CA1232999A - Process for preparing "living" polymers - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

"Living" polymers and their preparations from acrylic monomers of the formula CH2=C(Y)X where X is -CN, -CH=CHC(O)X' or C(O)X', X' being defined hydrocarbyl groups or derivatives thereof, and Y being -H, -CH3, -CN or CO2R where R is hydrocarbyl, and/or from hydrocarbyl-substituted maleimide monomers using defined organosilicon, organotin and organogermanium initiators and bifluoride ion co-catalysts are described. The invention provides homopolymers and copolymers of acrylate and/or methacrylate monomers, especially relatively monodisperse copolymers of methacrylate and acrylate comonomers. The polymers may be used in the manufacture of fibres, films and finishes for metal, glass and wood.

Case CR-8129B

Description

"LIVING" POLYMæRS AND PROCESS FOR TH~IR PREPARATION
De~cripl:ion Technical Field Thi6 invention relate~ to a proce66 for polymerizing polar a-olefinic monomer~ to "living"
polymers and to the "living" polymer6 produced by 6uch a proce6~.
Backqround The 1:1 addition of a,~-un~atura~ed ester6, ketone~, and nitriles to activated "donor~' compounds, for example, 6ilicon- or tin-containing ~donor~ compound6, is well known. Such reac~ions may be referred to as Michael type addition reaction~ and are catalyzed by ba6e6, 6uch as a fluoride or cyanide, or by Lewis acid6, 6uch as zinc chloride, boron trifluoride, titanium tetrachloride, or hydrogen bromide.
K. Saigo et al., Chem. Letter6, 2, 163 (1976) di6clo6e that when methylvinyl ketone or cyclohexenone is employed as a Michael acceptor in the presence of 0-silylated ketene acetals and titanium tetrachloride, the desired product i8 obtained in low yields and a polymeric by-produc~ is produced. The polymer wa6 not i601ated or identified and mean6 are di6closed for minimizing the by-product by modifying the titanium tetrachlocide cataly6t by including therewith tetraisopropyl titanate.
U.S.S.R. Patent 717,0S7 di~closes organo6ilicon acetals of the formula Ro-cH(cE~3)-osiR 3_n(0R )n~
and their u~e a6 intermedia~e6 in the preparation of perfume~ and in the production of polymers and flotation agent6, wherein R is C3H7, C6H5, C~-=CCH2, C~CC(CH3)~ or menthyl; R' i6 Cl_4 alkyl or C6E150CH(CE13), and n i5 O or 1.

~ , U.S.S.R. Patent 715,583 disclosefi trimethylsiloxyethyl esters of the formula RC(O)X~CII(CH3)-OSi(C~I3)3, useful as intermediate~ in the manufacture of medicinals, plasticizers, and polymers, ,and as agricultural pesticid~s and perfumes and in food manufacture, wherein X i6 oxygen or sul~ur and R i6 lower alkyl, chloroalkyl o~ optionally fiubstitu~ed alkenyl.
Stork et al., JACS 95, 6152 ~1~73) disclo6e the use of a-silylated vinyl ketones ~o prevent the pclymerization of ~imple alkyl vinyl ketones via their enolate ions during Michael addition reactions.
The use of trialkyl~ilyl groups as temporary protectant6 for hydroxyl function~, removal by ~ubsequent hydrolysis, is well known in the art, for example, Cunico et al., J. Org. Chem. 45, ~797, (1980).
U.S. Patent 4,351,924 discloses ~- and a,~-hydroxyhydrocarbyl-(alkyl methacrylate) polymers prepared by anionic polymerization, and block and 6tar polymers prepared therefrom by reaction with multifunctional bromomethyl compound6.
U.S. Patent 4,293,674 discloses dienyl ester6 of methacrylic acid, and homopolymers and copolymer6 thereof prepared by anionic polymerization~
Sato et al., Polymer 24, 1018 (1983) di6close syntheses of block copolymer6 by reacting living poly(N-phenylmethacrylamide) radicals with vinyl monomer6 such a~ methyl methacrylate.
U,S. Patents 4,414,372 and 4,417,034 disclose "living" polymers and processes for their preparation.
Disclosure of the Invention For further comprehenfiion of the invention, and of the objects and advantages thereof, reference may be made to the following desc~iption and to the appended claims in which the various novel features of the invention are more particularly set fort~.
The invention resides in a process comprising polymerizing ~he ~onomer selected from the group consisting of CH ~ C~

CH2~C(Y)X , \N/ and mixtures thereof R
w~erein:
~ i8 -CN, -CH~CHC(O)~' or -C(O)~';
Y i~ -H, -CH3, -CN or -C02R, provided, however, when X i6 CH~CHC(0~', Y is -H or -CH~;
~' is -oSi(R )3, -R, -OR or -NR'R";
each Rl, independently, i6 hydrocarbyl of up ~o 2~ carbon atoms:
R is hydrocarbyl of up to 20 carbon atoms, optionally containing one or more ether oxygen atoms within aliphati~ segment~
thereof, and optionally containing one or more functional sub6tituent6 that are unreactive under polymerizing conditionfi; and each of R' and R" i~ independently selected from Cl 4 alkyl by contacting the one or more monomers under polymerizing condition6 with:
(i) the initiator of the formula (R )3MZ
wherein:
Rl i6 a~ defined above;

Z i6 an activating ~ub~;tituent 6elected from ~ he group con~i~ting of R 2 R 2 o -CN, -C-CN, -C--CX~, ~3 R3 ~2 R2 ,. . .. .
C~--C- C----C--Z' I ~
~CH2 ~ ~CH2 ~n -N=C=C-R , -OC~C-RZ , -OC~=~CR
X' R3 z, ~CH2 ~m -OC_~CR2 and ~ixture6 thereQf

2~Jn ~' i6 a6 defined above for the monomer:
each of R2 and R3 i~ independently 6elected from H and hydrocarbyl of up to 20 carbon atoms. optionally containing one or more ether oxygen atom6 within aliphatic segmen~6 thereof, and optionally coneaining one or more functional 6ub6tituent6 that are ~nreactive under poly~erizing condition6 and Z' ifi O or N~ especially O or NR';
m i6 2, 3 or 4;
n is 3, 4 or 5; and M i6 Si, Sn, or Ge, provided, however when Z i6 -OC__CR " C-~y cH2 tJn ~cH2 Jm M i6 Sn or Ge; and (ii.) a co-cataly6t which i6 a ~ource of fluoride, cyanide or azide ion6 or a 6uitable Lewis acid or a ~;ource of bifluoride ions HF2~3 to produce ~living~ polymer having repeat uni~6 of the one or more monomers, ~aid proce~ further characterized in that:
(a3 Rl i6 ~, provided that at lea~t one group i~ not H; and~or (b) R i~ a polymeric radical containing at least 20 carbon atoms and optionally containing one or more ether oxygen atom~ within aliphatic ~egment~
thereof and optionally containing one or more functional 6ub~tituent6 that are unreactive under polymerizing condition~; and/or (c) at lea6t one of any ~ group in ~he monomer contain6 one or more reactive 6ub6titutent~ of the formula -Z'(0)C~C(Y13-CH2 wherein yl ifi H or CH3 and Z' is a6 defined above: and/or ~ d) the initiator i6 of the formula (Rl)2M~Z1~2 or OtM(Rl)2Zl]2 wherein l and M are as defined above and zl is -OC=C-R 2 ~'R3 wherein ~', R2 and R3 are a~ defined above; and/or

3~

5e) a~ lea~t one of any R, R2 and R3 in ~he initiator contain6 one or more initiating sub6titutent~ o~ ~he formula -Z2-M(~1)3 wherein M and Rl are a~ defined abo~e; and i6 a diradical 6elected from the group .. .. .
con~i6ting of -Z'-C~C(R2)(R3), -C(R2)-CX~, -Z'-C-C- , "
-C(R2~=CX' , C ~ C- , -OC _ C-O- Z I ~ I
~:CH2 ~J ~Y CE12 ~3 ,. . .
C- C- , -OC _ C- , -C-R and mixture6 ~ CH2 ~ ~ CH2Jn CN
thereof, wherein R2, R3, X', Z', m and n are a ., .
defined above, provided, however, when z2 i~ C C-.
~CH~
i~ Sn or Ge: and/or (f) Z i~ ~elected from the group con~i6ting of ~SR~ -OP(NR'R")2, -OP(OR )2~ -oP[oSi~R )3]2 and mixture~ ~hereof, wherein R, Rl, R' and R" are a6 defined above: and~or ~g) R2 and R3 taken together are ~Q~

~13C ~C

CH~

"
provided, however, Z is -C-CX~ or -OC=C(R )~R ~ and/or ~3 X' o Z2 ifi -Z ~ -C-C (R2)(R3)-: and/or (h~ Xl and either R2 or R3 taken together are ~~ C ~
Rl~ --R

., provided, however, Z i6 -C-CX ' or -OC2C(R )(~ ) R3 ~, o and~or z2 i~ -C(R2)-CX~
By "living" polymer i~ meant a polymer of the inveneion which contain6 at lea~t one active terminal group and i~ capable of polymerizing further in ~he pre6ence of monomer(s) and co-cataly~t.

3~3 It will be under~tood by one skilled in t~e art that the la6t four member6 of the afore6aid qroup from which the activating ~ub6tituent Z i6 6elected are the re6pective ketene imine or enol form6 of the previou6 four member6 of the group. The mixtures of such member6 which are operable herein include, but are not limited to, the corresponding cyano-imine or keto-enol ~ix~ures.
The polymer6 produced by the proce66 of the in~ention are "living" polymer6 of the formula X _ _ Z"[CH2-C ~ - CH CH -QM(R )3 Y o~C~N,C~o L
R a wherein:
Z" ic celected from the group con6i6ting of R2 R2 ~o~ ~ C~ C~ C~
-CN, -C-CN, -C ~CX', Z' \ and R3 R ~ 2~m ~CH2~

each of a and b i6 independently ~elected from O
or a number in the range 1 to about 100,000, provided, ~owever, (a + b) i6 at lea6t 3:
Q i6 the divalent radical 6elected from the group consisting of ~3~C ~
g ,~ .

-CH2-C-, -C~l~-C-Y. -~H2-C-Y , -CE12-C-Y
y -CH - CH- -CH - CH
. ..
~ \N f ~ N
R R
and ~ixtures thereof;
X i6 -CN, -CH=CIIC(O~' or -C(O)~':
Y i~ -H, -C~13, -CN o~ -CO2R, provided, however, when ~ i~
~CH=CHC(O)~:, Y is -H or -CH3:
~ -05i(~ )3~ -R, -OR or -NR'R";
each Rl, independently, is hydrocarbyl of up to 20 carbon atoms;
R is hydrocarbyl of 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;
each of R' and R" is independently selected from Cl_4 alkyl;
each of R and R is independently selected from H and hydrocarbyl of up to 20 carbon atoms, optionally containing one or more ether oxygen atoms within aliphatic s~gments thereof, and optionally containing one or more functional substitue~ts that are unre~ctive under polymerizing conditio~s;
Z~ i~ o or N, especial]y 0 or NR';
m i~ 2, 3 or 4:
n ifi 3, 4 or 5: and M i~ Si, Sn, or Ge, said polymer further characterized in that:
(a) Rl i6 H, provided ~hat at lea~t one Rl group i~ not H: and/or (b) Z~ i6 selected from -P(O)(NR'R~) -P(O)(ORl)2, -P()t~s~ )3~2 and -S~:
and/or (c) the "living~ polymer i~ of the formula Rp([Z PQM(R133 k~l+k()k)p or Rp~[Z PQ(R )~2M)p wherein:
Rp i~ a hydrocarbyl radical which i~
aliphatic, alicyclic, aromatic or aliphatic-aromatic containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon a~oms, of valence p, optionally containing one or more ether oxygen atoms, keto qroup~ and/or functional 6ubstituents that are unreactive under polymerizing conditions~
Z is a diradical 6elected from the group consisting of --Z'--C(O)--C-- ~ --C-- , --C-- , C ~ ~
R C~O)X' CN CH2 ~

., .
C -- ~ C--z J
--~CH2~

lOa and muxtures thereof;
Z', R , R , X~, m anld n are as defined above;
P i~ a divalent polyl~eric radical of the formula _ ._ (CH2-c ~ - - CH _ _ CH - ~
C ~ ~ C ~ a R
wherein X, Y, R, a and b are a~ defined above:
Q, M and Rl are a6 defined above:
k is 0 or 1: and p i6 an integer and i6 at least 1. but at lea~t 2 when k i6 O, provided, however, o (i) when Z3 is C - - C-~CE~2~) M is Sn or Ge;

(ii) when Z3 is -Z'-C(O)-C-E~2 and R3 taken together i6 H3C ~CEI3; and ~3 lOa 10b (iii) ~hen Z3 i~ C- , ~2 and ~' taken C ~ O ) X ' ~ogether i~ O \ / O

Rl~ \Rl Invention also resides in a process comprising quenching with an active hydrog~n ~source the "living" polymer of t:he formula selected from _ _ Z~[CH2-C ~ I CH CH I QM(R )3 Y 0~ ~ N f ~O
_ R _ a p ( )3-k]l+k()k)p and Rp([Z PQ(Rl)~zM) wherein:
Z" i6 6elected from t~e group consi~ting of R2 ~2 o C - C- " C--CN, --C-CN, -C--CX', Z' ~ and ¦ ¦ ;
R3 R3 ~ CH2~m ~CH2~n -P(O)(NR'R")2. -P(O)(OR )2~ -p(o)tosi(R )3]2 and -SR:
eac~ of a and b i~ independently selected from 0 or a number in t~e range 1 to about 100,000, provided, howe~er, (a-tb) i~ at lea~t 3:

10b ~4~ 3 lOc~
Q i6 the divalen~ radical 6elected from ~he grsup consi6ting of X CN - C~ - C~l = CO- CO-" " ..
-C~12- -' -CH~-C-Y, -C~2-C-Y -C~2-C-Y , -CH - C~ , -CH - CH

R R

and mixtures thereof:
X i~ -CN, -CH=CHC(O)X' or -C(O)X';
Y i~; -El, -CH3, -CN or -C02R, pro~ided, however, when ~ i6 -CH=CHC(0)~, Y i6 H or -CH3;
Si5Rl)3, -R, -OR or -NR'R";
each Rl, independently, is hydrocarbyl of up to 20 carbon atom~ or H, provided that at lea~t one Rl group i6 not H:
R i6 hydrocarbyl of up to 20 carbon atom~, optionally containing one or more ether oxygen atoms within aliphatic segment6 thereof, and optionally containing one or more functional 6ub~tituent6 that are unreactive under polymerizing condition6;
each of R' and R~ i6 independently selected from Cl 4 alkyl:
each of R and R i6 independently ~elec~ed from H and hydrocarbyl of up to 20 carbon a~oms, optionally containing one OL more ether oxygen atom6 within aliphatic segment6 thereof, and optionally containing one or more functional 6ub6tituents t~at are unreactive under polymerizing conditions:

lOc lOd Z' i6 0 or N, e~pecially 0 or NR';
m i8 2, 3 OL 4 n i~ ~, 4 or 5;
M i6 Si, 5n or Ge;
Rp i~ a hydrocarbyl radical which i~
aliphatic, alicyclic. aromatic or aliphatic-aromatic containing up to 20 carbon atom~, or A polymeric radical containing at lea6t 20 carbon atom6, of valence p, optionally containing one or more ether oxygen atom~, keto group6 andtor functional 6ub~tituent6 that are unreactive under polymerizing conditions;
Z3 i~ a diradical 6elected from the group consi~ting of ~2 R2 R2 0 --Z'--C(O)--C-- , --C-- , --C-- , C - C--R3 C(0)~' CN ~ CH
o ,. .
C - --C-z~ I
and mixture6 thereof; 2 ~
P is a divalent polymeric radical of the for~ula _ (C~2-C~--_CU - CE~--Y L ~ N ~ l . a lOd k is O or l; and p i~ an integer and i~ at lea~t 1, but a~
lea6t 2 when ~ i~ 0, provided, however, o ., , rt nJ

(ii) when Z i6 -Z'-C(O)-C-~3 R2 and R3 taken together ,~

~iii) when Z3 i~ ~C- , R2 and ~' taken C(O)~ ' together i6 0 ~ ~0 ~ C \ ; and Rl Rl (iv) when Z" is any of the first five groups listed above, at least one but not more than two Rl groups is H.

lOe It i6 readily apparent that the five members of the group defining Z" are the 6ame as the fir~t five member~ of the afore6aid group defining Z and are cyano or keto form6 of Z. Similarly, the third ~ember of the group deining Z~l i6 also the keto form of the aforesaid activating substituent ,~1 ~oreover, the five member~ of t~e group defining Z3 are the same a~ the keto and cyano member6 of the aforesaid group defining the activating diradical z2 . Ie al60 i6 apparent that Q i6 a "living'l polymer unit provided by the starting monomers of the proce~s of t~e invention, a~ originally depicted above, or 6uch unit in it~ enol or imine form. The "living" polymer6 contain terminal groups -M(Rl)~ at their "livin~ll ends or, when polymeri2ation i8 initiated by bifunctional initiator6 of the formula (R )2M(Z )2 or O[M(R )2Z ]2~ central groups -M(Rl)2- or -M(R )2-0-M(R )2- The~e terminal or central groups are attached to carbon if the adjacent Q unit i6 in it6 keto form, and to a hetero atom (o or N) if the adjacent Q unit i6 in it6 enol form. Both tautcmeric form6 may coexi6t in a given "living"
polymer of the in~ention.
In the description of t~e further characterization of the invention, any reference to symbol6 "a6 defined above" means not only a6 defined above in the further characterization but also as defined anyw~ere hereinabove. Thi6 caveat applie6 particularly to the definition6 of R, Rl, R2, R , Z and Z".
The "living" polymer of the invention can be a homopolymer or a copolymer, depending on the monomer or monomerE 6elected for u~e in the proces6 of the invention. Moreover, a6 will be di6cus6ed more fully hereinafter, the "li~ing~ polymer can be linear or ~J~s i~

branched and, depending on the selection of ~, Rp or Z" in the formulas, can be u6ed to prepare cros61inked polymers and block copolymer6.
Monomer~ which are 6ui~able for use in the practice of thi6 invention are, in general, known compounds and include, but are not limited to~ the following: methyl methacrylate; butyl methacrylate;
60rbyl acrylate and methacryla~e; 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 Yinyl ketone; ethyl 2-chloroacrylate; glycidyl methacrylate; 3-methoxypropyl methacrylate;
2-t~l-propenyl)oxy]ethyl methacrylate and acrylate;
phenyl acrylate; 2-~trimethylsiloxy)ethyl methacrylate; 2-tmethyl6iloxy)ethyl methacrylate;
allyl acrylate and methacrylate; unsaturated e6ter~ of polyols, particularly ~uch ester6 of a-methylenecarboxylic acids, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glyceryl triacrylate, mannitol hexaacrylate, 60rbitol hexaacrylate~, ethylene glycol dimethacrylate, hexamethylene diol diacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, ~,l,l-trimethylolpropane triacrylate, triethylene glycol diacrylate, l,4-cyclo~exanediol diacrylate, 1,4-benzenediol dimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol 3 ~3, 3 9 hexaacrylate, pentaerythritol tetraacrylate6, 1,3-propanediol diacrylate, 1,5-pentanediol dimethacryla~e, the bi6-acrylate6 and methacrylate~ of polyethylene glycol~ of molecular weight 200-4000, and a,~-polycaprolactonediol diacrylate; un~aturated N-alkylated amide6, 6uch a6 methylene bi~-(N-methylacrylamide), methylene bis-~N-methylmethacrylamide), ethylene bis-tN-methylmethacrylamide), 1,6-hexamethylene bi6-(N-methylacrylamide), bi6(y-N-methylmethacrylamidopropoxy)ethane;
~-N-methylmethacrylamidoethyl methacrylate;
3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate;
2-(perfluorohexyl)ethyl methacrylate;
2-(perfluoLooctyl)ethyl methacrylate: and mixture~
thereof. Preferred monomer6 include methyl methacrylate; glycidyl methacrylate; sorbyl methacrylate; ethyl acrylate; butyl acrylate; sorbyl acrylate; 2-(trimethyl6iloxy)ethyl methacrylate;
2-methaceyloxyethyl acrylate; 2-acetoxyethyl methacrylate; 2-(dimethylamino)ethyl methacrylate;
~-phenyl-N-methylacLylamide; p-xylylene diacrylate;
1,4-bi~(2-acryloxyethyl)benzene; pentaerythritol triacrylate; l,l,l-trimethylolpropane triacrylate;
pentaerythritol tetraacrylate; triethylene glycol diacrylate; triethylene glycol dimethacrylate;
l,l,l-trimethylolpropane trimethacrylate;

4-acryloxydiphenylmethane; and hexamethylenediol diacrylate and dimethacrylate. ~ethyl methacrylate i~
mo~t preferred.
A~ indicated above in the definition of R in the formulas for the monomer, 6ub6tituent6 that are unreactive under polymerizing condition6 include those having oxygen-, nitrogen-, or silicon-containing group6 which are devoid of reactive hydrogen atom~.

3~

Group6 6uch a6 osi ~R ) 3 and CON~Iz are nonreactive under such con~itions and, therefore, can be tolerated. On the other hand, group6 ~uch a~
Co2H and OH are reactive under polymerizing condieion6. In order for monomers containing such groups on the R 6ubstituent to be useful in t~e invention process, the groups mu6t be chemically protected, i.e. deactivated. Monomer6 containing ~uch deactivated group6 are useful in the preparation of polymer6 which, upon treatment to remove the protective group, have functional ~ite6 along the polymer chain. ~ono~rs which contain suffi~iently 6terically h;ndered amine and alcohol groups that remain inert under reaction condition~ may be u~ed directly ~ithout deactivation. The functional 6ite6 can impart 6pecial properties to the polymer products, including curability and photo~ensitivity.
The definition of R in the monomer formula~
al60 include6 sub6tituent~ which are reactive under polymerizing conditions and of the formula CH2=C(Y 3C(O)Z'- wherein Y and Z~ are a6 defined above. These reactive 6ubstituent6 provide additional centers for initiation of polymerization, leading to the growth of polymeric branches. The reactive ~ubstituent~ are derived from (meth)acrylates or ~meth)acrylamide6 which are them~elves operable monomer6 in the present invention. These 6ubstituents can react with initiator6 of the invention to provide new initiating 6ite6 from which polymeric branches can grow in the presence of monomer(6) and cocataly6t.
Initiator6 which are useful in the invention proce~s include, but are not limited to, the following [(l-methoxy-2-methyl-l-propenyl)oxy]trimethyl6ilane;
[(l-methoxy-2-methyl-1-propenyl)oxy]dimethyloctadecyl-14 :

3~
156ilane; [(1-methoxy-2-methyl-1-propenyl)oxy]methyl-fiilane; 2 (trimethyl6ilyl)i60butyronitrile; ethyl 2-(trimethyl~ilyl~acetate; methyl 2-methyl-2-(tributyl6tannyl)propanoate;
[(2-methyl-1-cyclohexenyl)oxy]tributylstannane;
trimethylsilyl nitrile; methyl 2-methyl-2--(trimethylgermanyl)propanoate;
[(4,5-dihydro-2-furanyl)oxy]trimethyl6ilane;
[(2-methyl-1-propenylidene)bis(oxy)]bi~[trimethyl-6ilane]; [(2-methyl-1-t2-(methsxymethoxy)ethoxy]-l-propenyl)oxy~trimethyl6ilane; methyl t(~-methYl-l-(trimethylsilyloxy)-l-propenyl)oxy]-acetate; [(l-(methoxymethoxy)-2-methyl-1-propenyl)-oxy]trimethyl6ilane: trimethyl a,a',a"-tri6(trimethyl6ilyl~-1,3,5-benzenetriacetate: dimethyl a,'~bis(~rimethyl6ilyl)-1,3-benzenediacetate:
~1,6-dimethoxy-l.S-hexadiene-1,6-diylbi6(oxy)]bi~Ctri-methyl6ilane]; [(2-ethyl-1-propoxy-1-butenyl)oxy]ethyl-dimethyl6ilane; ethyl 2-(trimethyl6tannyl)propanoate;
[(l-cyclohexenyl)oxy]trimethyl6tannane;
[(2-methyl-l-butenylidene)bi6(0xy)]bi6[trimethyl6ilane];
2-(trimethyl~ilyl)propanenitrile; ethyl (trimethylgermanyl)acetate: [(l-((l-dec-2-enyl)oxy)-2-methyl-l-propenyl)oxy]trimethyl6ilane; phenyl 2-methyl-2-(tributyl6tannyl)propanoate; methyl 2-(~riethyl6ilyl)acetate; dimethyl 2,5-bi~(trimethylgermanyl)hexanedioate:
[(2-methyl-1-cyclohexenyl)oxy]tributyl~tannane;
t(l-methoxy-2-methyl-1-propenyl)oxy]phenyldimethyl-~ilane: [(2-methyl-1-[2-(trimethyl6iloxy)ethoxy]-l-propenyl)oxy]trimethyl6ilane;
N,N-dimethyl-(trimethyl6ilyl)pho6phorodiamidite;
(trimethyl6ilyl)dimethyl pho~phite;
tri6~trimethyl6ilyl) pho6phite;
N,N-dimethyl-P-[3-methoxy-3-((trimethyl6ilyl)oxy)-2-16propenyl]pho6phonic diamide:
N,N-dimethyl-P-[3 methoxy-2-methyl-3-((trimethyl6ilyl)-oxy)-2-propenyl]pho6phonic diamide;
t3-methoxY-3-((trimethyl~ )oxyj-2-propenyl]
pho6phonic acid, bi~(trimethylsilyl) e~ter [3-methoxy-2-methyl-3-((trimethyl6ilyl)oxy)-2-propenyl~pho6phonic acid. bi6~trimethyl~ilyl) e6ter:
[3-methoxy-3-((trimethyl6ilyl)oxy)-2-propenyl]-pho6phonic acid, diethyl ester:
t(2-(1,1-dimethylethyl)-5-phenyl-1,3-dioxol-4-yl)-oxy]Crimethyl6ilane; [(2-methyl-5-phenyl-1,3-dioxol-4-yl)oxy]trimethyl~ilane:
t~methoxy)(1,7,7-trimethylbicyclo[2.2.1]heptan-2-ylidene)m~thoxy~trimethyl6ilane:
1,3-bi6[(1-methoxy-l-butenyl)oxy]-1~1,3,3-tetramethyl-di~iloxane;
bis[(l-methoxy-2-methyl-l-propenyl)oxy]methyl6ilane;
bis[(l-methoxy-2-methyl-l-propenyl)oxy]dimethyl6ilane:
and, except when a bifluoride cataly6t i6 u6ed, trimethyl(~ethylthio)~ilane: and trimethyl(phenylthio)6ilane.
Preferred initiator6 include [(l-methoxy-2-methyl-l-propenyl)oxy]trimethyl6ilane:
[(2-methyl-l-prcpenylidene)bi6(0xy)bi6[trimethyl-silane]: trialkyl6ilyl nitriles: and [(2-methyl-1-[2-(trimethyl6iloxy)ethoxyJ-l-propenyl)-oxy]trimethyl6ilane. Trimethyl6ilyl nitrile i6 mo6t preferred.
Example6 of initiator6 which can initiate more ~han one polymer chain include trimethyl a,a'a"-tri6(trimethylsilyl)-1,3,5-benzenetriacetate, dimethyl a, a ' -bi6(trimethyl6ilyl)-1,3-benzenediacetate, 1,6-dimethoxy-1,5-hexadiene--1,6-diylbi6(oxy)bi~-~trimethyl6ilane], and bi6[(1-methoxy-2-methyl-l-propenyl)oxy]methylsilane.
The initiatorfi u~ed in the invention are either known compound6 or can be prepared by known method6 from known 6tarting m,aterial6. Of the initiator6 li~ted abov~, trimlethyl6ilyl nitrile and ethyl trimethyl6ilyl acetate ,are commercially available. Initiator6 of the afore~aid formula (R )3MZ wherein Z i6 R 2 ,R 2 o -C-CN , -C - C-X' or the corresponding ketene imine or enol i60meric forms R2 3 ,R2 -N=C=C-R or -OC=C
~ 3 wherein ~ defined a6 above can be prepared from nitriles ~R )(R ) CHCN, e~ter6, ketone6, or 6ubstituted amide~ (R2)(R3)CHC(o)~' wherein ~ i6 as defined above by reaction with, for example, n-butyllithium or lithium dii60propylamide, followed by reaction with a halide of the formula (Rl)3MCl wherein Rl and M are a6 defined above.
Initiator~ of the aforesaid formula wherein R or R3 i6 CH3 al60 can be prepared from the monomer6 u~ing appropriate procedure6. For example, C~12=C(R3)C(O)X' can be reacted with (Rl)~MH
wherein Rl i6 a6 defined aboYe to produce (Rl)3MZ wherein Z i6 3 ~3 ~

CH~ 0 ., -C--C-~ ' R

In 6till another method, the preferred initiator6 which are trialkylE~ilyl nitrile~ can be prepared in 6itu by treating a ~rialkyl6ilyl chloride with an exce66 of cyanide ion from a suitable 60urce, 6uch a~ tetraalkylammonium cyanide. The re6idual cyanide ion can ~erve as a co-cataly~t for the polymerization.
Simila~ly, initiators of the formula~
(Rl)2M~Zl)2 or O[M(Rl)2Zl]2 wherein Rl, M and zl are a~ defined above are either known compound6 or can be prepared by the above methods employing, for example: dihalides of the formula (R1~2MC12 in pl~ce of halide6 ~Rl)}MCl in the reaction with lithium-containing intermediates as de6cribed above;
or dihydrides (Rl)2~-0-M~I(Rl)2 in place of (Rl)3~1 in the reaction with the monomer~ C~2=C(~3)C(o)~'.
U~eful initiator6 of the invention include tho~e wherein the activating 6ub6tituent Z or z al60 contain6 one or more reactive initiating sub6tituent6, re6ulting in branched polymer6. Such initiators can be prepared in situ by reacting a monomeric compound containing at least one reactive ~ubstituent with a "6imple" initiator (R1~3M~, or precur60r thereof, containing at lea~t one initiating 6ite.
It i6 to ~e under6tood that the useful initiators include nitriles, esters, amide~, and ke~one~, and their corresponding ketene imine and enol form6, all of which are active in the polymerization proces~ of this invention. Moreover, the initiators wherein the activating moiety Z contain~ R, R , and/or R3 can al60 have, like the monomer, one or more functional sub6tituent~ attached to an afore6aid R group, provided ~uch 6ubstituent~ do not interfere with polymerization. Functional ~ub6tituent~ which are useful include. but are not li~ited to, -oSi(Rl)3 . -C02R , -OC(O)R , --NR~R~ C~O)NR~R" , -CN , -OCH(R)OR , -OC(R)(R)OR , -O ~ , -Co2Si(R )3, -C~ - & H2~ -C(C~13) 2 -P(o)NR~R")2~ -P(O)[OSi(Rl)3]2 and -P(O)(ORl)2.
Such 6ub6tituent6, either directly or after treatment, for example, hydroly6i~, provide functional site~
along or at the end of polymer chains suitable for cro66-linking, chain exten6ion, chain branching, or for modifying propertie6 such a6 water 60rption, UV
ab60rption, and the like. In the practice of thi6 invention, a6 described below, an initiator moiety forms one end of a polymer chain or branch and hence said polymer6 can be terminally or centrally functionalized by appropriate initiator fielection and polymer treatment.
The co-cataly6t6 u6ed in the invention proce6~ are eit~er known compoundfi or can be prepared by known method6 from known compound6. Suitable, that i6, effective, co-catalyst6 which are useful in ~he invention proce66 include zinc iodide, bromide, and chloride, mono- and dialkylaluminum halide~, dialkylaluminum oxide6, tri6(dimethylamino)6ulfonium difluorotrimethyl~ilicate, tri6(dimethylamino)6ulfonium cyanide, tetraphenylar60nium cyanide, ~fw~ 39 ~ o tri6~dimethylamino)6ulfonium azide, tetraethylammonium azide, boron erifluoride etherate, alkali metal fluoride~, alkali metal cyanide6, alkali metal azide~, ~ri~(dimethyl~mino)6ulfonium difluorotriphenyl6tannate, tetrabutylammonium fluoride, tetramethylammonium fluoride, and tetraethylammonium cyanide. Preferred co-cataly6t6 include 60urce~ of fluoride ion6, e6pecially tri6(dimethylamino)fiulfonium difluorotrimethyl 6ilicate and tetrabutylammonium fluoride;
tetraalkylammonium cyanide6: zinc bromide, and zinc chloride. Other preferred co-catalysts include sources of bifluoride ions, such as, for example, tri~(dimethylamino)6ulfonium bif luoride, bifluoride6 of the alkali metal~, e~pecially pota6~ium, ammonium bifluoride, tetraalkylammonium bifluoride6 and tetraarylphosphonium bifluoride~.
Tri6(dimethylamino)6ulfonium bifluoride may be prepared by reacting tri6(dimethylamino)6ulfonium difluorotrimethyl6ilicate with water or a lower alkanol, for example, methanol; water i6 preferred 6ince higher yield6 are obtained.
The proce66 ,of the invention i6 carried out at about -100C to about 150C, preferably 0C to 50C, mo6t preferably at ambient temperature. A
~olvent i6 de6irable but not es6ential.
Suitable ~olvents are aprotic liquid~ in which the monomer, initiator and co-cataly6t are 6ufficiently 601uble for reaction to occur; that i6, the material~ are di~601ved at the concentration~
employed. Suitable 601vent6 include et~yl acetate, propionitrile~ toluene, xylene, bromobenzene, dimethoxyethane, diethoxyethane, diethylether, tetramethylene ~ulfone, N,N-dimethylformamide, 3~ f~ ?~ 3 3 N,N-dimethylacetamide. N-methylpyrrolidone. ani601e, 2-butoxyethoxytrimethyl6ilane, cellosolve acetate, crown ether~ 6uch as 18-crown-6, acetonitrile, and tetr~hydrofuran. Acetonitrile and tetrahydrofuran are preferred solvent6 w~en a co-sataly6t wherein the active ~pecies is an anion is used. When the co-cataly6t employed is a zinc compound, suitable solvents are limited to hydrocarbon6 and chlorinated hydrocarbon6, preferably dichloromethane or 1,2-dichloroethane.
The monomer6 u~ed in the proce~ of the invention are generally liquids and can be polymerized ~ithout a solvent, although a solvent i6 beneficial in controlling temperature during exothermic polymerization. When a solYent is used, the monomer may be dissolYed or dispersed therein at concentrations of a~ least 1 ~t %, preferably at least 10 wt %. The initiator i6 employed at a concentration 6uch that the monomer/initiator molar ratio is greater than 1, preferably greater than 5. The co-catalyst is normally present in fiuch an amount that the molar ratio of initiator to co-catalyst i~ in the range o.
to lO,ooo, preferably 10 to 100.
In the polymerization proces6 of the invention, it is preferable to charge the initiator, co-catalyst, and solvent, if used, to the polymerization ves6el before adding the monomer(s), especially if polymers of narro~ molecular weight di~tribution are desired. In ~elected cases, such as the polymerization of methyl methacrylate ini~iated by trimethylsilyl nitrile using a relatively low concen~ration of cyanide or fluoride ions as the co-catalyst, polymerization takes place after an induction period of 6everal minutes. In such case6, all materials, including the monomer(s), may be charged ~ogethe~ or independently, and mixed in place. 5uch an initiator/co-~ataly6t 6ystem i6 preferred ~o obtain relatively monodi~per~e polymer6.
By a monodi~perse polymer i~ meant one haYing a narrow molecular weight di~triblltion, ~hat i~. MW~Mn i6 about 1. At higher values of ~wt~n the polymer i6 6aid by ~he art to be polydi6per6e.
Although, a6 indicated above, it i~
preferable to charge all nece6~ary initiator, co-cataly~t and 601vent to the polymerization ve66el before adding monom~r(fi), ~b~equent polymerization rate being controlled by monomer addition, fur~her addition6 of co-cataly6t may 60me~ime6 be neces~ary to 6ustain polymerization.
The final (non-living) polymeric product obtained by mean6 of the proce66 of the invention i6 formed by quenching, that i5, by expo6ing the "living"
polymer to an active hydrogen 60urce, 6uch a~ moi~ture or an alcohol, for example, methanol.
The "living" polymer~ of the invention will remain "livingl' for 6ub6tantial period6 provided they are protected from active hydrogen 60urce6 6uch a6 water or alcohol~. Solution6 of "living" polymer6 in inert ~olvent6, 6uch a6 hydrocarbons, are e6pecially u6eful for pre&erving and conveying the "living"
polymer6. Film6 and fiber6 of the "living~ polymer6 may be ca6t or 6pun from 6uch solution~, or the polymer may be isolated from ~olution and further proce6~ed, for example, pelletized or granulated.
It i6 to be under6tood that the final (non-living) polymeric product doe~ not include the enol or imine 6pecie6 of ~ in the afore6aid formula for the ~living~ polymer of the invention. For example (as in Example6 3 and 12), a "living" polymer 3~

prepared by polymerizing methyl methacrylate u~ing methoxy-2-methyl-1-propenyl)oxy]trimethyl6ilane (MTS~ a6 the ini~iator contain6, at it6 living end, the enolic grouping polymer-C~DC \ which, C~13 osi(cH3)3 upon quenching, i6 converted to ~ OCEI3 polymer~CH-C ~

~ he proce~6 of the invention i8 u~eful for preparing homopolymer6 or copolymer6 of the monomer6 described abo~e. In either ca6e, the polymer6 obtained are "living" polymer~ which may be of high or low molecular weight and having a broad or narrow molecular weight di6tribution (MW/Mn). At a given temperature, ~ /Mn i~ primarily a function of the relative rate6 of initiation and polymerization. Rate of initiation, ri, depends on initiator and co-cataly6t type and relative concentration6.
Polymerization rate, rp, i6 a function of monomer reactivity and co-cataly~t type and concentration.
For monodisper~ity, ri/rp i6 equal to or greater than 1, that i6, the initiation rate i~ at lea6t a6 fa~t a6 the polymerization rate and all chain~ grow 6imultaneou61y. 5uch condition~ characterize the preparation of "living" polymer6 by anionic polymerization technique6 of the art wherein MW/Mn ratios only 61ightly above the theoretical limit of 1 are obtainable; for example, poly(methyl methacryla~e) f ~ ~Mn f about 1.01 to 1.1 are known in the art, a6 are copolymer6 of methyl methacrylate and other alkyl methacrylate6. Control of MW/Mn permits u~eful varlation in polymer physical propertie~, 6uch a~ gla6~ tram6ition temperature, hardne66, heat di6tortion tem]perature, and melt vi6c06ity .
The polymerization proce~ of the present invention involve~ a "living" mechani6m having 6everal ~imilarities with anionic polymerization. For example, initiation and polymerization may be represented by conventional equation~ wherein the initiator moiety (R )3M i6 located at one end of the polymer chain or branch which remain6 "living"
ever, when the monomer 6upply iB consumed; the activating ~ub6tituent Z or Z , or a tautomeric form thereof, or the activating diradical z2, or a tautomeric form thereof, i6 located at the other, non-living, end of the polymer chain or branch. The~e non-living end moietie6 are identifiable, refipectively, as member6 of the afore6aid group6 Z'l or Z . The terminal initiator moiety, unle66 chemically deactivated, i6 capable of initiating further polymerization with the same or different monomer, with re6ultant chain lengthening. Copolymer6 with 6pecific monomer 6equence~, or block polymer~, can thus be prepared.
Although the pre6ent procefi6 re6emble6 anionic polymerization, there are ~ignificant difference~ which have commercial 6ignificance. The6e difference~ include the ability to copolymerize methacrylate and acrylate monomer6, or combination~ of acrylate monomer6, for example, ethyl and ~orbyl acrylatefi, to relatively monodi6per6e copolymer6.

c~

5uch copolymer~ are difficult or impo66ible to obtain by known proce66e~ such a6 anionic polymerization or free-radical polymerization. ~oreover, wherea6 anionic polymerization proce~es which provide relatively monodi~per6e polym,er~ are carried out at low temperature6, u6ually well below -10C, which require expen6ive refrigeration equipment for commercial operation, the polymerization proce66 of the invention i6 operable over a wide temperature range, from about -100C to about 150C. It i6 conveniently operable with many commercially important monomers at about ambient temperature6.
The proce~s of thi6 invention can al60 be u6ed to prepare polymer6 containing one or more ~pecifically located functional groups which are unreactive under polymerizing conditions but are useful for 6ubsequent preparation of block copolymer6 or cro661inked polymer~. The functional group6 may be introduced by u6ing either a monomer or an initiator, or both, containing a protected functional 6ub6tituent, or by chemically deactivating (capping) the "living" end of the polymer chain or branch with a functionalized capping agent. If the capping agent contain6 more than one capping 6ite, then more than one polymer chain can be joined together or coupled to give doubled or "6tar"-branched polymers, similar to the doubled or 6tar-branched polymer6 obtained when the initiator contain6 more than one initiating 6ite, or the monomer contain6 more than one reactive ~ite capable of reacting with initiator6, a6 de6cribed previou61y. Even if the capping agent contain~ only one capping 6ite, the agent may al60 contain other functional group6 which provide reactive terminal 6ite6 to the polymer, u6eful for subsequent preparation of block copolymer6 or cro6s-linked polymer~, or for otherwi~e modifying polymer properties. Example6 of capp;ng agent6 containing one or more capping 6ite~ include 4-dimethoxymethylbenzyl bromide, 4-chloromethyl~tyrene, 4-methoxymethoxymethylben2yl Ibromide, 1,4-bi6(bromomethyl)benzene, 1,3,5-tri6(bromo~ethyl) ben~ene, terephthaldehyde and toluene dii60cyanate.
Capping agent~ containing one capping 6ite and one or more functional group6 that are unreacti~e under capping conditions include l-bromomethyl-4-dimethoxy~ethylbenzene, 1-bromomethyl-4-(methoxymethoxymethyl)benzene, 4-chloromethyl~tyrene, 4-ttrimethyl6ilylcarboxy)benzaldehyde, 4-nitrobenzaldehyde, 2,5-furanyldione, 1,3-bi6(carbonylamino)toluene and 4-~-bis(carbonylamino)diphenylmethane. In general, capping agent6 which are u6eful in the proce6~ of the invention include aliphatic, aromatic or aliphatic-aromatic compound6 containing one or more o capping function6 6uch a6 -CH0, -C-, -NC0, -Br, -Cl and -TiC13, and which may optionally al60 contain non-capping functional 6ub6tituent6, 6uch a6 -N02, -osi (R1)3 and -Co2Si(R1~3. Reaction of capping agent6 with the "living" polymer end6 proceed6 6imilarly to known reaction6 of non-polymeric trialkyl6ilanes. The capping reaction i6 normally car~ied out in an organic liquid wherein both polymer and capping agent are 601uble: frequently, the polymerization 601vent i~ ~uitable. The reaction i6 preferably carried out in the pre~ence of fluoride ion a6 cataly~t; tri6(dimethylamino)6ulfonium difluorotrimethyl6ilicate i~ a preferred cataly~t.
In the following examples of specific e~odiments of this invention, parts and percentages are by weiyi,t and temperature6 are in degreles Cel6iu6 unless otherwise 6pecified. T~e polydi6persity (D) of the polymer products of the examples i~ defined by D = MW~Mn, the molecular weight6 being determined by gel permeation chromatography (GPC). Unles6 otherwi~e 6pecified, the "living~' polymer product6 obtained in the invention proce~ were quenched by exposure to moist air before molecular weight6 were determined.

Copolymerization of Methyl Methacrylate and Hexa-lene DiacrYlate Thi~ example demonstrate~ the conver~ion of a difunctional monomer to a difunctional initiator wi Me~SiCN and 6ub6eguent polymerization of MMA to give a "double-ended" polymer, taking advantage of ~he fa6ter reaction of acrylate6 than methacrylate~.
To a 6tirred 601ution, under argon, of 0.64 ml (5 mmol) of trime~hyi6ilyl nitri~e and 0.5 ml of lM
tetraethylammonium cyanide/acetonitrile in 20 ml of acetonitrile was added ~imultaneou61y 10.8 ml (100 mmol) of methyl methacrylaCe and 0.566 g (2.5 mmol) of hexamethylene diacrylate. The temperature gradually ro6e from 21 to 23.6 during 20 min and then receded. After 60 min an exotherm occurred, cau6ing the temp*rature to ri~e to 42 during 10 min and then recede. The 601ution remained clear and relatively nonvi~cous, indicating that cro6slinking did not occur. After a total time of 2 h, 2 ml of methanol was added to remove the trimethyl6ilyl end groups, and the 601ution wa6 evaporated in vacuo to 10.8 g of ~olid poly~methyl methacrylate). GPC: ~n 3900~ Mw 4900 D 1.25 (theor. ~n 4278).

~ ' 7 ' ~

E~AMPL,E 2 Poly(Methyl Methacrylate)/Pol~ycaprolactone/Poly(Methyl Methacrylate) ABA Block Copolymer Thi~ example demonstrate6 the preparation of the diacrylate of a,~-polycaprolactone diol, conver6ion of the diacrylate to a difunctional initiator with Me3SiCN, and polymeri2ation of MM~
onto the end6. The polycaprolactone provide~ a ~oft segment, and the poly(MMA) provide6 hard 6egments.
P~lycaprolactone a,~-diacrylate wa6 prepared a~ follow~. A ~lution of 50 g of commercial polycaprolactone a,~-diol (M.W. ~1000) in 300 ml of toluene wa~ 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 9B~ acrylyl chloride was added at a rate 60 as to keep the temperature from exceeding 50. After stirring for 30 min at 50, the 601ution was cooled and filtered under argon. The solution was concentrated in vacuo and then pa6~ed o~er a column of neutral alumina under argon. The NMR 6pectrum of the re6ulting solution (230 g) showed 67.6% by weight of polycaprolactone diacrylate and 32.4~ toluene, with a formula weight of 992. GPC- Mn 1250. Mw 2200, D
1.76.
To a 601ution of 0.6 g (0.75 ml, 6.04 mmol) of trimethylfiilyl nitrile and 0.5 ml of lM tetra-ethylammonium cyanide/acetonitrile in 20 ml of acetonitrile, under argon, wa~ added 4.44 g (3.02 mmol) of 67.~ caprolactone diacrylate. After 20 min, 10.8 ml (100 mmol) of methyl methacrylate wa~ added.
An exotherm occurred 90 min after addition of the methyl methacryla~e. After lB h, 2 ml of methanol was added, and the ~olution wa6 evaporated in vacuo to 2~

13.5 g of 601id polymer. GPC: Mn 4120, Mw 7340 D 1.78 (theor. Mn 4303) NMR 6hows 4.24 methyl methacrylate unit~/caprolactone unit ~theor. 4.36).
E~AMPLE 3 Polymerization of M~thyl Methalcrylate and Ifiolation of Trimethox~siloxv-ended Polvmer Thi6 example demon6trates, by mean~ of carbon-13 NMR analy~i6, the pre6enee of silylenolate terminal group~ in a "living" polymer prepared by the proces6 of this invention. 6aid polymer being i601atable a8 a 601id without loss of activity.
A. Tetraethylammonium cyanide (16 mg, 0.1 mmol) in a reactor was heated gently under vacuum to 200 ~o remove moi6ture. After cooling under argon, tetrahydrofuran (TEIF) (20 ml) and MTS (2.0 ml, 10 mmol) were added to the reactor. ~MA (10.6 ml, 100 mmol) wa6 added dropwise over 30 min, during which time the temperature rose to 55.4. The reaction mixture was allowed to cool to 22 and 601vent was removed under vacuum while the reactor wa6 maintained at about 25. The white refiidue which re6ul~ed wa6 tran6ferred into a dry-box. An 800 mg 6ample wa6 removed, dissolved in deuterochloroform (CDC13, 3 ml) and analyzed by C-13 NMR: 0.6 g of the ~e6idue wa6 analyzed by GPC. GPC: Mn 777~ M~ 1010, D 1.30 (theor. Mn 1102). C-13 NMR: C-13 shielding peaks a6 follows:
Peak (PPm) A6sicnment 151.99 C-l ~9.78 C-2 54.2B C-3 29.56 C-4 55.42 C-5 -0.11 C-6 ' 3 CE13 ~ 3 ~ 3 3 2 , -Cll2-C - -CH -C = C
c~3 C2CH3 3 2 1 OSi(CE13~3 In the above formula for the polymer, n i~ about 9.
The remaining 6hielding peak~ corre~po~ding to carbon atoms of ~he polymer are con~ifitent with publi~hed C-13 NMR 6pectra of poly(methyl methacrylate) (J. Schaefer, Macromolecule6 10, 384 (1977): J. C.
Randall, "Polymer Sequence Determination, Carbon 13 NMR Method", Academic Pre6s, New York, 1977). The above a6signments for the terminal group in the polymer are con~istent ~ith the C-13 NMR 6pectrum of ~TS:
Peak (ppm) A66iqnment 1~9.50 C-l 90.40 C-2 56.17 C-3 16.61, 15.84 C-4 -0.20 C-5 3~ ~OCH3 / C--C\
CE13 2 1 OSi(CH3)3 B. The polymer p~epared and analyzed in PaLt A
was determined to be "living" in the following manner. The rema;ning polymer from Part A not used for analy6i~ was returned to the reactor. Under argon, THF (20 ml~ wa~ added, with fitirring~ to dis~olve the polymer and MMA (10 ml, 94 mmol) wa6 added. The ~emperature, originally 19, ro~P to 29.4, indicating tha~ further polymerization was effected with the "living'l polymer and fre~h monomer.
The mixture wa6 ~tirred for 3 h, quenched with methanol ~10 ml) and evaporated, y;elding 22.65 g of polymer. GPC: ~n 1430, fiw 1900, D 1.32 (theor.
Mn 2042).

Preparation of "Living`' Poly(Methyl Methacrylate) and Subsequent ~eacti~ns T~ereof Thi~ example demonstrate6 the preparation of ~'li~ing" poly(methyl methacrylate3 containing active terminal trimethyl6iloxy groups, and sub6equent reactions thereof.
A. "Livinq~' PolY(meth~l methacrYlate~
To a 601ution of 2.6 g (9.4 mmol) of [(2-methyl-1-[2-(trimethyl~iloxy)ethoxy]-1-propenyl)oxy~
trimethyl-6ilane in 10 ml of THF wa6 added 166 mg of tri6(dimethylamino)6ulfonium bifluoride. Then, a 601u~ion of 10 g (100 mmol) of MMA in 10 ml of THF wa6 added dropwise over 30 min. After the temperature dropped to 2Z, the reaction mixture containing PMMA
wa6 separated into three equal parts, under argon, for u6e in Parts B, C and ~ below.
B. Reaction with Bromine and Titanium Tetra-chloride The reaction6 involved are 6hown below. In all equations, R i6 0 ,CH3 , 2 3 (cH3)35iocH2cH2oc-c~ CH2-C )n C~13 CH3 Si~ Bromine react~ with approxîmately one-half of the living polymer in the 11.1 ml aliquot of polymerization mixture from Part A:

RCH2 ~OCH3 ~ C=C ~ + Br2 C~13 OSi(C~13)3 RCH2 ~ ~CS)2CH3 C\ + BrSi(CH3)3 CH3 Br IA) (ii) The relllaining living polymer in 'che 11.1 ml aliquot from Part A react6 with TiC14:
RCH2 ~ OCH3 ~ C=C ~ ~ TiC14 CH3 osi(cH3)3 C=C ~ + ClSi(C~3)3 CH3 OTiC13 (B) (iii) Coupling:

A + B --~ 2 , . CH2R + BrTiC13 One-third of the polymerization mixture from Part A (11.1 ml) wa6 cooled to 0 and treated with 0.3 g (1.9 mmol) of bromine in 5 ml of 1,2-dichloroethane. After the red bromine color di6appeared, a solution of 0.4 ml of TiC14 in 5 ml of 1,2-dichloroethane wa~ added, whereupon a j 9 ~ :

precipitate formed. The mixture wa6 allowed to warm to room temperature, stirred for 1 h, and then evapora~ed. The re6idue wa6 di6601ved in 20 ml of ace~one and precipitated frQm hexane to give 4.45 g of polymer. Thi6 wa~ identified by HPLC, NMR and GPC to be a di(trimethyl6ilyloxy)-P~A. hydrolyzable to dihydroxy PMMA. GPC: Mn 3600, ~w 4400~ D 1.23 (theor. Mn 2392)-C. Reaction with Benzyl Bromide (Capping) RCH2 ~ OCH3 / C=C ~ ~ < ~ CH2Br ~H3 OSi(CH3)3 F ~ R- CH2C-CH

R ha6 the 6ame meaning as in Part B.
An aliquot (11.1 ml) of original polymerization reaction mixture from Part A wa6 cooled to -43 under argon. To thi6 was added 0.7 g of benzyl bromide.
The 601ution wa6 ~tirred and allowed to warm to room temperature. After 6tirring for 15 min 3.5 ml of a 1.0 M acetonitrile solution of tri6(dimethylamino)-~ulfonium difluorotrimethyl6ilicate wa6 added. The 601ution was 6tirred at 25 for 1 1/2 h. after which was added 10 ml of methanol. The 601vent6 weee evapo-rated and the polymer wa6 precipitated from hexane;
4.25 g of powdery 601id polymer ~a6 recovered. GPC:
Mn 2300, Mw 3700~ D 1.61 ttheor- Mn lZ87).

~_ ~'? 3 ~ 3 ~

D. Reaction with 1~4-~Yl~l Bromide 2 RCH~ ~ OCH3 C-C + BrCH2 ~ CH2Br C~3~ 05i(C~13)3 C02CU3 ,,_, ~02CH3 --? R 2 , 2 ~ Cl-12-C----Cl-12R
c~l3 CE13 2 Brsi(cH3)3 R ha~ the ~ame meaning a~ in Part B.
Following the pr~cedure of Pa~t B, 11.1 ml of the reaction mixture wa6 treated with 0.5 g ~1.9 mmol) of 1,4-xylyl bromide, 1.1 g of tri~(dimethylamino)6ulfonium difluorotrimethyl6ilicate to give 4 . 31 g of a,~-ma~ked-dihydroxy PMMA.
GPC: Mn 3400' MW 4200, D 1.24 (theor. fin 2494).
EXAME'LE 5 PreDaration of Three-Branched Star Poly(Eth~l Acrylate~
To a ~olution of 0.93 ml (1 mmol) of 25S
trii60butylaluminum in toluene in 20 ml of methylene chloride wa~ added 9 ~1 of water (0.5 mmol). The resultiny 601ution wa6 cooled to -78, and 1.8 ml (9 mmol) of [(1-methoxy-2-methyl-1-propenyl)oxy]-trimethyl6ilane wa6 added followed by 0.89 g (0.86 ml, 3 mmol) of purified trimethylolpropane triacrylate.
After 10 minute~, 9.7 ml (90 mmol) of ethyl acrylate wa6 added at a rate 6uch that the temperature remained below -70. After 6tirring for 10 minutes at -78, 2 ml of methanol wa6 added, and the 601ution ~a6 evaporated in vacuo to 10.4 g of vi6cou6 poly(ethyl acrylate). Gel permeation chromatography (GPC) 6howed Mn 2190, Hw 3040~ D 1.39 (theoretical Mn 3300)' ~5 The t~imethylol~ropane 'Criacrylate u~ed in thi~
example wa~ purified by 6tirring 50 g with 1 liter of hexane. The hexane extract was pas~ed over a column of neutral alumina under argon and evaporated in vaeuo E~AMPLE 6 PreParation of Four-~ranched ,5tar PolY(Ethyl Acrylate To a ~olution, in 20 ml of methylene chloride, of 0.93 ml (1 mmol) of 25~ trii60butylaluminum in toluene wa~ added 9 ~1 of water. The re~ulting 601ution of "bi6(dii~0butylaluminum)0xide" wa6 cooled to -78 and treated with 2.4 ml (12 mmol) of [(l-methoxy-2-methyl-1-propenyl)oxy]trimethyl~ilane.
Then, 1.2g g (3 mmol) of 81.5~ pentaerythritol tetraacrylate in hexane-methylene chloride was added, keeping the temperature below -70. After 10 ~inutes 13 ml (120 mmol) of ethyl acrylate (purifed by pa6~age over neutral alumina under argon) was added at a rate to keep the temperature below -70. After 6tirring for 15 minute6 at -78, 3 ml of methanol was added, and the 601ution wa~ evaporated in vacuo to 16.2 g of VifiCOU~ poly(ethyl acrylate). Gel permeation chromatography ~howed Mn 2400, ~w Z~70~ D 1.24 (theoretical Mn 4752).
The pentaerythritol tetraacrylate used in the example was a commercial 6ample purified by trea~ment of 50 g with ~:1 hexane:methylene chloride, adding additional methylene chloride until 601ution occurred. Then, hexane wa6 added until a 6mall amount of liquid had 6eparated. The hexane 601ution wa~
decanted and evaporated in vacuo. The re6idue wa~
treated with 10 ml of methylene chloride and pa~6ed through a neutral alumina column under argon.

g Preparation of Three-Branched Star Poly(methYl methacrylateL
A. To 4.41 ml (3.838 g, 12.87 mmol) of tri~S~rimethyl~ilyl)pho6phite at 65 was ad~ed 610wly 1.0 g (4.29 mmol) of trimethylolpropanetriacrylate (purified by extraction with hexane and pa66age of extract through neutral alumina). After 1 h, NMR
showed no residual acrylate and wa6 in agreement with CH OEl C[CH 0~
3 2 2 C=CH , a vi6cous oil.
Me3SiO~ / O
CH;2-P(OSiMe3)2]3 Anal. Calcd- f' C42H101l5 3 9 H, ~.54; P, 7.80; Si, 21.21. Found: C, 41.05; H, 8.17; P, ~.87; Si, 19.91.
B. To a 601ution of 1.91 g (lr6 mmol) of the product of Part A in 30 ml of tetrahydrofuran wa6 added 0.1 ml of lM tri~(dimethylamino)6ulfonium bifluoride~acetonitrile and 15 g (16.2 ml, 150 mmol) of methyl methacrylate. A slow exothermic reaction wa6 observed. After stirring 18 h, the solution wa6 evaporated in vacuo to 12.6 g (80.7%) of 601id polymer.
GPC: Mn 13,000, Mw 28,600, D 2.20 (theoretical Mn 7500)-To convert the 6ilylpho~phonate terminal group6to pho6phonic acid group6, the product was stirred at reflux for 1 h with 15 ml of methylene chloride, 6 ml of methanol, and 1 ml of lM tetra~utylammonium fluoride/tetrahydrofuran. The solution wa~ evaporate~
and the residue wa~ di6601ved in methylene chloride, wa~hed with water, dried and concentrated. The purified three-star triphosphonic acid polymer wa6 3~

precipitated with hexane to g'ive 6 g of 601id polymer.
The NMR ~pectrum 6howed the ab~ence of any trimethyl6ilyl group6.
E~AMrLE 8 Preparation of a Triblock Terpolymer of Me~yl Methacrylate (MMA), n-Butyl Methacrylate (BMA), and Allyl Methacrvlate ~AMA), Catalyzed bY Bifluoride Ion.
A 250 ml reactor, fitted with an argon inlet, a 6tirrer, thermocouple and a 6yringe pump, wa6 charged with tetrahydrofuran (50 ml), tri~(dime~hylamino)-6ulfonium bifluoride (0.05 ml, lM in CH3CN) and [~2-methoxy-2-methyl-1-propenyl)oxy]trimethyl~ilane (1.25 ml, 6.25 mmol). MMA (10.7 g, 106.9 mmol) wa6 then added via a 6yringe pump over 15 minute~. T~e temperature ro~e from 24.8 to 51.6~ accompanied by an increase in the vi6c06ity of the mixture. The reaction mixture wa6 6tirred and allowed to cool to 38.6. Then BMA (9.0 g, 63.3 mmol) wa~ added over 15 minutes. The temperature ro~e to 43.2. The addition proce~s wa6 repeated with AMA (5.34 g, 42.5 mmol) and the temperature ro6e from 33 to 39.2. The clear colorles6 mixture wa6 6tirred until the temperature dropped to 23 and then wa6 treated with methanol (10 ml) containing phenothiazine (0.1 mg). The 601vent was evaporated and the re6idue was dried: yield 23.72 g. Mn 3800, Mw 4060, D 1.07 (theoretical Mn 4100). The poly~er 6howed Tgl -19, Tg2 38~, Tg3 lOB, corre6ponding to poly(allyl methacrylate), poly(n-butyl methacrylate) and poly(methyl methacrylate) 6egment~, re6pectively.

'~t~3 3a EXAMPL,E ~
Polymerization of Methyl Meth,acrylate with Bi6[(1-methoxy-2-methyl-l-propenyl)oxy]methylsilane and tri6(dimethvlamino~ulfonium Bifluoride To a ~olution, in 20 ml of anhydrous tetrahydrofuran, of bi~[(l-methoxy-2-methyl-l-propenyl)oxy]methyl6ilane (1.23 g, 5 mmol), prepared by the reaction of methyldichlorofiilane with the lithium enolate of methyl i~obutyrate tbp 54.8J0.5-57.2/0.7 mm), and 20 ~L of 1 ~ tri~(dimethylamino)6ulfonium bifluoride/acetonitrile wa~ added 10 g (10.8 ml, 100 mmol) of methyl methacrylate (purified by pa6sage over neutral alumina under argon) containing lo ~1 of 1 M
tri~(di~e~hylamino)6ulfonium bifluoride. An exothermic reaction per6i6ted during the monomer addition. After 30 minute6 5.0 g (5.4 ml, 50 mmol) of methyl methacrylate wa6 added, producing an exothermic reaction. Addition of 3 ml of methanol produced an apparent decrease in vi6c06ity. Evaporation in vacuo gave 17.5 g of 601id poly(methyl methacrylate).
Gel permeation chromatography 6hows Mn 1410, Mw 1550, ~ 1.10 (theoretical Mn 1600).

Polymerization of Methyl Methacrylate with t3-methoxy-2-methyl-3-((trimethyl6ilyl)oxy)-2-propenyl]pho6phonic Acid, Bis(trimethylsilyl) E6~er and Tri6(dimethylamino)sulfonium Bifluoride A. [3-Methoxy-2-methyl-3-((trimethyl-6ilyl)0xy)-2-propenylphosphonic acid, bi~(trimethyl~ilyl) e6ter wa6 prepared by 6tirring a mixture of equimolar amount6 of methyl methacrylate and tri~(trimethyl6ilyl)pho6phite at 114 for 3.5 h under argon. The product wa6 di6tilled in a 6mall 3~3~

Vigreux column, b.p. 91/0.23 ~m, Anal. Calcd. for C14H3505PSi3: 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 ~tirred ~olution of 3.1Z g {3.2 ml~
7.04 mmol) of the phosphonic acid e~ter prepared in Part A and 0.3 ml of a 1 M ~olution in acetonitrile of tri~(dimethyamino)6ulfonium bifluoride in 100 ml of tetrahydrofuran under an argon atmosphere wa6 added during 1 h 55 ml (50.9 g, 509 mmol) of methyl methacrylate (purified by passage over d ~hort column of neutral alumina). The 601ution wa~ 6tirred for two h after the end of the exotherm. Then, 30 ml of methanol a~d 2 ml of lM tetrabutylammonium~tetrahydro-furan wa6 added and the re6ulting 601ution was 6tirred at reflux for 1.5 h and concentrated in a rotary evaporator. The product wa6 precipitated from the concentrated 601ution by addition to water. The polymer was filtered and dried in a vacuum oven at 100~ to gi~e 49.7 g of poly(methyl methacrylate-l-pho6phonic acid). GPC: Mn 5900~ Mw 5900, D 1.00 ~t~eoretical Mn 6650); lEI NMR: ~(ppm from external Me4~i, CDC13 601Yent) 7.9 ppm [broad, PO(OH)2].

Polymerization of Methyl Methacrylate with Tri6(trimeth~1silYl~Pho6phite and Bifluoride Cataly6t To a ~tirred 601ution of 1.49 g (1.75 ml, 5 mmol~ of tris-~trimethyl6ilyl)pho6phite and 0.31 ml of 1 M tri6(dimethylamino~sulfonium bifluoride/aceto-nitrile in 15 ml of tetrahydrofuran under argon wa6 added 10 g (10.8 ml, 100 mmol) of methyl methacrylate.
After 20 minutes an exothermic reaction was ob6erved, and the temperature rose to 36. After 6tirring 1~ h 3 ~
~he vi6cous ~olution wa6 evaporated in vacuo to 1~.1 g of 601id pho6phonate-6ub6titul:ed poly(methyl methacryl~te). GPC: Mn 15,300, M~ 29,400, D 1.92 (~eoretical hn 2300).

Polymerization of Methyl Methacrylate and I601ation of Trimethy_6iloxy-ended Polvmer Thi6 example demonstrate~ by mean6 of carbon-13 NMR analy6i6 the pre6ence of 6ilylenolate terminal group6 in a "living" poly~er prepared by the proce66 of thi6 invention.
A. To a 6uspension of 20 mg (0.1 mmol) of tri~(dimethylamino)6ulfonium bifluoride in 5 ml of THF
wa6 added, unde~ argon, 1.0 ml (5 ~mol) of MTS. Then, 2.7 ml (25 mmol~ of MMA was added, whereupon the temperature rose from 22 to 50. The mixture was ~tirred until the temperature dropped to 22. Then, the reaction ve6sel was connected to a vacuum pump and the solven~6 were removed at 0.1 mm ~g u6ing a liquid nitrogen trap. A foamy polymer, 3.5 g, wa6 obtained.
T~i6 wa6 6ubjected to C-13 NMR analy6i6~
MTS wa~ u6ed as a 6tandard and the a66ignment of peak6 is 6hown below:

C~3 ~ / oSi(CH3)3 C=C

Carbon C-13 Shieldinq (pPm) C-l 149.50 C-2 90.40 C-3 56.17 C-4 16.61? 15.84 ~_5 -0.20 The most di6tinct and useful peak6 are t~ose corre~ponding to the sp2-hybridized carbon atom6 occurring at 90.40 and 149.50 ppm. The ab~orption of the corresponding carbon atom6 of the "living"
polymer 6hould occur in about the 6ame 6pec~ral region.

CH3 ~3 /OCH3 MeOOC-C-~C~2C ~5CH2-C=C
CH3 COO~e CH3 osi(cH3)3 Carbon C-13 Shieldinq (ppm~
C-l 151.1 C-2 8~.5 C-3 59.6 C-4 28.1 C-5 -1 to -1.5 As shown above, di~tinct peak6 occurred at 151.1 and 88.5 ppm, corresponding to the carbon atom6 of the C=C
moiety. The C=O ab60rption of the e6ter group~ of the polymer occurred between 175 and 176 ppm as multi-plet6. Integration of the peak~ due to C=O ver6u6 those due to C=C gave a degree of polymerization of about 6. The i601ated polymer t3.5 g) wa6 di6601~ed in 10 ml of THF and then treated with 5 ml of methanol. Upon evaporation and drying, 3.3 g of polymer wa6 obtained. GPC: Mn 550' ~w 600, D
l.Og (theor. Mn 602).

B. Following the procedure of Part A, trimethyl-~iloxy-ended poly(ethyl acrylate) wa6 i601ated from the reaction of 20 mg (0.1 mmol) of tri6~dimethyl-3~ 3~
~ 2amino)6ulfonium bifluoride, 1.0 ml of MTS, and 2.7 mlof ethyl acrylate in 5 ml of I'HF. The a66ignment of peak~ in the C-13 NM2 is ~hown below:
3 ~ C C~ 3 polymer-CH2 \ ~ OSiMe3 H 2 1 OEt H 2 1 \ OEt Model "Living"
polytethyl aclylate) C-13 Shieldings ~ppm) Carbon ~sdel Livina PEA
C-l 164 . 2 167 . 2 C-2 107.2 108.8 A. If ~65 g of a copolymer of methyl methacrylate,prepared as in Example 22 of U.S. Patent 4,417,034, is dissolved in 135 g of xylene, a solution containing ?3~ 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:

Part6 By (i) Silica Mill Ba6e Weiqht Acrylic polymer solution (from Part A) 389.65 ~ylene 200.92 Ethylene glycol monoethyl ether acetate 200.84 Fine divided ~ilica ~trea~ed with dimethyl dichloro ~ilane) 56.59 Total B48.00 The above con6~ituent~ can be charged in~o a conventional 6and mill and ground to form a mill base.
Parts By (ii~ Iron Pyropho6phate Mill Base Weight Acrylic polymer ~olution 4g4.24 (from Part A) Xylene 233.28 Iron pyropho6phate pigment 207.48 Total 935.00 The above con6tituent6 can be charged into a conventional 6and mill and ground to form a mill ba~e.
Part~ By (iii~ Indo Blue Mill Ba~e Weiqh~
Acrylic polymer 601ution (60% ~olids in a 601vent mixture of petroleum naphtha, ethylene glycol mGnoethyl ether acetate, and butanol. of a polymer of 6tyrene/butyl acrylate/hydroxy-ethyl acrylate/acrylic acid, weight ratio 50/38/8/4 prepared by conventional free radical polymerization) S0.00 Butyl acetate 43.00 Indanthrone Blue Toner 7.00 Total 100.00 The above confitituent6 can be mixed toge~her and then ground in a conventional ~and mill to form a mill ba6e~

~4 Part6 By (iv) lue Mill Ba6e Wei~ht _rt~on 1 Acrylic polymer solution (de~cribed for compo~,;tion (iii)) 14.30 Butyl acetate 57.70 Po tion 2 Mona6tral* Blue pigment8.00 Portion 3 Acrylic polymer 601ution (described for Portion 1) 20.00 Total 100.00 Portion 1 can be charged into a mixing ves~el and mixed for 15 minute6, Portion 2 can be added and mixed for 1 h and Portion 3 can be added and mixed for 1 h. The re6ulting composition can be ground in a conventional 6and mill to form a mill ba~e.
Part6 By (v) Aluminum Flake Mill ba6e _ Wei~ht ~crylic polymer 601ution (from Part A) `50~.41 ~ylene 198.91 Aluminum paste (65% aluminum flake in mineral ~pirit~ 8.68 Total Rg7 . oo The above con6tituent6 can be thoroughly mixed together to forn a mill ba6e.
* denotes ~ra~e mark ~3~

Part6 By (vi) Para-Toluen Sulfonic Acid Solution ~eiaht Para-toluene sulfonic acid 131.54 Methanol 515.08 Dimethyl oxazolidine 92.38 Total 7~9.00 The above con6tituents can be thoroughly blended together to form an acid 601ution.
A light blue paint can be prepared by thoroughly blendin~ together the following con6tituents:

~ 9 Part6 ~y 2ig~t_ Silica mill ba6e (de~;cribed above in Par~ ~i)) 196.00 Iron pyropho6phate mill base ~described above in l?art (ii)) 29.45 Acrylic polymer fiolution (f.rom Part A) 210.22 2-(2'-hydroxyphenyl)-benzotriazole 8.67 Nickel bi6--~0-ethyl(3,5 di-tertiary-butyl-4-hydroxy-ben~yl)pho~phonate~ 4.34 Tetraki~ met~ylene 3-(3',5'-dibutyl-4'-hydroxyphenyl)-propionate methane 0.~1 Methanol 30.27 Blue mill base (de6cribed above in Part ~iv)) 5.07 Indo blue mill ba6e (de6cribed above in Part (iii)) 19.39 Aluminum flake mill ba~e (described above in Part (v)) 66.67 Melamine rein (methoxy/butoxy-methyl melamine) 174.~4 Meth~l amyl ketone 25.~3 Methyl isobutyl ke~one2~.~6 Dii60butyl ketone Z4.73 Para-toluene ~ulfonic acid fiolution (de6cribed above in Part (vi)) 7.36 Amine 601ution t25~ dimethyl oxazolidin2 in methanol)14.72 To~al 841.00 The above described composition can be sprayed onto a ~teel panel primed with an alkyd re6in primer and baked for 30 minut,e6 at abou~ lZ0 to give a finish which is expected to be glos6y and hard, with a good appearance, re~i~tant to weathering, 601vent6, 6cratche6 and chipping. ~hese ~roperties indicate utility for f inishing automobile6 and truck6.
C. A clear enamel composition can be prepared by blending:
Part~ By Weiqht Acrylic polymer solution (from Part A) 89.04 Melamine resin (methoxymethyl melamine) 35.00 Para-toluene 6ulfonic acid 0.20 Xylene 42.43 Total 166.~7 D. A 6teel panel can be sprayed with the color coat of Part B, fla6h dried, then 6prayed with the clear coat of Part C and then baked at 120 for 30 minute~. It i~ expected that a color coat/clear coat fini6h wsuld be formed that has excellent glo and appearance and would be durable and weatherable and useful as an exterior finish for truck6 and automobiles.

The following con6tituents can be blended together to form a lacquer paint:

~2~s~
4~
Part~ By _~eiqht Po tion 1 Ace~one 9.30 Alkyd re~in solution ~85~ ~olid6 alkyd resin of ethylene glycol/phthalic anhydride/coconut oil ha~ing a hydroxyl No. of about 20 and an acid No. of about 8-10 in toluene and ~aving a Gardner Holdt vi6co~ity of about ~
measured at 25) 9.53 ~ortion 2 Aluminum flake ~ill ba6e (29.8~ polyme~hyl methacrylate~
12.4~ aluminum flake and 57.B~
601vent mixture of toluene and acetone) 15.48 Blue Mill ba6e (10%
"Mona6tral" blue flake, 16S poly-methyl methacrylate*, 74%
~olvent mix~ure of toluene and acetone) 3.39 Carbon Black Mill Ba6e (6~ carbon black pigment, 24%
polymethyl methacrylate~, 70 ~olvent mixture of toluene, acetone, ethylene glycol monoether acetate, butyl acetate 0.33 Green Mill Ba6e (8.3% ~Mona6tral" green pigment, 21.1% polymethyl-methacrylate*, 70.6% 601Yent mixture of toluenetacetone/
xylene) 0.

Portion 3 Sîlicone solution (4~ 6ilicone SF69 in xylene 0.03 PMMA ~olution ~40~ 601ids of polymethyl methacrylate in THF (prepared a6 in 'Example 21 of U.S. Patent 4,417,034)26.96 C~B ~olution (25% ~olid6 cellulo6e acetate butyrate having a 37% butyryl content 2 second vi~c06ity in toluene/
acetone, 70/30 ratio~ 12.9B
CAB Solution II (15% 601id6 cellulose acetate butyrate having a 38~ butyryl content and a 20 6econd vi6co~ity in ~oluene/acetone, 70/30 ratio 21.64 Total 100.00 ~polymer prepared by conventional free-radical polyme~ization Portion 1 can be charged into a mixing vessel and mixed for 10 minute~, portion 2 can be added and mixed for 10 minute6 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 6teel panel~ primed with an alkyd resin primer and coated with a 6ealer. Three coats may be ~prayed onto the panel6 and the panel6 baked at about 165 for 30 minutes to provide a finish of about 2.2 mil6 thickne~6.
The resul~in~ fini~h i6 expected to be 6mooth, glos~y, water re~i6tant, gasoline resi~tant, chip resistant and weatherable, with excellent distinctne~ of image, useful a~ a high quality automotive coating.

Arl aqua metallic air drying enamel wa6 prepared from the following:
28.5 parts Carbon black 11.0 parts Phthalo blue toner 42.5 parts "Monastral" Green cake 19.0 part6 Phthalo blue cake 157.0 part6 Aluminum paste-medium 8.0 part6 Titanium dioxide pigment ~90.0 part~ Polymer (prepared a6 in Example l~A of U.S. PatPnt 4,417,034) 110.0 part6 ~ylene 110.0 parts Cellosolve a~etate 4.0 part6 Cobalt naphthenate The above compo6ition was 6prayed onto a ~teel panel primed with an alkyd resin primer and allowed to cure at ambient temperature. After about a week, the fini~h was hard and re6i6tant to 601vent6 and 6cratches.
Best Mode For Carr~ina Out The Invention The best mode presently contemplated for carrying out the invention i6 demonstrated and/or represented by Example6 1 to 9 and 12 to 15.
Indu6trial APPlicability The invention proce66 provide6 u6eful and well known polymers containing functional ~ubstituent~, for example, homopolym~r6 and copolymer6 of acrylate and/or methacrylate monomers, 6uch polymers heretofore being made u6ually by anionic polymeriza~ion technigue6. The invention pxoces6 also provide6 a means for making certain commercially de6irable, relatively monodi~per6e copolymer6 of methacrylate and acrylate comonomer6, ~3~ 3~

6uch copolymer6 being difficult or impo66ible to obtain by known proces~e6 6uch as anionic polymerization or free-radical polymerization. The invention proces6 al60 provides "living" polymer which may be ca~t or 6pun, for example, into a film or fiher, from 601ution or di6persion (in or using an aprotic 601vent) or i~olated, proces~ed, and then further polymerized. The 601ution6 or disper6ion6 may al~o be formulated with clear or opaque pigment~
and other ingredients which can be converted into protective coatings and fini6he~ for manufactured article6, such a6 metal, glas6 and wood.
Various type6 of fini6he~ can be made which take advantage of the propertie6 of the polymer~
di6closed herein. These include 601vent-based and water-based finishe6, powder coating6, electrocoating composition6 including anodic and cathodic, coatings to be applied by 6praying or other technique6, coatings which contain cros6 linker6 including, but not limited to, melamine resins and isocyanate re6ins, and coatings which can be cured by a variety of technique6 including heat, various type6 of radiant energy, expo6ure to air, and variou6 vapors, 6uch as moi6ture or amines. ~fter the "living"
polymer~ disclo6ed herein have been quenched, 6uch a6 by reaction with water or alcohol6, the need to avoid moi6ture may no longer exist, and aqueous coating composition6 can be made therefrom.
Although preferred embodiment6 of the invention have been illu6trated and described hereinabove, it i6 to be under~tood that there i6 no intent to limit the invention to the preci6e construction6 herein di6clo6ed, and it is to be further under6tood that the right i6 re6erved to all change~ and modification~ coming within the scope of the invention a~ defined in the appended claim6.

Claims (51)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. In a process comprising polymerizing the monomer selected from the group consisting of CH2=C(Y)X, and mixtures thereof wherein:
X is -CN, -CH=CHC(O)X' or -C(O)X';
Y is -H, -CH3, -CN or -CO2R, provided, however, when X is CH=CHC(O)X', Y is -H or -CH3;
X' is -OSi(R1)3, -R, -OR or -NR'R";
each R1, independently, is hydrocarbyl of up to 20 carbon atoms;
R is selected from the group consisting of (i) hydrocarbyl of up to 20 carbon atoms, (ii) hydrocarbyl of up to 20 carbon atoms containing one or more ether oxygen atoms within aliphatic segments thereof, and (iii) hydrocarbyl of up to 20 carbon atoms and containing one or more functional substituents that are unreactive under polymerizing conditions; and each of R' and R" is independently selected from C1-4 alkyl by contacting the one or more monomers under polymerizing conditions with:
(i) the initiator of the formula (R1)3MZ
wherein:
R1 is as defined above;

Z is an activatinq substituent selected from the group consisting of and mixtures thereof X' is as defined above for the monomer;
each or R2 and R3 is independently selected from (i) H, (ii) hydrocarbyl of up to 20 carbon atoms, (iii) hydrocarbyl of up to 20 carbon atoms and containing one or more ether oxygen atoms within aliphatic segments thereof, and (iv) hydrocarbyl of up to 20 carbon atoms and containing one or more functional substituents that are unreactive under polymerizing conditions; and Z' is O or N;
m is 2, 3 or 4;

n is 3, 4 or 5: and M is Si, Sn, or Ge, provided, however when Z is or , M is Sn or Ge; and (ii) a co-catalyst which is a source of bifluoride ions HF?, to produce "living" polymer having repeat units of the one or more monomers, said process further characterized by at least one of:
(a) R1 is H, provided that at least one R1 group is not H;
(b) R is selected from the group consisting of (i) a polymeric radical containing at least 20 carbon atoms, (ii) a polymeric radical containing at least 20 carbon atoms and containing one or more ether oxygen atoms within aliphatic segments thereof, and (iii) a polymeric radical containing at least 20 carbon atoms and containing one or more functional substituents that are unreactive under polymerizing conditions;
(c) at least one of any R group in the monomer contains one or more reactive substituents of the formula -Z'(O)C-C(yl)=CH2 wherein yl is H or CH3 and Z' is as defined above;
(d) the initiator is of the formula (R1)2M(Z1)2 or O[M(R1)2Z1]2 wherein R1 and M are as defined above and Z1 is wherein X', R2 and R3 are as defined above;
(e) at least one of any R, R2 and R3 in the initiator contains one or more initiating substituents of the formula -Z2-M(R1)3 wherein M and R1 are as defined above; and Z2 is as diradical selected from the group consisting of , , , , , , , , and mixtures thereof, wherein R2, R3, X', Z', m and n are defined above, provided, however, when Z2 is , M is Sn or Ge;
(f) Z is selected from the group consisting of -SR, -OP(NR'R")2, -OP(OR1)2, -OP[OSi(R1)3]2 and mixtures thereof.
wherein R, R1, R' and R" are as defined above;
(g) R2 and R3 taken together are provided, however, Z is or Z2 is ; and (h) X' and either R2 or R3 taken together are provided, however, Z is or and/or Z2 is .

2. Process of Claim 1 wherein at least one of said R, R2 and R3 groups contains one or more ether oxygen atoms within and aliphatic segment thereof.

3. Process of Claim 1 wherein at least one of said R, R2 and R3 groups contains at least one functional substituent that is unreactive under polymerizing conditions.

4. Process of Claim 1 wherein at least one of said R groups in the monomer(s) contains one or more reactive substituents.

5. Process of Claim 1 wherein at least one of said R, R2 and R3 groups in the initiator contains one or more initiating substituents.

6. Proces of Claim 1 wherein the monomer is CH2=C(Y)X and M is Si.

7. Process of Claim 6 wherein X is -C(O)X'.

8. Process of Claim 7 wherein Y is -H or -CH3.

9. Process of Claim 8 wherein X' is -OR.

10. Process of Claim 9 wherein R is substituted with at least one -OSi(R1)3 or -C(O)OR
group.

11. Process of Claim 9 wherein R is substituted with at least one -OC(R)(R)OR, -OC(H)(R)OR
or group.

12. Process of Claim 9 wherein R is substituted with oxiranyl.

13. Process of Claim 9 wherein R is C1-20 alkyl, sorbyl, 2-methacryloxyethyl, 2-[(1-propenyl)oxy]ethyl, allyl or 2-(dimethylamino)ethyl.

14. Process of Claim 9 wherein R contains one or more reactive substituents and Z' is -O-.

15. Process of Claim 14 wherein R is a polymeric aliphatic hydrocarbon radical containing one or more ether oxygen atoms.

16. Process of Claim 15 wherein R also contains one or more keto groups.

17. Process of Claim 14 wherein R is C1-10 alkyl.

18. Process of Claim 17 wherein R is and contains two reactive substituents.

19. Process of Claim 17 wherein R is ?CH2?2-10 and contains one reactive substituent.

20. Process of Claim 17 wherein R is and contains three reactive substituents.

21. Process of Claim 6 wherein X is -CN.

22. Process of Claim 6 wherein Z is -CN.

23. Process of Claim 6 wherein Z is -C(R2)(R3)CN.

24. Process of Claim 23 wherein at least one of R2 and R3 is -H.

25. Process of Claim 6 wherein Z is -C(R2)(R3)-C(O)X' or -OCX'=C(R2)(R3).

26. Process of Claim 25 wherein at least one of R2 and R3 is H.

27. Process of Claim 25 wherein R2 and R3 are CH3.

28. Process of Claim 25 wherein at least one of R2 and R3 contains one or more initiating substituents.

29. Process of Claim 28 wherein, in the one or more initiating substituents, R1 is CH3, M is Si and Z2 is or .

30. Process of Claim 27 wherein X' in the initiator is -OSi(CH3)3.

31. Process of Claim 27 wherein X' in the initiator is -OCH3.

32. Process of Claim 29 wherein X' is -OCH3 and R2 is H.

33. Process of Claim 32 wherein the initiating substituent is in C1-4 alkyl.

34. Process of Claim 32 wherein the initiating substituent is in a poly(caprolactone) radical of at least 20 carbon atoms.

35. Process of Claim 32 wherein the one or two initiating substituents are in a phenyl radical.

36. Process of Claim 6 wherein the initiator is (R1)2M(Z1)2 or O[M(R1)2Z1]2, M is Si, at least one of R1 is CH3 and R2 and R3 are CH3.

37. Process of Claim 6 wherein Z is -SR, -OP(NR'R")2, -OP(OR1)2 or -OP[OSi(R1)3]2.

38. Process of Claim 37 wherein R1, R' and R" are CH3.

39. Process of Claim 25 wherein R2 or R3 is -CH2P(O)(NR'R")2, -CH2P(O)[OSi(R1)3]2 or -CH2P(O)(OR1)2.

40. Process of Claim 39 wherein R2 or R3 is H or CH3 and R1, R' and R" are CH3.

41. Process of Claim 41 wherein Z is

42. Process of Claim 41 wherein Z' is oxygen, R2 is H and m is 2.

43. Process of Claim 30 wherein at least one of R2 and R3 is substituted with at least one functional group that is unreactive under polymerizing conditions.

44. Process of Claim 31 wherein at least one of R2 and R3 is substituted with at least one functional group that is unreactive under polymerizing conditions.

45. Process of Claim 1 wherein R1 is -CH3.

46. Process of Claim 45 wherein Z is -CN.

47. Process of Claim 1 carried out at about -100°C to about 150°C.

48. Process of Claim 47 carried out at 0°C to 50°C.

49. Process of Claim 1 wherein Z' is O or NR'.

50. Process of Claim 9 wherein R contains one or more reactive substituents and Z' is N.

51. Process of Claim 9 wherein R contains one or more reactive substituents and Z' is NR'.