and distillation as described 
in Example 21B, there was obtained 65.21 g (68% yield) of 
(ethenyloxy)vinylmethylphenylsilane distilling at 78.8.degree./5.0.degree. 
mm-80.0.degree./4.8 mm. The .sup.1 H NMR Spectrum (Cl.sub.3 CD) exhibited 
resonances at .delta.=0.50 ppm (CH.sub.3 --Si), .about.4.1 and 4.5 ppm 
(CH.sub.2 of vinyl on oxygen), a complicated multiline pattern at 
.delta.=5.7-6.6 ppm (vinyl group on silicon and the CH of the vinyl group 
on oxygen) and at .delta.=7.2-7.7 ppm (C.sub.6 H.sub.5) with the relative 
intensities consistent with (ethenyloxy)vinylmethylphenylsilane. 
C. Polymerization of (ethenyloxy)vinylmethylphenylsilane 
This polymerization was carried out as described in Example 21C with the 
following quantities of materials: 
Zinc iodide: 1.37 g 
Benzaldehyde: 0.44 mL 
Methylene chloride: 15 mL 
(Ethenyloxy)vinylmethylphenylsilane: 22 mL. 
The silane was added to the stirred mixture of zinc iodide, benzaldehyde 
and methylene chloride over a period of 46 minutes. After the addition was 
completed, the mixture was stirred at room temperature for about 18 h. The 
mixture was then worked up as described in Example 21C, and there was 
obtained 18.82 g (.about.100% yield) of a viscous polymeric residue. The 
.sup.1 H NMR spectrum (Cl.sub.3 CD) exhibited broad resonances at 
.delta.=0.30 ppm (CH.sub.3 --Si), .delta.=1.52 ppm (CH.sub.2 in the 
polymer chain), .delta.=5.98 ppm (Si--CH.dbd.CH.sub.2), and at 
.delta.=7.0-7.8 (C.sub.6 H.sub.5), in the expected relative intensities. 
Since the phenyl proton resonance from the benzaldehyde end group in the 
polymer is hidden by the large phenyl--Si proton resonance, it is not 
possible to estimate the number of monomer units per initiator unit. 
EXAMPLE 24 
Preparation of (ethenyloxy)vinyldimethylsilane 
All equipment was dried at 135.degree. and allowed to cool under dry 
nitrogen. All operations were carried out under dry nitrogen. 
A. Reaction of lithium ethenoxide with vinyldimethylchlorosilane 
Lithium ethenoxide solution, prepared as in Example 21A, was cooled in an 
ice bath, and with stirring, 75.6 mL (66.85 g, 0.554 mole) of 
chloro(vinyldimethyl)silane was added during 49 minutes. The mixture was 
stirred for an additional hour at ice bath temperature and then at room 
temperature for several hours. The mixture was filtered, the solid residue 
was rinsed with anhydrous ether, and the rinsings were added to the 
filtrate. Distillation of the filtrate through a small spinning band still 
gave 45.47 g (64% yield) of (ethenyloxy)vinyldimethylsilane distilling at 
95.6.degree.-99.6.degree.. The .sup.1 H NMR spectrum (Cl.sub.3 CD) 
exhibited resonances at .delta.=0.23 ppm (CH.sub.3 --Si), 4.11 and 4.42 
ppm (CH.sub.2 of the vinyl on oxygen) and a complicated multiline pattern 
at .delta.=5.62-6.50 ppm (vinyl group on silicon and the CH of the vinyl 
on oxygen), with relative intensities expected for 
(ethenyloxy)vinyldimethylsilane. The infrared spectrum (neat) exhibited 
bands at 3050 cm.sup.-1 and 3020 cm.sup.-1 (.dbd.CH), 2960 cm.sup.-1 (sat. 
CH), 1630 cm.sup.-1 (O--C.dbd.C), 1595 cm.sup.-1 (Si--C.dbd.C), 1250 and 
790 cm.sup.-1 (Si--CH.sub.3), and at 1175 cm.sup.-1 (unsaturated C--O), 
and is consistent with the vinyldimethylsilyl vinyl ether structure. 
B. Polymerization of (ethenyloxy)vinyldimethylsilane 
This polymerization was carried out as described in Example 21C with the 
following quantities of materials: 
Zinc iodide: 0.69 g 
Benzaldehyde: 0.22 mL 
Methylene chloride: 15 mL 
(Ethenyloxy)vinyldimethylsilane: 6.81 mL. The silane prepared in Part A was 
added to the stirred mixture of zinc iodide, benzaldehyde, and methylene 
chloride over a period of 20 minutes. The polymerization was exothermic 
from the start and the temperature rose to a maximum of 41.2.degree. from 
22.6.degree.. After the addition was completed, the mixture was stirred 
for about 20 h at room temperature. The mixture was filtered to remove 
undissolved salt, and the filtrate was distilled on the water pump to 
remove the solvent. The polymeric residue was further dried for several 
hours at about 0.5 mm under mild heating (up to about 42.degree.). The 
polymeric product obtained weighed 3.55 g (62% yield). The .sup.1 H NMR 
spectrum (Cl.sub.3 CD) exhibited resonances consistent with a polymer 
structure resulting from the benzaldehyde-initiated polymerization of the 
vinyl ether group, that is, broad resonances for CH.sub.2 and CH (adjacent 
to a silyloxy group) and resonances for CH.sub.3 --Si and C.sub.6 H.sub.5 
groups. In addition, there was a complex multiline pattern at .delta.= 
5.3-6.5 ppm which is due to the vinyl group on silicon. This position of 
the vinyl resonance in the polymer is almost exactly where it occurred in 
the monomer (.delta.=5.62-6.50 ppm). The intensity of this vinyl resonance 
is substantially equal to the combined intensities of the saturated CH and 
CH.sub.2 groups of the polymer, thus indicating that the vinyl group on 
the silicon did not participate in the polymerization. The infrared 
spectrum (neat) exhibited bands at 2950 cm.sup.-1 (saturated CH), 1490 
cm.sup.-1 (aromatic C.dbd.C) and 1250 and 780 cm.sup.-1 (Si--CH.sub.3) 
which are consistent with a polysilyl vinyl ether with methyl and phenyl 
substituents on the silicon. It also exhibited bands at 3040 and 3000 
cm.sup.-1 (.dbd.CH) and at 1590 cm.sup.-1 (Si--C.dbd.C), which confirm the 
presence of an unpolymerized vinyl group on silicon. 
Experiment 1 
Attempted Polymerization of EBDS in the Presence of Zinc Bromide Only 
The reaction of Example 11 was repeated, except that the terephthaldehyde 
was omitted. Only about 0.2 g of a comparatively high molecular weight 
polymer was isolated (M.sub.n 7850, M.sub.w 17,400), consistent with the 
expected result in the absence of an effective aldehydic initiator. 
BEST MODE FOR CARRYING OUT THE INVENTION 
The best mode present contemplated for carrying out the invention is 
illustrated by Examples 1, 2, 4, 8, 10, 11, 14, 15 and 16. 
INDUSTRIAL APPLICABILITY 
The invention process provides polymers which can be converted by 
hydrolysis to vinyl alcohol polymers which are widely used industrially in 
packaging film, fibers, adhesives, textile sizes, paper making and 
numerous other applications. Polymers of formula 1, which are "living", 
may be cast or spun, for example, into film or fiber, from solution, or 
isolated, processed, and then further polymerized and/or converted into 
polymers of formula 2 or formula 3. Polymers of formulas 1, 2 and 3 can be 
hydrolyzed to vinyl alcohol polymers before or after converting into 
shaped articles, such as films, fibers and compression molded objects.