"""Living"" polymers and process for their preparation"

"Living" polymers and their preparation from acrylic-type or maleimide monomers and organosilicon, -tin or -germanium initiators.

TECHNICAL FIELD 
This invention relates to a process for polymerizing polar .alpha.-olefinic 
monomers to "living" polymers and to the "living" polymers produced by 
such a process. 
BACKGROUND 
The 1:1 addition of .alpha.,.beta.-unsaturated esters, ketones, and 
nitriles to activated "donor" compounds, for example, silicon- or 
tin-containing "donor" compounds, is well known. Such reactions may be 
referred to a Michael type addition reactions and are catalyzed by bases, 
such as a fluoride or cyanide, or by Lewis acids, such as zinc chloride, 
boron trifluoride, titanium tetrachloride, or hydrogen bromide. 
K. Saigo et al., Chem. Letters, 2, 163 (1976) disclose that when 
methylvinyl ketone or cyclohexenone is employed as a Michael acceptor in 
the presence of O-silylated ketene acetals and titanium tetrachloride, the 
desired product is obtained in low yields and a polymeric by-product is 
produced. The polymer was not isolated or identified and means are 
disclosed for minimizing the by-product by modifying the titanium 
tetrachloride catalyst by including therewith tetraisopropyl titanate. 
U.S.S.R. Pat. No. 717,057 discloses organosilicon acetals of the formula 
EQU RO--CH(CH.sub.3)--OSiR'.sub.3-n (OR").sub.n, 
and their use as intermediates in the preparation of perfumes and in the 
production of polymers and flotation agents, wherein R is C.sub.3 H.sub.7, 
C.sub.6 H.sub.5, CH.tbd.CCH.sub.2, CH.tbd.CC(CH.sub.3).sub.2 or menthyl; 
R' is C.sub.1-4 alkyl or C.sub.6 H.sub.5 OCH(CH.sub.3), and n is 0 or 1. 
U.S.S.R. Pat. No. 715,583 discloses trimethylsiloxyethyl esters of the 
formula RC(O)X--CH(CH.sub.3)--OSi(CH.sub.3).sub.3, useful as intermediates 
in the manufacture of medicinals, plasticizers, and polymers, and as 
agricultural pesticides and perfumes and in food manufacture, wherein X is 
oxygen or sulfur and R is lower alkyl, chloroalkyl or optionally 
substituted alkenyl. 
Stork et al., JACS 95, 6152 (1973) disclose the use of .alpha.-silylated 
vinyl ketones to prevent the polymerization of simple alkyl vinyl ketones 
via their enolate ions during Michael addition reactions. 
The use of trialkylsilyl groups as temporary protectants for hydroxyl 
functions, removal by subsequent hydrolysis, is well known in the art, for 
example, Cunico et al., J. Org. Chem. 45, 4797, (1980). 
U.S. Pat. No. 4,351,924 discloses .omega.- and 
.alpha.,.omega.-hydroxyhydrocarbyl-(alkyl methacrylate) polymers prepared 
by anionic polymerization, and block and star polymers prepared therefrom 
by reaction with multifunctional bromomethyl compounds. 
U.S. Pat. No. 4,293,674 discloses dienyl esters of methacrylic acid, and 
homopolymers and copolymers thereof prepared by anionic polymerization. 
Sato et al., Polymer 24, 1018 (1983) disclose syntheses of block copolymers 
by reacting living poly(N-phenylmethacrylamide) radicals with vinyl 
monomers such as methyl methacrylate. 
DISCLOSURE OF THE INVENTION 
For further comprehension of the invention, and of the objects and 
advantages thereof, reference may be made to the following description and 
to the appended claims in which the various novel features of the 
invention are more particularly set forth. 
The invention resides in the process comprising polymerizing the monomer 
selected from the group consisting of 
##STR1## 
and mixtures thereof wherein: 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"; 
each R.sup.1, independently, is a hydrocarbyl radical which is an 
aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical 
containing up to 20 carbon atoms; 
R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or 
mixed aliphatic-aromatic radical containing up to 20 carbon atoms, 
optionally containing one or more ether oxygen atoms within aliphatic 
segments thereof and optionally containing one or more functional 
substituents that are unreactive under polymerizing conditions; and 
each of R' and R" is independently selected from C.sub.1-4 alkyl 
by contacting the one or more monomers under polymerizing conditions with: 
(i) the initiator of the formula (R.sup.1).sub.3 MZ wherein: 
R.sup.1 is as defined above; 
Z is an activating substituent selected from the group consisting of 
##STR2## 
and mixtures thereof X' is as defined above for the monomer; 
each of R.sup.2 and R.sup.3 is independently selected from H and 
hydrocarbyl, defined as for R above; 
Z' is O or NR'; 
m is 2, 3, or 4; 
n is 3, 4 or 5; and 
M is Si, Sn, or Ge, provided, however, when Z is 
##STR3## 
M is Sn or Ge; and (ii) a co-catalyst which is a source of fluoride, 
cyanide or azide ions or a suitable Lewis acid, for example, zinc 
chloride, bromide or iodide, boron trifluoride, an alkylaluminum oxide or 
an alkylaluminum chloride, to produce "living" polymer having repeat units 
of the one or more monomers, said process further characterized in that: 
(a) R.sup.1 is H, provided that at least one R.sup.1 group is not H; and/or 
(b) R is a polymeric radical containing at least 20 carbon atoms and 
optionally containing one or more ether oxygen atoms within aliphatic 
segments thereof and optionally containing one or more functional 
substituents that are unreactive under polymerizing conditions; and/or 
(c) at least one of any R group in the monomer contains one or more 
reactive substitutents of the formula --Z'(O)C--C(Y.sup.1).dbd.CH.sub.2 
wherein Y.sup.1 is H or CH.sub.3 and Z' is as defined above; and/or 
(d) the initiator is of the formula (R.sup.1).sub.2 M(Z.sup.1).sub.2 or 
O[M(R.sup.1).sub.2 Z.sup.1 ].sub.2 wherein R.sup.1 and M are as defined 
above and Z.sup.1 is 
##STR4## 
wherein X', R.sup.2 and R.sup.3 are as defined above; and/or (e) at least 
one of any R, R.sup.2 and R.sup.3 in the initiator contains one or more 
initiating substitutents of the formula --Z.sup.2 --M(R.sup.1).sub.3 
wherein 
M and R.sup.1 are as defined above; and 
Z.sup.2 is a diradical selected from the group consisting of 
##STR5## 
and mixtures thereof, wherein R.sup.2, R.sup.3, X', Z', m and n are as 
defined above, provided, however, when Z.sup.2 is 
##STR6## 
M is Sn or Ge; and/or (f) Z is selected from the group consisting of 
--SR, --OP(NR'R").sub.2, --OP(OR.sup.1).sub.2, --OP[OSi(R.sup.1).sub.3 
].sub.2 and mixtures thereof, 
wherein R, R.sup.1, R' and R" are as defined above; and/or 
(g) R.sup.2 and R.sup.3 taken together are 
##STR7## 
provided, however, Z is 
##STR8## 
and/or (h) X' and either R.sup.2 or R.sup.3 taken together are 
##STR9## 
provided, however, Z is 
##STR10## 
By "living" polymer is meant a polymer of the invention which contains at 
least one active terminal group and is capable of polymerizing further in 
the presence of monomer(s) and co-catalyst. 
It has been independently discovered that bifluoride ions 
HF.sub.2.sup..crclbar. are also excellent co-catalysts in the process of 
the invention. 
It will be understood by one skilled in the art that the last four members 
of the aforesaid group from which the activating substituent Z is selected 
are the respective ketene imine or enol forms of the previous four members 
of the group. The mixtures of such members which are operable herein 
include, but are not limited to, the corresponding cyano-imine or 
keto-enol mixtures. 
The polymers produced by the process of the invention are "living" polymers 
of the formula 
##STR11## 
wherein: Z" is selected from the group consisting of 
##STR12## 
each of a and b is independently selected from 0 or a number in the range 
1 to about 100,000, provided, however, (a+b) is at least 3; 
Q is the divalent radical selected from the group consisting of 
##STR13## 
and mixtures thereof; and all remaining symbols are as defined above, said 
polymer further characterized in that: 
(a) R.sup.1 is H, provided that at least one R.sup.1 group is not H; and/or 
(b) Z" is selected from --P(O)(NR'R").sub.2, --P(O)OR.sup.1).sub.2, 
--P(O)[OSi(R.sup.1).sub.3 ].sub.2 and --SR; and/or 
(c) the "living" polymer is of the formula 
EQU R.sub.p ([Z.sup.3 PQM (R.sup.1).sub.3-k ].sub.1+k (O).sub.k).sub.p 
wherein: 
Rp is a hydrocarbyl radical which is aliphatic, alicyclic, aromatic or 
mixed aliphatic-aromatic containing up to 20 carbon atoms, or a polymeric 
radical containing at least 20 carbon atoms, of valence p, optionally 
containing one or more ether oxygen atoms, keto groups and/or functional 
substituents that are unreactive under polymerizing conditions; 
Z.sup.3 is a diradical selected from the group consisting of 
##STR14## 
and mixtures thereof; Z', R.sup.2, R.sup.3, X', m and n are as defined 
above; 
P is a divalent polymeric radical of the formula 
##STR15## 
wherein X, Y, R, a and b are as defined above; 
Q, M and R.sup.1 are as defined above; 
k is 0 or 1; and 
p is an integer and is at least 1 when k is 1 or at least 2 when k is 0, 
provided, however, 
(i) when Z.sup.3 is 
##STR16## 
M is Sn or Ge; (ii) when Z.sup.3 is 
##STR17## 
R.sup.2 and R.sup.3 taken together is 
##STR18## 
and (iii) when Z.sup.3 is 
##STR19## 
R.sup.2 and X' taken together is 
##STR20## 
It is readily apparent that the five members of the group defining Z" are 
the same as the first five members of the aforesaid group defining Z and 
are cyano or keto forms of Z. It also is apparent that Q is a "living" 
polymer unit provided by the starting monomers of the process of the 
invention, as originally depicted above, or such unit in its enol or imine 
form. The "living" polymers contain terminal groups --M(R.sup.1).sub.3 at 
their "living" ends or, when polymerization is initiated by bifunctional 
initiators of the formula (R.sup.1).sub.2 M(Z.sup.1).sub.2 or 
O[M(R.sup.1).sub.2 Z.sup.1 ].sub.2, central groups --M(R.sup.1).sub.2 
--O--M(R.sup.1).sub.2 --. These terminal or central groups are attached to 
carbon if the adjacent Q unit is in its keto form, and to a hetero atom (O 
or N) if the adjacent Q unit is in its enol form. Both tautomeric forms 
may coexist in a given "living" polymer of the invention. 
In the description of the further characterization of the invention, any 
reference to symbols "as defined above" means not only as defined above in 
the further characterization but also as defined anywhere hereinabove. 
This caveat applies particularly to the definitions of R, R.sup.1, 
R.sup.2, R.sup.3, Z and Z". 
The "living" polymer of the invention can be a homopolymer or a copolymer, 
depending on the monomer or monomers selected for use in the process of 
the invention. Moreover, as will be discussed more fully hereinafter, the 
"living" polymer can be linear or branched and, depending on the selection 
of X, R.sub.p or Z" in the formulas, can be used to prepare crosslinked 
polymers and block copolymers. 
Monomers which are suitable for use in the practice of this invention are, 
in general, known compounds and include, but are not limited to, the 
following: methyl methacrylate; butyl methacrylate; sorbyl acrylate and 
methacrylate; lauryl methacrylate; ethyl acrylate; butyl acrylate; 
acrylonitrile; methacrylonitrile; 2-ethylhexyl methacrylate; 
2-(dimethylamino)ethyl methacrylate; 2-(dimethylamino ethyl acrylate; 
3,3-dimethoxypropyl acrylate; 3-methacryloxypropyl acrylate; 
2-acetoxyethyl methacrylate; p-tolyl methacrylate; 
2,2,3,3,4,4,4-heptafluorobutyl acrylate; methylene malononitrile; ethyl 
2-cyanoacrylate; N,N-dimethyl acrylamide; 4-fluorophenyl acrylate; 
2-methacryloxyethyl acrylate and linoleate; propyl vinyl ketone; ethyl 
2-chloroacrylate; glycidyl methacrylate; 3-methoxypropyl methacrylate; 
2-[(1-propenyl)oxy]ethyl methacrylate and acrylate; phenyl acrylate; 
2-(trimethylsiloxy)ethyl methacrylate; 2-(methylsiloxy)ethyl methacrylate; 
allyl acrylate and methacrylate; unsaturated esters of polyols, 
particularly such esters of .alpha.-methylenecarboxylic acids, for 
example, ethylene glycol diacrylate, diethylene glycol diacrylate, 
glycerol diacrylate, glyceryl triacrylate, mannitol hexaacrylate, sorbitol 
hexaacrylates, ethylene glycol dimethacrylate, hexamethylene diol 
diacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol 
trimethacrylate, 1,1,1-trimethylolpropane triacrylate, triethylene glycol 
diacrylate, 1,4-cyclohexanediol diacrylate, 1,4-benzenediol 
dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol 
hexaacrylate, pentaerythritol tetraacrylates, 1,3-propanediol diacrylate, 
1,5-pentanediol dimethacrylate, the bis-acrylates and methacrylates of 
polyethylene glycols of molecular weight 200-4000, and 
.alpha.,.omega.-polycaprolactonediol diacrylate; unsaturated N-alkylated 
amides, such as methylene bis-(N-methylacrylamide), methylene 
bis-(N-methylmethacrylamide), ethylene bis-(N-methylmethacrylamide), 
1,6-hexamethylene bis-(N-methylacrylamide), 
bis(.gamma.-N-methylmethacrylamidopropoxy)ethane 
.beta.-N-methylmethacrylamidoethyl methacrylate; 
3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate; and mixtures thereof. 
Preferred monomers include methyl methacrylate; glycidyl methacrylate; 
sorbyl methacrylate; ethyl acrylate; butyl acrylate; sorbyl acrylate; 
2-(trimethylsiloxy)ethyl methacrylate; 2-methacryloxyethyl acrylate; 
2-acetoxyethyl methacrylate; 2-(dimethylamino)ethyl methacrylate; 
N-phenyl-N-methylacrylamide; p-xylylene diacrylate; 
1,4-bis(2-acryloxyethyl)benzene; pentaerythritol triacrylate; 
1,1,1-trimethylolpropane triacrylate; pentaerythritol tetraacrylate; 
triethylene glycol diacrylate; triethylene glycol dimethacrylate; 
1,1,1-trimethylolpropane trimethacrylate; 4-acryloxydiphenylmethane; and 
hexamethylenediol diacrylate and dimethacrylate. Methyl methacrylate is 
most preferred. 
As indicated above in the definition of R in the formulas for the monomer, 
substituents that are unreactive under polymerizing conditions include 
those having oxygen-, nitrogen-, or silicon-containing groups which are 
devoid of reactive hydrogen atoms. Groups such as OSi(R.sup.1).sub.3 and 
CONH.sub.2 are nonreactive under such conditions and, therefore, can be 
tolerated. On the other hand, groups such as CO.sub.2 H and OH are 
reactive under polymerizing conditions. In order for monomers containing 
such groups on the R substituent to be useful in the invention process, 
the groups must be chemically protected, i.e. deactivated. Monomers 
containing such deactivated groups are useful in the preparation of 
polymers which, upon treatment to remove the protective group, have 
functional sites along the polymer chain. Monomers which contain 
sufficiently sterically hindered amine and alcohol groups that remain 
inert under reaction conditions may be used directly without deactivation. 
The functional sites can be impart special properties to the polymer 
products, including curability and photosensitivity. 
The definition of R in the monomer formulas also includes substituents 
which are reactive under polymerizing conditions and of the formula 
CH.sub.2 .dbd.C(Y.sup.2)C(O)Z'--wherein Y.sup.2 and Z' are as defined 
above. These reactive substituents provide additional centers for 
initiation of polymerization, leading to the growth of polymeric branches. 
The reactive substituents are derived from (meth)acrylates or 
(meth)acrylamides which are themselves operable monomers in the present 
invention. These substituents can react with initiators of the invention 
to provide new initiating sites from which polymeric branches can grow in 
the presence of monomer(s) and cocatalyst. 
Initiators which are useful in the invention process include, but are not 
limited to, the following: 
[(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane; 
[(1-methoxy-2-methyl-1-propenyl)oxy]dimethyloctadecylsilane; 
[(1-methoxy-2-methyl-1-propenyl)oxy]methylsilane; 
2-(trimethylsilyl)isobutyronitrile; ethyl 2-(trimethylsilyl)acetate; 
methyl 2-methyl-2-(tributylstannyl)propanoate; 
[(2-methyl-1-cyclohexenyl)oxy]tributylstannane; trimethylsilyl nitrile; 
methyl 2-methyl-2-(trimethylgermanyl)propanoate; 
[(4,5-dihydro-2-furanyl)oxy]trimethylsilane; 
[(2-methyl-1-propenylidene)bis(oxy)]bis[trimethylsilane]; 
[(2-methyl-1-[2-(methoxymethoxy)ethoxy]-1-propenyl)oxy]trimethylsilane; 
methyl [(2-methyl-1-(trimethylsilyloxy)-1-propenyl)oxy]acetate; 
[(1-(methoxymethoxy)-2-methyl-1-propenyl)oxy]trimethylsilane; trimethyl 
.alpha.,.alpha.',.alpha."-tris(trimethylsilyl)-1,3,5-benzenetriacetate; 
dimethyl .alpha.,.alpha.'-bis(trimethylsilyl)-1,3-benzenediacetate; 
[1,6-dimethoxy-1,5-hexadiene-1,6-diylbis(oxy)]bis[trimethylsilane]; 
[(2-ethyl-1-propoxy-1-butenyl)oxy]ethyldimethylsilane; ethyl 
2-(trimethylstannyl)propanoate; [(1-cyclohexenyl)oxy]trimethylstannane; 
[(2-methyl-1-butenylidene)bis(oxy)]bis[trimethylsilane]; 
2-(trimethylsilyl)propanenitrile; ethyl (trimethylgermanyl)acetate; 
[(1-((1-dec-2-enyl)oxy)-2-methyl-1-propenyl)oxy]trimethylsilane; phenyl 
2-methyl- 2-(tributylstannyl)propanoate; methyl 2-(triethylsilyl)acetate; 
dimethyl 2,5-bis(trimethylgermanyl)hexanedioate; 
[(2-methyl-1-cyclohexenyl]oxy]tributylstannane; 
[(1-methoxy-2-methyl-1-propenyl)oxy]phenyldimethylsilane; 
[(2-methyl-1-[2-(trimethylsiloxy)ethoxy]-1-propenyl)oxy]trimethylsilane; 
trimethyl(methylthio)silane; trimethyl(phenylthio)silane; 
N,N-dimethyl-(trimethylsilyl)phosphorodiamidite; (trimethylsilyl)dimethyl 
phosphite; tris(trimethylsilyl)phosphite; 
N,N-dimethyl-P-[3-methoxy-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic 
diamide; 
N,N-dimethyl-P-[3-methoxy-2-methyl-3-((trimethylsilyl)oxy)-2-propenyl]phos 
phonic diamide; [3-methoxy-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic 
acid, bis(trimethylsilyl) ester; 
[3-methoxy-2-methyl-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic acid, 
bis(trimethylsilyl)ester; 
[3-methoxy-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic acid, diethyl 
ester; 
[(2-((1,1-dimethylethyl)-5-phenyl-1,3-dioxol-4yl)oxy]trimethylsilane; 
[(2-methyl-5-phenyl-1,3-dioxol-4-yl)oxy]trimethylsilane; 
[(methoxy)(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)methoxy]trimethyl 
silane; 1,3-bis[(1-methoxy-1-butenyl)oxy]-1,1,3,3-tetramethyldisiloxane; 
bis[(1-methoxy-2-methyl-1-propenyl)oxy]methylsilane; 
bis[(1-methoxy-2-methyl-1-propenyl)oxy]dimethylsilane. Preferred 
initiators include [(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane; 
[(2-methyl-1-propenylidene)bis(oxy)]bis[trimethylsilane]; trialkylsilyl 
nitriles; and 
[(2-methyl-1-[2-(trimethylsiloxy)ethoxy]-1-propenyl)oxy]trimethylsilane. 
Trimethylsilyl nitrile is most preferred. 
The initiators used in the invention are either known compounds or can be 
prepared by known methods from known starting materials. Of the initiators 
listed above, trimethylsilyl nitrile and ethyl trimethysilyl acetate are 
commercially available. Initiators of the aforesaid formula 
(R.sup.1).sub.3 MZ wherein Z is 
##STR21## 
or the corresponding ketene imine or enol isomeric forms 
##STR22## 
wherein X' is defined as above can be prepared from nitriles 
(R.sup.2)(R.sup.3) CHCN, esters, ketones, or substituted amides 
(R.sup.2)(R.sup.3)CHC(O)X' wherein X' is as defined above by reaction 
with, for example, n-butyllithium or lithium diisopropylamide, followed by 
reaction with a halide of the formula (R.sup.1).sub.3 MCl wherein R.sup.1 
and M are as defined above. 
Initiators of the aforesaid formula wherein R.sup.2 or R.sup.3 is CH.sub.3 
also can be prepared from the monomers using appropriate procedures. For 
example, CH.sub.2 .dbd.C(R.sup.3)C(O)X' can be reacted with 
(R.sup.1).sub.3 MH wherein R.sup.1 is as defined above to produce 
(R.sup.1).sub.3 MZ wherein Z is 
##STR23## 
In still another method, the preferred initiators which are trialkylsilyl 
nitriles can be prepared in situ by treating a trialkylsilyl chloride with 
an excess of cyanide ion from a suitable source, such as 
tetraalkylammonium cyanide. The residual cyanide ion can serve as a 
co-catalyst for the polymerization. 
Similarly, initiators of the formulas (R.sup.1).sub.2 M(Z.sup.1).sub.2 or 
O[M(R.sup.1).sub.2 Z.sup.1 ].sub.2 wherein R.sup.1, M and Z.sup.1 are as 
defined above are either known compounds or can be prepared by the above 
methods employing, for example: dihalides of the formula (R.sup.1).sub.2 
MCl.sub.2 in place of halides (R.sup.1).sub.3 MCl in the reaction with 
lithium-containing intermediates as described above; or dihydrides 
(R.sup.1).sub.2 HM--O--MH(R.sup.1).sub.2 in place of (R.sup.1).sub.3 MH in 
the reaction with the monomers CH.sub.2 .dbd.C(R.sup.3)C(O)X'. 
Useful initiators of the invention include those wherein the activating 
substituent Z or Z.sup.1 also contains one or more reactive initiating 
substituents, resulting in branched polymers. Such initiators can be 
prepared in situ by reacting a monomeric compound containing at least one 
reactive substituent with a "simple" initiator (R.sup.1).sub.3 MZ, or 
precursor thereof, containing at least one initiating site. 
It is to be understood that the useful initiators include nitriles, esters, 
amides, and ketones and their corresponding ketene imine and enol forms, 
all of which are active in the polymerization process of this invention. 
Moreover, the initiators wherein the activating moiety Z contains R, 
R.sup.2, and/or R.sup.3 can also have, like the monomer, one or more 
functional substituents attached to an aforesaid R group, provided such 
substituents do not interfere with polymerization. Functional substituents 
which are useful include, but are not limited to, 
##STR24## 
Such substituents, either directly or after treatment, for example, 
hydrolysis, provide functional sites along or at the end of polymer chains 
suitable for cross-linking, chain extension, chain branching, or for 
modifying properties such as water sorption, UV absorption, and the like. 
In the practice of this invention, as described below, an initiator moiety 
forms one end of a polymer chain or branch and hence said polymers can be 
terminally or centrally functionalized by appropriate initiator selection 
and polymer treatment. 
The co-catalysts used in the invention process are either known compounds 
or can be prepared by known methods from known compounds. Suitable, that 
is, effective, co-catalysts which are useful in the invention process 
include zinc iodide, bromide, and chloride, mono- and dialkylaluminum 
halides, dialkylaluminum oxides, tris(dimethylamino)sulfonium 
difluorotrimethylsilicate, tris(dimethylamino)sulfonium cyanide, 
tetraphenylarsonium cyanide, tris(dimethylamino)sulfonium azide, 
tetraethylammonium azide, boron trifluoride etherate, alkali metal 
fluorides, alkali metal cyanides, alkali metal azides, 
tris(dimethylamino)sulfonium difluorotriphenylstannate, tetrabutylammonium 
fluoride, tetramethylammonium fluoride, and tetraethylammonium cyanide. 
Preferred co-catalysts include sources of fluoride ions, especially 
tris(dimethylamino)sulfonium difluorotrimethyl silicate and 
tetrabutylammonium fluoride; tetraalkylammonium cyanides, zinc bromide, 
and zinc chloride. Other co-catalysts include the independently discovered 
sources of bifluoride ions, such as, for example, 
tris(dimethylamino)sulfonium bifluoride, bifluorides of the alkali metals, 
especially potassium, ammonium bifluoride, tetraalkylammonium bifluorides 
and tetraarylphosphonium bifluorides. Tris(dimethylamino)sulfonium 
bifluoride may be prepared by reacting tris(dimethylamino)sulfonium 
difluorotrimethylsilicate with water or a lower alkanol, for example, 
methanol; water is preferred since higher yields are obtained. 
The process of the invention is carried out at about -100.degree. C. to 
about 150.degree. C., preferably 0.degree. C. to 50.degree. C., most 
preferably at ambient temperature. A solvent is desirable but not 
essential. 
Suitable solvents are aprotic liquids in which the monomer, initiator and 
co-catalyst are sufficiently soluble for reaction to occur; that is, the 
materials are dissolved at the concentrations employed. Suitable solvents 
include ethyl acetate, propionitrile, toluene, xylene, bromobenzene, 
dimethoxyethane, diethoxyethane, diethylether, tetramethylene sulfone, 
N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 
anisole, 2-butoxyethoxytrimethylsilane, cellosolve acetate, crown ethers 
such as 18-crown-6, acetonitrile, and tetrahydrofuran. Acetonitrile and 
tetrahydrofuran are preferred solvents when a co-catalyst wherein the 
active species is an anion is used. When the co-catalyst employed is a 
zinc compound, suitable solvents are limited to hydrocarbons and 
chlorinated hydrocarbons preferably dichloromethane or 1,2-dichloroethane. 
The monomers used in the process of the invention are generally liquids and 
can be polymerized without a solvent, although a solvent is beneficial in 
controlling temperature during exothermic polymerization. When a solvent 
is used, the monomer may be dissolved or dispersed therein at 
concentrations of at least 1 wt %, preferably at least 10 wt %. The 
initiator is employed at a concentration such that the monomer/initiator 
molar ratio is greater than 1, preferably greater than 5. The co-catalyst 
is normally present in such an amount that the molar ratio of initiator to 
co-catalyst is in the range 0.1 to 10,000, preferably 10 to 100. 
In the polymerization process of the invention, it is preferable to charge 
the initiator, co-catalyst, and solvent, if used, to the polymerization 
vessel before adding the monomer(s), especially if polymers of narrow 
molecular weight distribution are desired. In selected cases, such as the 
polymerization of methyl methacrylate initiated by trimethylsilyl nitrile 
using a relatively low concentration of cyanide or fluoride ions as the 
co-catalyst, polymerization takes place after an induction period of 
several minutes. In such cases, all materials, including the monomer(s), 
may be charged together or independently, and mixed in place. Such an 
initiator/co-catalyst system is preferred to obtain relatively 
monodisperse polymers. By a monodisperse polymer is meant one having a 
narrow molecular weight distribution, that is, M.sub.w /M.sub.n is about 
1. At higher values of M.sub.w /M.sub.n the polymer is said by the art to 
be polydisperse. 
Although, as indicated above, it is preferable to charge all necessary 
initiator, co-catalyst and solvent to the polymerization vessel before 
adding monomer(s), subsequent polymerization rate being controlled by 
monomer addition, further additions of co-catalyst may sometimes be 
necessary to sustain polymerization. 
The final (non-living) polymeric product obtained by means of the process 
of the invention is formed by exposing the "living" polymer to an active 
hydrogen source, such as moisture or an alcohol, for example, methanol. 
The "living" polymers of the invention will remain "living" for substantial 
periods provided they are protected from active hydrogen sources such as 
water or alcohols. Solutions of "living" polymers in inert solvents, such 
as hydrocarbons, are especially useful for preserving and conveying the 
"living" polymers. Films and fibers of the "living" polymers may be cast 
or spun from such solutions, or the polymer may be isolated from solution 
and further processed, for example, pelletized or granulated. 
It is to be understood that the final (non-living) polymeric product does 
not include the enol or imine species of Q in the aforesaid formula for 
the "living" polymer of the invention. For example (as in Example 3), a 
"living" polymer prepared by polymerizing methyl methacrylate using 
[(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane (MTS) as the initiator 
contains, at its living end, the enolic grouping 
##STR25## 
which, upon quenching, is converted to 
##STR26## 
The process of the invention is useful for preparing homopolymers or 
copolymers of the monomers described above. In either case, the polymers 
obtained are "living" polymers which may be of high or low molecular 
weight and having a broad or narrow molecular weight distribution (M.sub.w 
/M.sub.n). At a given temperature, M.sub.w /M.sub.n is primarily a 
function of the relative rates of initiation and polymerization. Rate of 
initiation, r.sub.i, depends on initiator and co-catalyst type and 
relative concentrations. Polymerization rate, r.sub.p is a function of 
monomer reactivity and co-catalyst type and concentration. For 
monodispersity, r.sub.i /r.sub.p is equal to or greater than 1, that is, 
the initiation rate is at least as fast as the polymerization rate and all 
chains grow simultaneously. Such conditions characterize the preparation 
of "living" polymers by anionic polymerization techniques of the art 
wherein M.sub.w /M.sub.n ratios only slightly above the theoretical limit 
of 1 are obtainable; for example, poly(methyl methacrylate) of M.sub.w 
/M.sub.n of about 1.01 to 1.1 are known in the art, as are copolymers of 
methyl methacrylate and other alkyl methacrylates. Control of M.sub.w 
/M.sub.n permits useful variation in polymer physical properties, such as 
glass transition temperature, hardness, heat distortion temperature, and 
melt viscosity. 
The polymerization process of the present invention involves a "living" 
mechanism having several similarities wih anionic polymerization. For 
example, initiation and polymerization may be represented by conventional 
equations wherein the initiator moiety (R.sup.1).sub.3 M is located at one 
end of the polymer chain or branch which remains "living" even when the 
monomer supply is consumed; the activating substituent Z is located at the 
other end of the polymer chain or branch. The terminal initiator moiety, 
unless chemically deactivated, is capable of initiating further 
polymerization with the same or different monomer, with resultant chain 
lengthening. Copolymers with specific monomer sequences, or block 
polymers, can thus be prepared. 
Although the present process resembles anionic polymerization, there are 
significant differences which have commercial significance. These 
differences include the ability to copolymerize methacrylate and acrylate 
monomers, or combinations of acrylate monomers, for example, ethyl and 
sorbyl acrylates, to relatively monodisperse copolymers. Such copolymers 
are difficult or impossible to obtain by known processes such as anionic 
polymerization or free-radical polymerization. Moreover, whereas anionic 
polymerization processes which provide relatively monodisperse polymers 
are carried out at low temperatures, usually well below -10.degree. C., 
which require expensive refrigeration equipment for commercial operation, 
the polymerization process of the invention is operable over a wide 
temperature range, from about -100.degree. C. to about 150.degree. C. It 
is conveniently operable with many commercially important monomers at 
about ambient temperatures. 
The process of this invention can also be used to prepare polymers 
containing one or more specifically located functional groups which are 
unreactive under polymerizing conditions but are useful for subsequent 
preparation of block copolymers or crosslinked polymers. The functional 
groups may be introduced by using either a monomer or an initiator, or 
both, containing a protected functional substituent, or by chemically 
deactivating (capping) the "living" end of the polymer chain or branch 
with a functionalized capping agent. If the capping agent contains more 
than one capping site, then more than one polymer chain can be joined 
together or coupled to give doubled or "star"-branched polymers, similar 
to the doubled or star-branched polymers obtained when the initiator 
contains more than one initiating site, or the monomer contains more than 
one reactive site capable of reacting with initiators, as described 
previously. Even if the capping agent contains only one capping site, the 
agent may also contain other functional groups which provide reactive 
terminal sites to the polymer, useful for subsequent preparation of block 
copolymers or cross-linked polymers, or for otherwise modifying polymer 
properties. Examples of capping agents containing one or more capping 
sites include p-dimethoxymethylbenzyl bromide, p-chloromethylstyrene, 
p-methoxymethoxymethylbenzyl bromide, 1,4-bis(bromomethyl)benzene, 
1,3,5-tris(bromomethyl) benzene, terephthaldehyde and toluene 
diisocyanate. Capping agents containing one capping site and one or more 
functional groups that are unreactive under capping conditions include 
1-bromomethyl-4-dimethoxymethylbenzene, 
1-bromoethyl-4-(methoxymethoxymethyl)benzene, 4-chloromethylstyrene, 
4-(trimethylsilylcarboxy)benzaldehyde, 4-nitrobenzaldehyde, 
2,5-furanyldione and 1,3-di(carbonylamino)-1,5,5-trimethylbenzene. In 
general, capping agents which are useful in the process of the invention 
include aliphatic, aromatic or aliphatic-aromatic compounds containing one 
or more capping functions such as --CHO, 
##STR27## 
--NCO, --Br, --Cl and --TiCl.sub.3, and which may optionally also contain 
non-capping functional substituents, such as --NO.sub.2, 
--OSi(R.sup.1).sub.3 and --CO.sub.2 Si(R.sup.1).sub.3. Reaction of capping 
agents with the "living" polymer ends proceeds similarly to known 
reactions of non-polymeric trialkylsilanes. The capping reaction is 
normally carried out in an organic liquid wherein both polymer and capping 
agent are soluble; frequently, the polymerization solvent is suitable. The 
reaction is preferably carried out in the presence of fluoride ion as 
catalyst; tris(dimethylamino)sulfonium difluorotrimethylsilicate is a 
preferred catalyst. Examples of initiators which can initiae more than one 
polymer chain include trimethyl 
.alpha.,.alpha.',.alpha."-tris(trimethylsilyl)-1,3,5-benzenetriacetate, 
dimethyl .alpha.,.alpha.'-bis(trimethylsilyl)-1,3,-benzenediacetate, 
1,6-dimethoxy-1,5-hexadiene-1,6-diylbis(oxy)bis[trimethylsilane], and 
bis[(1-methoxy-2-methyl-1-propenyl)oxy]methylsilane.

In the following examples of specific embodiments of this 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, the "living" polymer products obtained in the invention process 
were quenched by exposure to moist air before molecular weights were 
determined. 
It is to be understood that Examples 4, 7, 8, 9, 10 and 11 involve use of a 
bifluoride catalyst, which catalyst is the invention of another and which 
is further described in copending application Ser. No. 389,111 filed June 
17, 1982, (now U.S. Pat. No. 4,414,372). 
EXAMPLE 1 
Copolymerization of Methyl Methacrylate and Hexamethylene Diacrylate 
This example demonstrates the conversion of a difunctional monomer to a 
difunctional initiator with Me.sub.3 SiCN and subsequent polymerization of 
MMA to give a "double-ended" polymer, taking advantage of the faster 
reaction of acrylates than methacrylates. 
To a stirred solution, under argon, of 0.64 ml (5 mmol) of trimethylsilyl 
nitrile and 0.5 ml of 1M tetraethylammonium cyanide/acetonitrile in 20 ml 
of acetonitrile was added simultaneously 10.8 ml (100 mmol) of methyl 
methacrylate and 0.566 g (2.5 mmol) of hexamethylene diacrylate. The 
temperature gradually rose from 21.degree. to 23.6.degree. during 20 min 
and then receded. After 60 min an exotherm occurred, causing the 
temperature to rise to 42.degree. during 10 min and then recede. The 
solution remained clear and relatively nonviscous, indicating that 
crosslinking did not occur. After a total time of 2 h, 2 ml of methanol 
was added to remove the trimethylsilyl end groups, and the solution was 
evaporated in vacuo to 10.8 g of solid poly(methyl methacrylate). GPC: 
M.sub.n 3900, M.sub.w 4900, D 1.25 (theor. M.sub.n 4278). 
EXAMPLE 2 
Poly(Methyl Methacrylate)/Polycaprolactone/Poly(Methyl Methacrylate) ABA 
Block Copolymer 
This example demonstrates the preparation of the diacrylate of 
.alpha.,.omega.-polycaprolactone diol, conversion of the diacrylate to a 
difunctional initiator with Me.sub.3 SiCN, and polymerization of MMA onto 
the ends. The polycaprolactone provides a soft segment, and the poly(MMA) 
provides hard segments. 
Polycaprolactone .alpha.,.omega.-diacrylate was prepared as follows. A 
solution of 50 g of commercial polycaprolactone .alpha.,.omega.-diol 
(M.W..about.1000) in 300 ml of toluene was refluxed under a Dean and Stark 
water separator for 18 h. Then, 20 ml (150 mmol) of triethylamine was 
added, and 10.2 g (9.1 ml, 110 mmol) of 98% acrylyl chloride was added at 
a rate so as to keep the temperature from exceeding 50.degree.. After 
stirring for 30 min at 50.degree., the solution was cooled and filtered 
under argon. The solution was concentrated in vacuo and then passed over a 
column of neutral alumina under argon. The NMR spectrum of the resulting 
solution (230 g) showed 67.6% by weight of polycaprolactone diacrylate and 
32.4% toluene, with a formula weight of 992, GPC: M.sub.n 1250, M.sub.w 
2200, D 1.76. 
To a solution of 0.6 g (0.75 ml, 6.04 mmol) of trimethylsilyl nitrile and 
0.5 ml of 1M tetraethylammonium cyanide/acetonitrile in 20 ml of 
acetonitrile, under argon, was added 4.44 g (3.02 mmol) of 67.6% 
caprolactone diacrylate. After 20 min, 10.8 ml (100 mmol) of methyl 
methacrylate was added. An exotherm occurred 90 min after addition of the 
methyl methacrylate. After 18 h, 2 ml of methanol was added, and the 
solution was evaporated in vacuo to 13.5 g of solid polymer. GPC: M.sub.n 
4120, M.sub.w 7340, D 1.78 (theor. M.sub.n 4303). NMR shows 4.24 methyl 
methacrylate units/caprolactone unit (theor. 4.36). 
EXAMPLE 3 
Polymerization of Methyl Methacrylate and Isolation of 
Trimethoxysiloxy-ended Polymer 
This example demonstrates, by means of carbon-13 NMR analysis, the presence 
of silylenolate terminal groups in a "living" polymer prepared by the 
process of this invention, said polymer being isolatable as a solid 
without loss of activity. 
A. Tetraethylammonium cyanide (6 mg, 0.1 mmol) in a reactor was heated 
gently under vacuum to 200.degree. to remove moisture. After cooling under 
argon, tetrahydrofuran (THF) (20 ml) and MTS (2.0 ml, 10 mmol) were added 
to the reactor. MMA (10.6 ml, 100 mmol) was added dropwise over 30 min, 
during which time the temperature rose to 55.4.degree.. The reaction 
mixture was allowed to cool to 22.degree. and solvent was removed under 
vacuum while the reactor was maintained at about 25.degree.. The white 
residue which resulted was transferred into a dry-box. An 800 mg sample 
was removed, dissolved in deuterochloroform (CDCl.sub.3, 3 ml) and 
analyzed by C-13 NMR; 0.6 g of the residue was analyzed by GPC. GPC: 
M.sub.n 777, M.sub.w 1010, D 1.30 (theor. M.sub.n 1102). C-13 NMR: C-13 
shielding peaks as follows: 
______________________________________ 
Peak (ppm) Assignment 
______________________________________ 
151.99 C-1 
89.78 C-2 
54.28 C-3 
29.56 C-4 
55.42 C-5 
-0.11 C-6 
______________________________________ 
##STR28## 
- In the above formula for the polymer, n is about 9. The remaining 
shielding peaks corresponding to carbon atoms of the polymer are 
consistent with published C-13 NMR spectra of poly(methyl methacrylate) 
(J. Schaefer, Macromolecules 10, 384 (1977); J. C. Randall, "Polymer 
Sequence Determination, Carbon 13 NMR Method", Academic Press, New York, 
1977). The above assignments for the terminal group in the polymer are 
consisent with the C-13 NMR spectrum of MTS: 
______________________________________ 
Peak (ppm) Assignment 
______________________________________ 
149.50 C-1 
90.40 C-2 
56.17 C-3 
16.61, 15.84 C-4 
-0.20 C-5 
______________________________________ 
##STR29## 
B. The polymer prepared and analyzed in Part A was determined to be 
"living" in the following manner. The remaining polymer from Part A not 
used for analysis was returned to the reactor. Under argon, THR (20 ml) 
was added, with stirring, to dissolve the polymer and MMA (10 ml, 94 mmol) 
was added. The temperature, originally 19.degree., rose to 29.4.degree., 
indicating that further polymerization was effected with the "living" 
polymer and fresh monomer. The mixture was stirred for 3 h, quenched with 
methanol (10 ml) and evaporated, yielding 22.65 g of polymer. GPC: M.sub.n 
1430, M.sub.w 1900, D 1.32 (theor. M.sub.n 2042). 
EXAMPLE 4 
Preparation of "Living" Poly(Methyl Methacrylate) and Subsequent Reactions 
Thereof 
This example demonstrates the preparation of "living" poly(methyl 
methacrylate) containing active terminal trimethylsiloxy groups, and 
subsequent reactions thereof. 
A. "Living" Poly(methyl methacrylate) 
To a solution of 2.6 g (9.4 mmol) of 
[(2-methyl-1-[2-trimethylsiloxy)ethoxy]-1-propenyl)oxy] trimethyl-silane 
in 10 ml of THF was added 166 mg of tris(dimethylamino)sulfonium 
bifluoride. Then, a solution of 10 g (100 mmol) of MMA in 10 ml of THF was 
added dropwise over 30 min. After the temperature dropped to 22.degree., 
the reaction mixture containing PMMA was separated into three equal parts, 
under argon, for use in Parts B, C and D below. 
B. Reaction with Bromine and Titanium Tetrachloride 
The reactions involved are shown below. In all equations, R is 
##STR30## 
(i) Bromine reacts with approximately one-half of the living polymer in the 
11.1 ml aliquot of polymerization mixture from Part A: 
##STR31## 
(ii) The remaining living polymer in the 11.1 ml aliquot from Part A reacts 
with TiCl.sub.4 : 
##STR32## 
(iii) Coupling: 
##STR33## 
One-third of the polymerization mixture from Part A (11.1 ml) was cooled to 
0.degree. and treated with 0.3 g (1.9 mmol) of bromine in 5 ml of 
1,2-dichloroethane. After the red bromine color disappeared, a solution of 
0.4 ml of TiCl.sub.4 in 5 ml of 1,2-dichloroethane was added, whereupon a 
precipitate formed. The mixture was allowed to warm to room temperature, 
stirred for 1 h, and then evaporated. The residue was dissolved in 20 ml 
of acetone and precipitated from hexane to give 4.45 g of polymer. This 
was identified by HPLC, NMR and GPC to be a di(trimethylsilyloxy)-PMMA, 
hydrolyzable to dihydroxy PMMA. GPC: M.sub.n 3600, M.sub.w 4400, D 1.23 
(theor. M.sub.n 2392). 
C. Reaction with Benzyl Bromide (Capping) 
##STR34## 
R has the same meaning as in Part B. 
An aliquot (11.1 ml) of original polymerization reaction mixture from Part 
A was cooled to -43.degree. under argon. To this was added 0.7 g of benzyl 
bromide. The solution was stirred and allowed to warm to room temperature. 
After stirring for 15 min 3.5 ml of a 1.0M acetonitrile solution of 
tris(dimethylamino)sulfonium difluorotrimethylsilicate was added. The 
solution was stirred at 25.degree. for 11/2 h, after which was added 10 ml 
of methanol. The solvents were evaporated and the polymer was precipitated 
from hexane; 4.25 g of powdery solid polymer was recovered. GPC: M.sub.n 
2300, M.sub.w 3700, D 1.61 (theor. M.sub.n 1287). 
D. Reaction with 1,4-Xylyl Bromide 
##STR35## 
R has the same meaning as in Part B. 
Following the procedure of Part B, 11.1 ml of the reaction mixture was 
treated with 0.5 g (1.9 mmol) of 1,4-xylyl bromide, 1.1 g of 
tris(dimethylamino)sulfonium difluorotrimethylsilicate to give 4.31 g of 
.alpha.,.omega.-masked-dihydroxy PMMA. 
GPC: M.sub.n 3400, M.sub.w 4200, D 1.24 (theor. M.sub.n 2494). 
EXAMPLE 5 
Preparation of Three-Branched Star Poly(Ethyl Acrylate) 
To a solution of 0.93 ml (1 mmol) of 25% triisobutylaluminum in toluene in 
20 ml of methylene chloride was added 9 .mu.l of water (0.5 mmol). The 
resulting solution was cooled to -78.degree., and 1.8 ml (9 mmol) of 
[(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane was added followed by 
0.89 g (0.86 ml, 3 mmol) of purified trimethylolpropane triacrylate. After 
10 minutes, 9.7 ml (90 mmol) of ethyl acrylate was added at a rate such 
that the temperature remained below -70.degree.. After stirring for 10 
minutes at -78.degree., 2 ml of methanol was added, and the solution was 
evaporated in vacuo to 10.4 g of viscous poly(ethyl acrylate). Gel 
permeation chromatography (GPC) showed M.sub.n 2190, M.sub.w 3040, D 1.39 
(theoretical M.sub.n 3300). 
The trimethylolpropane triacrylate used in this example was purified by 
stirring 50 g with 1 liter of hexane. The hexane extract was passed over a 
column of neutral alumina under argon and evaporated in vacuo. 
EXAMPLE 6 
Preparation of Four-Branched Star Poly(Ethyl Acrylate) 
To a solution, in 20 ml of methylene chloride, of 0.93 ml (1 mmol) of 25% 
triisobutylaluminum in toluene was added 9 .mu.l of water. The resulting 
solution of "bis(diisobutylaluminum)oxide" was cooled to -78.degree. and 
treated with 2.4 ml (12 mmol) of 
[(1-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane. Then, 1.29 g (3 mmol) 
of 81.5% pentaerythritol tetraacrylate in hexane-methylene chloride was 
added, keeping the temperature below -70.degree.. After 10 minutes 13 ml 
(120 mmol) of ethyl acrylate (purified by passage over neutral alumina 
under argon) was added at a rate to keep the temperature below 
-70.degree.. After stirring for 15 minutes at -78.degree., 3 ml of 
methanol was added, and the solution was evaporated in vacuo to 16.2 g of 
viscous poly(ethyl acrylate). Gel permeation chromatography showed M.sub.n 
2400, M.sub.w 2970, D 1.24 (theoretical M.sub.n 4752). 
The pentaerythritol tetraacrylate used in the example was a commercial 
sample purified by treatment of 50 g with 7:1 hexane:methylene chloride, 
adding additional methylene chloride until solution occurred. Then, hexane 
was added until a small amount of liquid had separated. The hexane 
solution was decanted and evaporated in vacuo. The residue was treated 
with 10 ml of methylene chloride and passed through a neutral alumina 
column under argon. 
EXAMPLE 7 
Preparation of Three-Branched Star Poly(methyl methacrylate) 
A. To 4.41 ml (3.838 g, 12.87 mmol) of tris(trimethylsilyl)phosphite at 
65.degree. was added slowly 1.0 g (4.29 mmol) of 
trimethylolpropanetriacrylate (purified by extraction with hexane and 
passage of extract through neutral alumina). After 1 h, NMR showed no 
residual acrylate and was in agreement with 
##STR36## 
a viscous oil. 
Anal. Calcd. for C.sub.42 H.sub.101 O.sub.15 P.sub.3 Si.sub.9 : C, 42.32; 
H, 8.54; P, 7.80; Si, 21.21. Found: C, 41.05; H, 8.17; P, 8.87; Si, 19.91. 
B. To a solution of 1.91 g (1.6 mmol) of the product of Part A in 30 ml of 
tetrahydrofuran was added 0.1 ml of 1M tris(dimethylamino)sulfonium 
bifluoride/acetonitrile and 15 g (16.2 ml, 150 mmol) of methyl 
methacrylate. A slow exothermic reaction was observed. After stirring 18 
h, the solution was evaporated in vacuo to 12.6 g (80.7%) of solid 
polymer. GPC: M.sub.n 13,000, M.sub.w 28,600, D. 2.20 (theoretical M.sub.n 
7500). 
To convert the silylphosphonate terminal groups to phosphonic acid groups, 
the product was stirred at reflux for 1 h with 15 ml of methylene 
chloride, 6 ml of methanol, and 1 ml of 1M tetrabutylammonium 
fluoride/tetrahydrofuran. The solution was evaporated and the residue was 
dissolved in methylene chloride, washed with water, dried and 
concentrated. The purified three-star triphosphonic acid polymer was 
precipitated with hexane to give 6 g of solid polymer. The NMR spectrum 
showed the absence of any trimethylsilyl groups. 
EXAMPLE 8 
Preparation of a Triblock Terpolymer of Methyl Methacrylate (MMA), n-Butyl 
Methacrylate (BMA), and Allyl Methacrylate (AMA), Catalyzed by Bifluoride 
Ion 
A 250 ml reactor, fitted with an argon inlet, a stirrer, thermocouple and a 
syringe pump, was charged with tetrahydrofuran (50 ml), 
tris(dimethylamino)sulfonium bifluoride (0.05 ml, 1M in CH.sub.3 CN) and 
[(2-methoxy-2-methyl-1-propenyl)oxy]trimethylsilane (1.25 ml, 6.25 mmol). 
MMA (10.7 g, 106.9 mmol) was then added via a syringe pump over 15 
minutes. The temperature rose from 24.8.degree. to 51.6.degree. 
accompanied by an increase in the viscosity of the mixture. The reaction 
mixture was stirred and allowed to cool to 38.6.degree.. Then BMA (9.0 g, 
63.3 mmol) was added over 15 minutes. The temperature rose to 
43.2.degree.. The addition process was repeated with AMA (5.34 g, 42.5 
mmol) and the temperature rose from 33.degree. to 39.2.degree.. The clear 
colorless mixture was stirred until the temperature dropped to 23.degree. 
and then was treated with methanol (10 ml) containing phenothiazine (0.1 
mg). The solvent was evaporated and the residue was dried; yield 23.72 g. 
M.sub.n 3800, M.sub.w 4060, D 1.07 (theoretical M.sub.n 4100). The polymer 
showed Tg.sub.1 -19.degree., Tg.sub.2 38.degree., Tg.sub.3 108.degree., 
corresponding to poly(allyl methacrylate), poly(n-butyl methacrylate) and 
poly(methyl methacrylate) segments, respectively. 
EXAMPLE 9 
Polymerization of Methyl Methacrylate with 
Bis[(1-methoxy-2-methyl-1-propenyl)oxy]methysilane and 
tris(dimethylamino)sulfonium Bifluoride 
To a solution, in 20 ml of anhydrous tetrahydrofuran, of 
bis[(1-methoxy-2-methyl-1-propenyl)oxy]methylsilane (1.23 g, 5 mmol), 
prepared by the reaction of methyldichlorosilane with the lithium enolate 
of methyl isobutyrate (bp 54.8.degree./0.5-57.2.degree./0.7 mm), and 20 
.mu.L of 1M tris(dimethylamino)sulfonium bifluoride/acetonitrile was added 
10 g (10.8 ml, 100 mmol) of methyl methacrylate (purified by passage over 
neutral alumina under argon) containing 10 .mu.l of 1M 
tris(dimethylamino)sulfonium bifluoride. An exothermic reaction persisted 
during the monomer addition. After 30 minutes 5.0 g (5.4 ml, 50 mmol) of 
methyl methacrylate was added, producing an exothermic reaction. Addition 
of 3 ml of methanol produced an apparent decrease in viscosity. 
Evaporation in vacuo gave 17.5 g of solid poly(methyl methacrylate). 
Gel permeation chromatography shows M.sub.n 1410, M.sub.w 1550, D 1.10 
(theoretical M.sub.n 1600). 
EXAMPLE 10 
Polymerization of Methyl Methacrylate with 
[3-methoxy-2-methyl-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic Acid, 
Bis(trimethylsilyl) Ester and Tris(dimethylamino)sulfonium Bifluoride 
A. [3-Methoxy-2-methyl-3-((trimethylsilyl)oxy)-2-propenyl]phosphonic acid, 
bis(trimethylsilyl) ester was prepared by stirring a mixture of equimolar 
amounts of methyl methacrylate and tris(trimethylsilyl)phosphite at 
114.degree. for 3.5 h under argon. The product was distilled in a small 
Vigreux column, b.p. 91.degree./0.23 mm, Anal, Calcd. for C.sub.14 
H.sub.35 O.sub.5 PSi.sub.3 : C, 42.18; H, 8.85; P, 7.77, Si 21.14. Found: 
C, 42.17; H, 8.54, P, 8.07; Si 21.12. 
B. To a stirred solution of 3.12 g (3.2 ml, 7.84 mmol) of the phosphonic 
acid ester prepared in Part A and 0.3 ml of a 1M solution in acetonitrile 
of tris(dimethyamino)sulfonium bifluoride in 100 ml of tetrahydrofuran 
under an argon atmosphere was added during 1 h 55 ml (50.9 g, 509 mmol) of 
methyl methacrylate (purified by passage over a short column of neutral 
alumina). The solution was stirred for two h after the end of the 
exotherm. Then, 30 ml of methanol and 2 ml of 1M 
tetrabutylammonium/tetrahydrofuran was added and the resulting solution 
was stirred at reflux for 1.5 h and concentrated in a rotary evaporator. 
The product was precipitated from the concentrated solution by addition to 
water. The polymer was filtered and dried in a vacuum oven at 100.degree. 
to give 49.7 g of poly(methyl methacrylate-1-phosphonic acid). GPC: 
M.sub.n 5900, M.sub.w 5900, D 1.00 (theoretical M.sub.n 6650); .sup.1 H 
NMR: .delta.(ppm from external Me.sub.4 Si, CDCl.sub.3 solvent) 7.9 ppm 
[broad, PO(OH).sub.2 ]. 
EXAMPLE 11 
Polymerization of Methyl Methacrylate with Tris(trimethylsilyl)phosphite 
and Bifluoride Catalyst 
To a stirred solution of 1.49 g (1.75 ml, 5 mmol) of 
tris-(trimethylsilyl)phosphite and 0.31 ml of 1M 
tris(dimethylamino)sulfonium bifluoride/acetonitrile in 15 ml of 
tetrahydrofuran under argon was added 10 g (10.8 m, 100 mmol) of methyl 
methacrylate. After 20 minutes an exothermic reaction was observed, and 
the temperature rose to 36.degree.. After stirring 18 h the viscous 
solution was evaporated in vacuo to 12.1 g of solid 
phosphonate-substituted poly(methyl methacrylate). GPC: M.sub.n 15,300, 
M.sub.w 29,400, D 1.92 theoretical M.sub.n 2300). 
EXAMPLE 12 
A. If 365 g of a copolymer of methyl methacrylate and 
2-trimethylsiloxyethyl methacrylate, prepared as in Example 22 of 
copending application Ser. No. 389,110, filed June 17, 1982, now U.S. Pat. 
No. 4,417,034 is dissolved in 135 g of xylene, a solution containing 73% 
solids by weight can be obtained. 
B. The following compositions can be prepared and then blended together to 
form a high-solids light blue enamel: 
______________________________________ 
Parts By 
(i) Silica Mill Base Weight 
______________________________________ 
Acrylic polymer solution 
389.65 
(from Part A) 
Xylene 200.92 
Ethylene glycol monoethyl 
200.84 
ether acetate 
Fine divided silica (treated 
56.59 
with dimethyl dichloro silane) 
Total 848.00 
______________________________________ 
The above constituents can be charged into a conventional sand mill and 
ground to form a mill base. 
______________________________________ 
Parts By 
(ii) Iron Pyrophosphate Mill Base 
Weight 
______________________________________ 
Acrylic polymer solution 
494.24 
(from Part A) 
Xylene 233.28 
Iron pyrophosphate pigment 
207.48 
Total 935.00 
______________________________________ 
The above constituents can be charged into a conventional sand mill and 
ground to form a mill base. 
______________________________________ 
Parts By 
(iii) Indo Blue Mill Base Weight 
______________________________________ 
Acrylic polymer solution 50.00 
(60% solids in a solvent mixture 
of petroleum naphtha, 
ethylene glycol monoethyl ether 
acetate, and butanol, of a polymer of 
styrene/butyl acrylate/hydroxy- 
ethyl acrylate/acrylic acid, weight 
ratio 50/38/8/4 prepared by 
conventional free radical 
polymerization) 
Butyl acetate 43.00 
Indanthrone Blue Toner 7.00 
Total 100.00 
______________________________________ 
The above constituents can be mixed together and then ground in a 
conventional sand mill to form a mill base. 
______________________________________ 
Parts By 
(iv) Blue Mill Base Weight 
______________________________________ 
Portion 1 
Acrylic polymer solution 
14.30 
(described for composition (iii)) 
Butyl acetate 57.70 
Portion 2 
"Monastral" Blue pigment 
8.00 
Portion 3 
Acrylic polymer solution 
20.00 
(described for Portion 1) 
Total 100.00 
______________________________________ 
Portion 1 can be charged into a mixing vessel and mixed for 15 minutes, 
Portion 2 can be added and mixed for 1 h and Portion 3 can be added and 
mixed for 1 h. The resulting composition can be ground in a conventional 
sand mill to form a mill base. 
______________________________________ 
Parts By 
(v) Aluminum Flake Mill base 
Weight 
______________________________________ 
Acrylic polymer solution 
509.41 
(from Part A) 
Xylene 198.91 
Aluminum paste (65% aluminum 
188.68 
flake in mineral spirits) 
Total 897.00 
______________________________________ 
The above constituents can be thoroughly mixed together to form a mill 
base. 
______________________________________ 
Parts By 
(vi) Para-Toluene Sulfonic Acid Solution 
Weight 
______________________________________ 
Para-toluene sulfonic acid 
131.54 
Methanol 515.08 
Dimethyl oxazolidine 92.38 
Total 739.00 
______________________________________ 
The above constituents can be thoroughly blended together to form an acid 
solution. 
A light blue paint can be prepared by thoroughly blending together the 
following constituents: 
______________________________________ 
Parts By 
Weight 
______________________________________ 
Silica mill base (described 
196.00 
above in Part (i)) 
Iron pyrophosphate mill base 
29.45 
(described above in Part (ii)) 
Acrylic polymer solution 
210.22 
(from Part A) 
2-(2'-hydroxyphenyl)- 8.67 
benzotriazole 
Nickel bis-[O--ethyl(3,5 di- 
4.34 
tertiary-butyl-4-hydroxy- 
benzyl)phosphonate] 
Tetrakis methylene 3-(3',5'- 
0.41 
dibutyl-4'-hydroxyphenyl)- 
propionate methane 
Methanol 30.27 
Blue mill base (described above 
5.07 
in Part (iv)) 
Indo blue mill base 19.39 
(described above in Part (iii)) 
Aluminum flake mill base 
66.67 
(described above in Part (v)) 
Melamine resin (methoxy/butoxy- 
174.24 
methyl melamine) 
Methyl amyl ketone 25.03 
Methyl isobutyl ketone 
24.46 
Diisobutyl ketone 24.70 
Para-toluene sulfonic acid 
7.36 
solution (described above 
in Part (vi)) 
Amine solution (25% dimethyl 
14.72 
oxazolidine in methanol) 
Total 841.00 
______________________________________ 
The above described composition can be sprayed onto a steel panel primed 
with an alkyd resin primer and baked for 30 minutes at about 120.degree. 
to give a finish which is expected to be glossy and hard, with a good 
appearance, resistant to weathering, solvents, scratches and chipping. 
These properties indicate utility for finishing automobiles and trucks. 
C. A clear enamel composition can be prepared by blending: 
______________________________________ 
Parts By 
Weight 
______________________________________ 
Acrylic polymer solution 
89.04 
(from Part A) 
Melamine resin 35.00 
(methoxymethyl melamine) 
Para-toluene sulfonic acid 
0.20 
Xylene 42.43 
Total 166.67 
______________________________________ 
D. A steel panel can be sprayed with the color coat of Part B, then baked 
at 120.degree. for 30 minutes, flash dried and then sprayed with the clear 
coat of Part C. It is expected that a color coat/clear coat finish would 
be formed that has excellent gloss and appearance and would be durable and 
weatherable and useful as an exterior finish for trucks and automobiles. 
EXAMPLE 13 
The following constituents can be blended together to form a lacquer paint: 
______________________________________ 
Parts By 
Weight 
______________________________________ 
Portion 1 
Acetone 9.30 
Alkyd resin solution 9.53 
(85% solids alkyd resin of 
ethylene glycol/phthalic 
anhydride/coconut oil having 
a hydroxyl No. of about 20 
and an acid No. of about 8-10 
in toluene and having a Gardner 
Holdt viscosity of about 2 
measured at 25.degree. ) 
Portion 2 
Aluminum flake mill base 15.48 
(29.8% polymethyl methacrylate*, 
12.4% aluminum flake and 57.8% 
solvent mixture of toluene and 
acetone) 
Blue Mill base (10% 3.39 
"Monastral" blue flake, 16% poly- 
methyl methacrylate*, 74% 
solvent mixture of toluene 
and acetone) 
Carbon Black Mill Base 0.33 
(6% carbon black pigment, 24% 
polymethyl methacrylate*, 70% 
solvent mixture of toluene, 
acetone, ethylene glycol 
monoether acetate, butyl 
acetate 
Green Mill Base 0.36 
(8.3% "Monastral" green 
pigment, 21.1% polymethyl- 
methacrylate*, 70.6% solvent 
mixture of toluene/acetone/ 
xylene) 
Portion 3 
Silicone solution (4% silicone 
0.03 
SF69 in xylene 
PMMA solution (40% solids 26.96 
of polymethyl methacrylate in 
THF (prepared as in Example 21 
of application Serial No. 389,110, 
filed June 17, 1982, now U.S. Pat. No. 4,417,034) 
CAB solution (25% solids 12.98 
cellulose acetate butyrate 
having a 37% butyryl content 
2 second viscosity in toluene/ 
acetone, 70/30 ratio) 
CAB Solution II (15% solids 
21.64 
cellulose acetate butyrate 
having a 38% butyryl content 
and a 20 second viscosity in 
toluene/acetone, 70/30 ratio 
Total 100.00 
______________________________________ 
*polymer prepared by conventional freeradical polymerization 
Portion 1 can be charged into a mixing vessel and mixed for 10 minutes, 
portion 2 can be added and mixed for 10 minutes and then portion 3 can be 
added and mixed for 20 minutes to form a lacquer paint. 
The reduced lacquer can be sprayed onto phosphatized steel panels primed 
with an alkyd resin primer and coated with a sealer. Three coats may be 
sprayed onto the panels and the panels baked at about 165.degree. for 30 
minutes to provide a finish of about 2.2 mils thickness. 
The resulting finish is expected to be smooth, glossy, water resistant, 
gasoline resistant, chip resistant and weatherable, with excellent 
distinctness of image, useful as a high quality automotive coating. 
EXAMPLE 14 
An aqua metallic air drying enamel was prepared from the following: 
______________________________________ 
28.5 parts Carbon black 
11.0 parts Phthalo blue toner 
42.5 parts "Monastral" Green cake 
19.0 parts Phthalo blue cake 
157.0 parts Aluminum paste-medium 
8.0 parts Titanium dioxide pigment 
390.0 parts Polymer (prepared as in 
Example 13A of application 
Serial No. 389,110 filed 
June 17, 1982, now U.S. Pat. No. 4,417,034) 
110.0 Parts Xylene 
110.0 parts Cellosolve acetate 
4.0 parts Cobalt naphthenate 
______________________________________ 
The above composition was sprayed onto a steel panel primed with an alkyd 
resin primer and allowed to cure at ambient temperature. After about a 
week, the finish was hard and resistant to solvents and scratches. 
Best Mode For Carrying Out The Invention 
The best mode presently contemplated for carrying out the invention is 
demonstrated and/or represented by Examples 1 to 9 and 12 to 14. 
Industrial Applicability 
The invention process provides useful and well known polymers containing 
functional substituents, for example, homopolymers and copolymers of 
acrylate and/or methacrylate monomers, such polymers heretofore being made 
usually by anionic polymerization techniques. The invention process also 
provides a means for making certain commercially desirable, relatively 
monodisperse copolymers of methacrylate and acrylate comonomers, such 
copolymers being difficult or impossible to obtain by known processes such 
as anionic polymerization or free-radical polymerization. The invention 
process also provides "living" polymer which may be cast or spun, for 
example, into a film or fiber, from solution or dispersion (in or using an 
aprotic solvent) or isolated, processed, and then further polymerized. The 
solutions or dispersions may also be formulated with clear or opaque 
pigments and other ingredients which can be converted into protective 
coatings and finishes for manufactured articles, such as metal, glass and 
wood. 
Although preferred embodiments of the invention have been illustrated and 
described hereinabove, it is to be understood that there is no intent to 
limit the invention to the precise constructions herein disclosed, and it 
is to be further understood that the right is reserved to all changes and 
modifications coming within the scope of the invention as defined in the 
appended claims.