CA1256646A - Oxyanion-catalyzed polymerization - Google Patents

Abstract

TITLE
Oxyanion-Catalyzed Polymerization ABSTRACT
This invention resides in a polymerization process which is catalyzed by an oxyanion which can form a conjugate acid having a pKa (DMSO) of about 5 to about 24.

Description

~L2~

TITLE
Oxyanion-Catalyzed Polymerization BACKGR~UND OF THE INVENTION
Field of the Invention . . _ This invention resides in a polymerization process which is catalyzed by oxyanions, and to polymers produced thereby.
Background United States Patents 4,414,372; 4,417,034;
4,524,196; and 4,508,880, Canadian Patents 1 186 434 and 1 186 435, and commonly assigned Cana~ian Patent Applications Serial Nos. 467,173 of W.B. Farnham et al, filed 1984 November 06, 467,166 of O.W~ Webster, filed 1984 November 06, and 496,427 o~ W.R. Hertler et al, filed 1985 November 28~ hereinafter referred to as "the aforesaid patents and applicationsN, disclose processes for polymerizing polar monomers to "living polymers. In certain of the aforesaid patents and applications there is disclosed a process of preparing a "living" polymer, the process comprising contacting under polymerizing conditions at least one polar monomer with (i) a polymerization initiator compound comprising a tetracoordinate metal selected from Si, Ge and Sn having at least one activating substituent or activating diradical attached thereto, and (ii) a suitable co-catalyst~ the polymerization being characterized by the presence, in the growing and in the grown polymer, of a moiety containing said metal at "living" ends and said activating substituent or diradical, or a tautomer thereof, at "nonliving" ends of said polymer, the initiator optionally having one or m~re substituents that are inert under polymerizing conditions. The aforesaid patents and applications also disclose processes of polymerizing the monomer selected from the group consisting of CH2=C(Y)X, ~'i ~

~12'56~fi CH====CH
N /

and mixtu~e~ thereof whe~ein:
X i8 -CN, -CH=CHC~0)~' or -C(0)X';
Y i~ -H, -CH3, -CN or -CO2R, provided, however, when ~ i~ -CH=CHC(0)~', Y is -H or -CH3;
- 10 X' i~ -oSi(Rl)3, -R, -OR o~ -~R'R";
each Rl, independently, i6 a hydroca~byl I radical which i8 an aliphatic, alicyclic, aromat~c or ~ixed aliphatic-aromatic radlcal containing up to 20 carbon atoms;
R i6 a hydrocarbyl radical ~hich i~ an aliphatic, alicyclic, aromatic or mi~ed aliphatic-acomatic ~adical containing up to 20 carbon atom~, optionally con~aining one or more ether oxygen atoms within aliphatic 6egment~ theeeof and optionally containing one Ol more functional 6ubstituents that are unreactive under polymerizing conditions; and each of R' and R" i~ independently selected rom Cl 4 alkyl 25 by contacting the one or more monomers under polymerizing condition~ wath:
(i) the initiator of the formula ~Rl)3~Z
whe~ein:
Rl i~ as de~ined above;
Z i6 an activating substituent selected from the group consisting of ~ ~z~

R2 ~2 0 -CN, -C-CN, -C- CX', ~3 R3 - . .. .
C--C-- C -- C--L~CH2J~ CH2Jn -N=C=C-R3 ~-oC =c_R2 . -OC .CR2 , ~ I
R~ Z' ~CH

-OC - _CR2 lcH2 Jn and mix~ures ~hereof wherein:
~' i8 as defined above for the monomer:
each of R2 and R3 ifi independently selected fLom H and hydrocarbyl, defined as for R above;
Z' i~ O or NR' wherein ~' i6 a~ defined above:
m is 2, 3 or ~;
n i~ 3, 4 or 5; and ~L25~664~

M i~ Si, Sn, or Ge, pcovided, however, when Z
i~

2 "
-OC~ ~CR C- C-~H2Jn ~CH2 ¦

M i& Sn or Ge; and ~ii) a co-cataly6t which is a source of bifluoride ~ons HF~, or a 60urce of fluoride, cyanide or azide ion~ or a suitable Lewi~
acid, for example, zinc chloride, bromide or iodide, boron trifluoride, alkylaluminum oxide or an alkylaluminum chloride, to produce ~living~ polymel having lepeat unit6 of ~he one or more monomer6, ~aid proce6ses further characterized in that:
(a) Rl is H, provided that at lea6t one g~oup is not H; and/or (b) R i6 a polymeric radical containing at lea6t 20 carbon atom6 and optionally containing one or more ether oxygen atoms within aliphatic segment6 thereof and optionally containing one or more functional sub6tituents that are unreactive under polymecizing conditions; and/or (c) at least one of any R group in the monomer contain6 one or more reactive 6ubstituent6 of the formula -Z'(O)C-C(Yl)=CH2 wherein yl i6 H or CH3 and Z' i6 a6 defined above: and/or ~25~646 (d) the ini~iator i6 of ~he formula (Rl)2M(Zl)~ or O[M(Rl)2Z1~2 wherein Rl and M are as defined above and zl is -OC=C-R2 ~R3 wherein ~', R2 and R3 are as defined above; and/or (e) at least one of any R, R2 and R3 in the initiator contain6 one or ~ore initiating substituent6 of the formula -Z2-M(Rl)3 wherein - 10 M and R are as defined above: and z2 is a diradical selec~ed from the group con6i6ting of -Z'-C=C(R2)~R3). -C(R2)-CX', -Z'-C-C- 0 0 ~3 o -c(a2)=cx~ , c - c- . -oc - ---c- .
O- Z I Z
~CH2 ~ ~ ~2 O
ll l l C - - C- , -OC- C- , -C-R2 and mixture6 lCH2 ~ ~ H2 ~

thereof, wherein R2, R3, ~', Z', m and ~ are a6 de~ined above, provided. however, when z2 i8 ~-, H2~n i8 Sn or Ge; and/or (f) Z is selected from the group consisting of -SR, -OP(NR'R")2. -OP(OR~
-oP[oSi(R ~3]2 and mixture6 thereof, wherein R, Rl, R' and R" are as defined above: and/or ~g~ R2 and R3 taken together are E~3 ~ 3 P~ O

provided, however, Z i8 -C-CX' or -oC=C(R23(R3) and/or R ~' ..
z2 i~ -Z'-C-C(R2)SR3)-: and/or (h) ~' and either R2 or R3 taken together aLe ~C~O

R ~
~20 ..
provided, however, Z is -C-CX' or -OC=C(R )(R ) R3 ~, , O
25 and/or Z~ is -C(R2)-CX'.
As further disclofied in the aforesaid patents and applications, althou~h the~e proce~6es resemble anionic polymeriza~ion, ~heLe are significant ~ 30 di~ferences which have commercial ~ignificance. The~e difterence~ include ~he ability to copolymerize methacrylate and acrylate monomers, or combinations of acrylate monomer~, for example, e~hyl and 60rbyl acrylates, to relatively monodisperse copoly~ers.
35 Such copolymers are difficult or impos6ible to obtain by known proces6es such as anionic polymeri~ation or ~25 E;64~6 free-radi~al polymerization. ~oreo~er, wher~as anionlc ~olymerlzation proeesse~ ~hieh provide ~elatively monodi~per~e polymer are careied out at low temperatuea~. usually well below -10C;. which ~equire expen ive refrig~EatiDn ~gu~pment for commercial operation. the polymerization proces es of the paten~s are operable over a wide temperature range, ~eom about -100C to about 150C. and ehey are conveniently operable with many commercially important monomers at about ambient temperature~.
Commonly assigned Canadian Application Serial No. 483,153, filed June 04, 1985 of W.B. ~arnham et al, disc1Oses certain tris(disubstituted amino)sulfonium perfluoroalkoxide~, includi~g tri6(dimethylamino)-6ulfonium trifluoromethoxiae, and the use of this ~ompound a~ a cataly~t in the polymerization processe~
of U.5. Patents 4,414,372 and ~ ,034. Such use is outside the scope of the invention which i~ di~clo~ed and claimed hereinbelow. since tri~(dimethylamino~-~ulfonium trifluoromethoxide i~ not a salt sompri~ing an oxyanion which can form a conjugate acid having the ~equisite pRa.
It i6 an ob~ect of this invention t~ provide additional cataly6t6 (referred to in the aforesaid patent6 and applications as "co-~atalys~s'l) which can be u~ed in the proce~se6 disclos~d ~n the ~fore~aid patent6 and application~. Another object i8 to provide proce~6e~ which are ~i~ilar ~o the processes f di~clo~ed in the afore~aid patent6 and applicatlon~ in that ~hey can be ca~ried out with the same monome~s and initlators to produce the ~ame "livl~g" poly~er~, but di~ering in the type o~ cataly~t u~ed. Still another object i~ to ~rovide catalysts which are suitable in the proces6es of the afoce6aid paten~ and application~ but whieh are inoperable ~n eonventional ~.2S664~i art-recognized anionic proce~ses for polymerizing the ~ame type of ~onomer. A further object i8 to provide such catalysts which are ceadily and economically peepa~able. These and other object~ will.be apparent from the di~closu~e that ~ollow~.
DETAILRD DESCRIPTION OF THE INVENTIO~
The invention herein reside~ ~n the polymerizaeion p~oces~ comprisi~g contacti~g under polymerizing condi~ions at lea~t one polar monomer - 10 with ~i) a polymerization initiator ~ompound comprising a tetracocrdinate element selected from Si, I Ge and Sn having at least o~e activating ~ubstituent or activating diradical attached thereto, ~a~d eadical or diradical optionally having one o~ ~ore ~ubstituent~ that are inert undec polymerizing condition~, and (ii) a cataly~ which i~ a salt compri6ing a suitable cation and an o~yanion which can form a conjugate acid having a p~a (D~SO) of about 5 to about 2~, preferably about 6 to ~bout Zl, more preferably 8 to 18. Al~o prefecably, the polymer produced is "living" in that the polymeriza~ion i6 chaeacterized by the presence, in ehe growing and in the grown polymer, of a moiety containing the aforesaid element at Uliving" ends and the activating ~ubstituent or diradical, or a tautomer thereof, at "nonliving" end~ of ~he polymer.
By conjugate acid is meant the acid formed by protonating the catalytic oxyanion; for 2xample, the conjugate acid of acetate anion i~ acetic acid, and that o biaceta~e anion i~ acetic acid dimer. By pKa (DMSO) of the conjugate acid i6 ~eant the neqative logarithm of the acidity con~tant of the conjugat~
acid, measured in dimethylsulfoxide (DMSO) at 25C.
~ethod~ for measuring p~a value~ of various acidic compounds, including oxyacids, are a~undantly ~, ~ ~2566~a~

described in the literature, for example, by F. G.
Bordwell et al., J. OLg. Chem., 45, 3305 (1980); 46.
4327 (1981); 47, 32Z4 (1982); and 49, 14~4 (1984). A
general review of pKa and oxyanion behaviOr in organic ~olvents i~ provided by M. M. Davis in "A~id-Base ~ehavior in Aproti~ Organic Solvents," Natl. Bur.
Stand. Monograph, p. 105 (19683.
Oxyanion salts which are operable in the - pre~ent invention contain`cations that are inert under polymerizin~ conditions, yet render the catalyst available in the polymerizing medium; the medium can include one or more solubili~ing agents, ~uch a6 ceown ether~. The cations ~ay be pendant function~ on a polymeric backbone, as, for axample, in polyamine ~alts. Prefecably, the cation is a quaternary ammonium or tri~(dialkylamino~ulfonium ~TAS) cation or an alkali or alkaline earth ~etal. More preferably, the cation is tetraalkylammonium oe tri~(dialkylamino)6ulfonium (TAS) whecein the alkyl group contains 1 to 20 carbon atom~, preferably 1 ~o 8 ! carbon atom~. Mo~t preferably, the cation iB
tetraethylammonium, teera(n-butyl)ammonium or ~ri6(dimethylamino)sulfonium.
Oxyanion ~ources which are particularly u~eful in the present invention include ~al~s of carboxylic and bica~boxylic acid~, 6ulfinic acids, phosphinic and phosphoric acids, phenols and biphenols, nitrou6 and cyanic acids, - trihydrocaLbyl~ilanol~, and higher oligomeric forms of ~hese acids, having the aforesaid pKa. Included among ~uch acids are tho~e of the formula [Q~XlOH~p]q wherein X is C(O), S(O) or a ~ingle bond, p is an integer and i~ at leas~ 1, q is an integer and i6 a~
leafit 1, preferably 1 or 2, and ~, of valence p, i~
CN, N~O), P(O), PHtO3, R4 or R4Si wherein each :L~5~ 6 a~, taken independently, i6 Cl 20 hydroca~byl o~ a polymeric ~adical containing at least 20 carbon atom6, optionally having subfitituen~6 that are ine~t under polymerizing conditions, o~ optionally ints~upted within aliphatic ~egments thereof with one o~ mole heteroatom6, such as ether o~ygen sr thioether ~ulfur, or one or mor0 keto group~. preferably~ ~1 is C~O) or a ~ingle bond, Q is R4, which preferably i~
Cl 8 hydro~arbyl or sub6tituted Cl 3 hydrocarbyl, and g i8 1 or 2: moLe pre$erably, Q is R4 which is phenyl, substituted phenyl or Cl 9 alkyl. Pceferred ! anion6 are also ambident, .tha~ i8. they ale anions which can ~eact at ~ore than one si~e. Repre~entative example6 of a~bident oxyanion eatalys~s include acetate, biacetate, benzoate, bibenzoate, cyanate, nitrite, 4-nit~ophenolate and bi(4-nitrophenolate).
Representative sub6tituents that are ~ert under polymerizing conditions include -CN, -~2~ -OCH3,

3, CF3, -Clo -F, -02SC~3 and -N(CH3)2, provided that when the sub6tituent i~ -~, the carbon atom adjacent ~o _Xl_ ifi un8ub~tituted O
A8 iS already evident f~om the above, the ; oxyanion6 which are useful as catalys~6 in the proce66 of ~he invention include as~ociated or hydroqen-bonded anions~ such a6 bianions which can be focmed from one or more o~ the above acids, for example, by treating a monoanion ~alt or a related base, such a~
tetrabutylammonium hydroxide, with one or more of the aPoresaid acids: ~uch oxyanion~ are usually preferred c 30 herein. Non-limiting examples of such oxyanions include bica~boxylates o~ the formula (RC02)2H
wherein R i8 as defined above (each R ~elec~ed independently3, such as biacetate, bib*nzoate, bi(4-nitrobenzoate~ and bi(4-dimethylaminobenzoa~e), ~2~;66~6 bi~-nitrophenolate) and biphenolate; and RC02HF, wherein ~ i~ a~ de~ined abo~e, 6uch as acetobifluoride.
As equilibria are belleved to b~ establi~hed between mono- and bianion~ and the one o~ more acid6, operable oxyanion catalyst~ include mixtures compri6ing fialt~ of mono- and/or bianions and their conjugate acid~. Preferred oxyanion ca~aly~ts are prepared by adding to one equivalent of a monooxyanion source about 0.1 to about 2 equivalents, pLeferably about 1 equivalent, of its conjugate aci~; ~uch treatment re~ult6 in par~ial or complete conversion of monoan~on to bianion. Although mo~e than about Z
equivalent6 of conjugate acid may be tolerated, it must be kept in mind that the acid may react with the initiator and ~hus reduce the concentration of initiator below it6 desired level. For thi~ ~ea~on, therefore, ~ubstantial exce~ses of conjugate acid are to be avoided. Stated in another way, small amounts of ~ree conjugate acid remaining associated with mono-an~/or bioxyanion salt~ as a consequence of their prepara~ion can be tolerated wlthout deleterious effect on the polymerization proce~s. Such i8 demonstrated in Examples 14 and 46.
Representative oxyanion ~ource compounds which are operable herein include the TAS and the tetramethyl-, tetraethyl- and tet~a(n-butyl)ammonium ~alt6 of the following anion~ (the pKa values of the corresponding conjugate acid~, if available in the art, are given in paLentheses): nitrite ONO , cyanate CNO , acetate (11.5), cyanoacetate (6.3), benzoate (10.5), 3-~hlorobenzoa~e (9.S~,

4-chlorobenzoate ~10.1), 4-methoxybenzoa~e (11.0), 4-cyanobenzoa~e (8.9), 4-nitLobenzoa~e (9.0), 3-nltrobenzoate (9.2), 2-nitrobenzoate (8.1~, 4-t~ifluoromethylbenzoate [9.5~, ~L~S66~6 4-methyl~ulfinylbenzoate (9.1), 4-nitrophenolate (11.0), 3-nitrophenolate ~13.7), 2 nitrophenolate (11.9), 4-fluorophenolate (17.6), 4-cyanophenolate tl3.1), 2,4,6-tri~hlorophenolate (lU.23~ phenolate (lB.l), 4-methoxyphenolate (18.2), 4-e~hoxyphenolate (~3.8), p-toluene~ulfinate, pentafluorophenolate (8.8), pentachlorophenolate ~7.1), d-10-camphor~ulfinate, picolinate, acrylate (10.5), pentanoate, octanoate, ~rimethylacetate, 2-ethylhexanoate, 2-methylphenolate, 4-methylphenolate, 6-trifluoLomethyl-4-thiahexanoate, ! trimethyl~ilanolate, 6alicylate (6.3), N-methyl-p-toluenesulfonamidate, phenylphosphinate and the bianion6 previously listed hereinabove.
~6 demon6trated and di clo6ed in the example~
hereinafter, monomer i6 preferably fad to the leaction vessel after the oxyanion catalyst ~ource compound, initiator and 601Yent, if any, have been charged. The oxyanion cataly6t source compound can be added as a solution in a suitable non-aqueous solvent, such as tetrahydrofu~an, toluene, trifluoromethylbenzene or j acetonitrile. Alternatively, a solution o~
monooxyanion catalyst source may be treated in situ (in the reaction vessel) with one or ~ore oxyacids having pKa value6 in the afore6aid range, to provide bianions a6 previou~ly de6cribed. The concentration of catalyst a~ well as the initia~or and monomer concen~ations employed in the polymerization are the - 6ame as dlsclosed in the afo~e6aid patent~ ~nd ~ 30 application6, as are the other conditions employed in the polymerization process o this invention.
As illu~trated in Example ~8 herein, the oxyanion cataly6ts of the present inventio~ are al~o useful in ~he proce6s of aforementioned application ~L2~ 6 Canadian Serial No. 496,422 wherein selected chain-transfer agents are employed.
In the followins example~. the molecular weights of the polymer product6 (Mw and M~l were measured by gel permeation chromatography (GPC). The polydispersity of the polymer i~ defined by V=My/Mn~
Unless otherwise ~pecified, any "living" polymer products which ~ere obtained were quenched by exposu e to ~oi6 air or methanol before molecular weights wer~ 0 dete~mined. All temperature~ are in degr~e~ Cel~ius.
ExamDle 1 Polymerization o Methyl Methacrylate Catalvzed b~ TrimethYlsilanolate I~on_ Twenty-~ive mg of potassium trimethyl-silanolate di~olved in teteahydrofuran (THP) wa~
added to 0.70 ~L of t[l-methoxy-2-methyl-1-propenyl)-oxy]trimethylsilane (~TS~; 5 mL of methyl ~ethacrylate (~MA) was added by syringe to this mixture. The temperature rose immediately, reaching 65. After the temperature returned to 30, 4 ~L of ~MA was added.
The temperature again rose to 65 and the 801ution became very vi6cous, indicating further polymerization of the initially-~ormed ~'living~ polymer. After 1.25 h another 4 mL of MMA was added: no exotherm was noted.
ExamPle 2 Part A. Trimethylsilyl P-Toluenesulfirl~te p-Toluene~ulfinic acid (20.6 g, 0.13 mol3 wa~
su~pended in hexamethyldi~ilazane (25 mL). Thi6 ~ixture ~as heated at reflux for 2 h under nitrogen.
at which time a~monia evolution ceased. The re6ulting cloudy 601ution wa~ then cooled to ~oom temperature before emOving volatile~ under vacuum (0.025 mm).
The remaining oil was then ~ractionated through vigorously dried glas~ware to give trimethyl~ilyl . i, . . .

~;25~ 6 p-tsluenesulfinate (18.2 g, 61% yield) afi a ~olorles~
oil: bp 65-67 (0.065 mm): lH NMR (CDC13): 0.2 (s, -5iMe3, 9H~, 2.3 ( , CH3-Ph-, 3H), and 7.3 ppm (ABq, J = R 4 Hz, ~1 3 = 27.3 ~z, Ph~H~s, 4H).
Anal Calcd. for CloHl6o~sis: C, 52.59: H, 7.06:
Si, 12.30. Found: C, 52.19; H, 6.86, Si, 11.92.
Part B. Tris(dimethylamino)sulfonium(TAS) _ _ P-Toluenesulfinate _ Tri~ethylsilyl p-toluenesulfinate Prom Part A
- 10 (12.00 g, 52.$ mmol) was added deopwise to a ~tirred - solution of tris(d;methylamino)sulfonium(TAS) trimethyldifluorosilica~e (14.47 g, 52.5 mmol) in "degassed" acetonitrile (50 mL~ cooled to 0 under nitrogen. The ~esulting solution was stirred for 30 min be$ore warming it to coom temperature. The volatiles were removed under vacuum (0.025 mm) to give tri6(dimethylamino)sulfonium p~toluenesulfinate (1605U g, 99% yield) a~ a white cey~talline ~olid: mp 90-960; lH NMR (CDC13): 2.30 (s, CH3-Ph-o 3H).
2.81 (s. (CH3)2N, 18H) and 7.37 (ABq, J = 5n9 Hz~
~1 3 = 3~.4 Hz, Ph-H's, 4H); 19F NMR showed that there were no fluorine-containing impuritie6 pre6ent- Anal. Calcd. for C13H25N302S2 C, 48.87; H, 7.~9; N, 13.15: S, 20.07. Found: C, 48.77;
H, 8.03; N, 13.63 S, 19.72.
Part C. Polymerization of Methyl Methacrylate Catalyzed by TAS P--Toluenesulfinate To a solution of 5 mL of MMA and 0.7 g of ~TS
_ in tetrahydrofuran (THF) at 23 was added a solution of 0.05 g of the catalyst compound prepared as ;n Part B, i~ 1:1 THF/acet~nitrile. The temperatuce ro6e 610wly to about 47. After 45 minutes, another 5 mL
of MMA was added and the tempecature co8e as before.
After 1 h at room temperatur0, a third 5 mL poetion of 3S MMA was added and the temperature rose to about 440, ~:~s6~

indicatins ~urther polymerization, a ~lear indication that the polymer ~as "livi.ng". ~vaporation of vola-tiles gave lB . 8 g of polymer. GPC: Mn 3390~ Mw 4820, D 1.42. ' ~hen TAS d-10-camphorsulfinate was ~ub~tituted for TAS p-toluene~ulfinate in Part C, exothe~mic polymerization of ~MA wa~ ~imilarly effected.
RxamPle~3 Part A. Tri~(dimethYlamino)sulfonium 4-Nitrophenolate [(4-Nitrophenyl)oxy]trimethylsilane (11.5 mL, 60 mmol) wa6 added dropwise to a stirred solution of i TA~ trimethyldifluorosilicate (16.5 g) in out-ga~ed acetonitrile (60 ~L), cooled to -10 under nitrogen.
The reaction mixture was stirred for 1 h at -10 and then allowed to warm to ambient tempera~ure.
Volatiles were removed under vacuum to give a yellow i oil (18.5 g). Elemental analy~is and lH NMR and 19F NMR ~CD3CN) confirmed the title product in good purity.
Part B. Polymerization of MMA Catalyzed by TAS 4-NitroPhenolate A solu~ion of MTS (0.75 g, 4.31 mmol) in THF
~15 mL) was treated with a THF 601ution of the TAS
4-nitrophenolate ~0.05 g in 0.5 mL of THF) prepared in Part A. MMA t5 mL) was then added by ~ycinge.
~ Exothermic ~emperature ci~e wa~ controlled by a ! cooling bath. After 1 h at room temperature, a futher 5 mL of MMA was added, agaîn followed by a temperature ri~e. After cooling and 601ven~ removal, ~ 30 11.5 g of the expected polymer was obtained.
GPC: Mn 1890, ~ 2180, D 1~15 ~L25~

ExamPle 4 Part A. Tris(dimethYlamino)sulfonium Acetate (Acetyloxy)trimethylsilane (14 mL, 94 mmol) was added dropwise to a ~tirred 601ution ~f TAS
trimethyldifluorosilicate (24.7 g, 87.7 mmol) in sut-gassed acetonitrile (75 mL), cooled to ~10 under nitrogen. The solution wa~ tirred for 30 minutes at 0, warmed to ambient tempecature and evaporated under vacuum to gi~e 20.6 g of a white 601id which wa~ shown by elemental analysi6 and lH NMR (CDC13) to be the title compound.
Par~ B. PolYmerization of MMA Catalvzed b~ TAS Acetate To a solution of MTS (0.75 g) in THF was added 0.05 g of TAS ac~etate, prepared in Part A, dissolved in T~F. MMA ~5 mL) was added and the exotherm which occurred was controlled by a cooling bath. After 1 h,

5 mL of ~MA wafi added and the temperature rose to 45~. After 1 h, a third 5 mL portion of MMA wa~
added, again followed by an exotherm. After volatiles removal, 19.6 g of the expected polymer wa~ recovered.
GPC: Mn 2920, Mw 9260, D 3.17.
ExamPle_5 Part A. TetraethYlammonium 4-NitroPhenolate A ~ixture of 4-nitrophenol (13.9 g, 0.10 mol) and benzene (250 mL~ was treated with tetraethyl-ammonium hydroxide (14.7 g, 0.10 mol), added as a 20%
aqueous ~olution. The mixture was heated under re~lux until all watec was removed by azeo~ropic distillation.
- The ~olution wa~ allowed to 5001 with continued ~ 30 sticring. ~pon ~tanding, 25.4 g of a yellow solid was obtained; it was recrystallized from THF. lH MMR
(CDC13) confirmed ~he title compound.

~Z5~6~

Pact B. Polymerization of ~MA Catalyzed by Tetrae~hYlammonium 4-NitroPhenolate To a solution of M~S (0.75 g~ in ~HF (20 mL) was added 0.075 g of tetraethylammonium 4 nit~o-phenolate, prepared in Part A. and the re6ultingmixtu~e was treated with ~MA (5 mL). The exotherm which wa~ obtained was controlled ~o below 35~ by a cold bath and 810w rate of MMA addi~ion. After 1 h at room temperatuLe, 5 mL of MMA was added: an exotherm - 10 was obtained and the above procedure wa~ repeated.
After 1 h at room temperatule, a third 5 mL portion of ~MA wa~ added and an exotherm was again noted. After removal of volatiles, 17.8 g of the expected polymer was obtained. GPC: ~n 2900, ~ 3950, D 1.36.
Example 6 Polymerization of ~ethyl Me~hacrylate CatalYzed bY Tetraethvlammonium Nitrite Tetraethylammonium nitrite was prepared by the ~eaction of 6ilver nitrite and tetraethylammonium chloride in wate~. To a stirred solution of 0.87 g (1.0 mL, 5 ~mol) of MTS, and 20 ~L of 1 ~ tetra-ethylammonium nitri~e/acetonit~ile in 20 mL of aceto-nitrile was added 10 g (10.8 mL, 100 mmol) of methyl methacrylate (purified by pa6sage over neutral alumina under argon). One h after the end of ~he exothermic reaction an aliquo~ wa6 removed for analysis by GPC
and the poly(methyl ~ethac~ylate) (PMMA) was found to have ~n 1880, ~ 2470, D 1.32 (theor. ~n 2100) with le~s than 1% of a high molecular weight component - 30 (Mn 1,333,000) by GPC. Addition oE S g (5.4 mL, 50 mmol) of methyl methacrylate gave an exothermic ~eaction. After 30 min. 3 mL of methanol was added and the solution was evaporated in vacuo to 15.2 g of solid poly(methyl methacrylate). The P~MA had an ~n 2630, ~ 3170, D 1.20 (~heor. Mn 3100) with les6 than 1% of a high molecular weight component (Mn 1~ R39, 000~,

6~6 lB
xamP 1 e ?
Polymerization of Methyl Methacrylate Catalyzed by Tetrabutylammonium Nitrite To a stirred ~olution of 20 ~L of l M
tetrabutylammonium nitzite/acetonitrile in 25 ~L of tetrahydrofuran was added 10 g (10.8 mL, 100 mmol) of methyl methacrylate, purified afi in Example 6. After 3 mL of the monome~ had been added, the addi~ion was ~opped fo~ 1 h, after whi~h time an aliquo~ of the reaction mixture was removed for analy~i~ for polymer.
GPC analysis showed the absence of detectable polymer.
Then 0.87 g (1.0 mL, 5 ~mol) of MTS ~a~ added, giving an exothermic reaction. The remaining methyl methacrylate was then added. After 1 h~ an aliquot of 1 15 the reaction mixture ~as removed for GPC analy~is:
I Mn 2070, Mw 2450, D 1.18 (theor. ~n 2100). Then, 5 I g (5.4 mL, 50 mmol) of methyl metha~ryla~e was added, I giving an exothecmic polymerization, indicating that the polymer was "living". Removal of solvent ~n vacuo gave 16.5 g of solid poly(methyl methacrylate):
~n 2840, ~w 3690, D 1.30 (theor. Rn 3100).
Example 8 Polymerization of Methyl Methacrylate Ca~alyzed by TetraethYlammonium CY~nate To a solution of 20 ~L of 1 M
I tetraethylammonium cyanate/acetonitrile in ~5 mL of - I tetrahydrofuran was added 10 g (10.8 mL, 100 mmol~ of me~hyl methacrylate. pucifed as in Example 6. After 3 mL of the monomer was added, the addition was stopped ~` 30 for 1 h. after which time an aliquot of the reaction mixture was removed for analysi6 for polymer. GPC
analysis showed the absence of detectable polymer.
Then, 0.87 g (1.0 mL, 5 mmol) of MTS was added, giving an exothermic reaction. The remaining methyl ~5~6~

methacrylate was then added. ~fter 1 h an aliquot of the reaction mixture wa~ removed for GPC analysis:
Mn 2690, ~ 3240, D 1.20 ~theor. ~n Z100).
Then, 5 g (5.4 mL, 50 mmol) of methyl me~hacrylate wa~
added, giving an exothermic polymerization, ~ndicating that the polymer was "living". Removal of the solvent in vacuo gave 16.5 g of ~olid poly(methyl methacry-late): Mn ~130, ~w 5360, ~ 1.30 (theor. Mn 3100).
Exam~le g Polymerization of Butyl Acrylate Catal~zed bY Tetraethylammonium Cyanate ~! To a stirred solution of 0.44 g (0.5 mL, 2.5 mmol) of MTS and 20 ~L of 1 M ~etraethylammonium cyanate/acetonitrile in 40 mL of teerahydrofuran was added 610wly 32 g (35.8 mL. 250 mmol) of butyl acrylate, purified by pas~age over a ~hort co]um~l of neutral alumina under a~gon. The exothelmic polymerization occurred ~lowly during monomer addi~ion and a~celerated after the monomer wa6 added. Two more additions of 20 ~L of 1 M ~etraethylammonium ~ cyanate/acetonit~ile were made, producing a 6mall exotherm with the fir~t addition and no ~xotherm with the final addition. After addition of 3 ~L of methan~l~ evapoLation in vacuo gave 36 g of liquid re~idueO ~MR analy6is showed the pre~ence of 92.2%
poly(butyl acrylate) ~nd 7.8% butyl acrylate. GPC
analysis of the polymer showed Mn 9510, ~ 23gO0, D 2.52 (theor. M~ 12,900).
ExamPle 10 Polymerization of Ethyl Acrylate CatalYzed bY Tetrabutylammonium Cyanate ~o a solution of 0.87 ~ (1.0 ~L, 5 mmol) of ~'l'S and 20 ~L of 1 M tetLabutylammonium cyanate~
tetrahydrofuran in 20 mL of tetrahydrofuran wa~ added 10 g (10.8 mL, 100 mmol~ of ethyl acrylate, purified 1~

~:2S66a.!~

as in Example 6. ~he initial exother~ faded after 2 mL Df monomer was added and resumed after all of the monomer had been added, carrying the temperature to 5~. After 1 h, addition o~ 5 g t5.~ mL,~50 mmol) of ethyl acrylate gave no exotherm. After 30 minute6, 3 mL of methanol was added, and the solution was evaporated in vac,uo ~o provide 10 g of liquid poly-(ethyl acrylate). NMR analysis of ~he polymer ~howed the presence of a ~race of ethyl acrylate. GPC
- 10 analysis showed a bimodal di~tribution, with the pcincipal fraction haYing Mn 67~0, ~w 14BOO. D 2.18 ~theor. ~ 2100).
ExamP-le 11 Polymerization of Methyl Methacrylate ,Catalyzed by Tetrabutylammonium Cyana~e To a solution of 0.87 g (1.0 mL, 5 mmol) of MTS and 71 mg (0.25 ~mol) of tetrabutylammonium ~yanate in 20 mL of acetonierile was added 10 y (10.8 mL, 100 mmol) of methyl methacrylate purified as in Example 6. The exothermic polymerization continued throughout the monomer addition. One h after the end of the addition. 5 g S5-4 mL, 50 ~mol) of methyl me~hacrylate wa~ added, producing an exothermic polymerization. After 30 minutes 3 mL of methanol was added, and the ~olution was evaporated in vacuo to proYide 16.3 g of ~olid poly(methyl methacrylate).
GPC analy~is showed a biomodal distribution (peak maxîma at 2B18 and 12,590) with -- Mn 2930, Mw 6690, D 3.03 (theor. ~n 3100).
30 ExamPles l? to 46 General Procedure for the Polymeriza~ion of Methyl Methacryla~e Catalyzed bY Various Tetra(n-butvl)ammonium OxYanion Salt~
To a 100 mL Lound-bottom flask containing a ~tirred ~olution of 30 mL of te~rahydrofuran and 0.20 ~0 664~i mL (1.0 mmol) of ~TS wa~ added 0.02 mmol of - tetrabutylammonium ("ate") catalyst (dissolved in acetonitrile in a concentration ~anging from 0.28 to 0.55 ~olar3. After 5 minute~ 5.0 ~ (46.7 mmol) of methyl methacrylate was added dropwise at a ~ate of 1.0 mL/min. The ~eaction mixture exothermed. Exactly one h from the time at ~hich the peak temperature ~as observed, a 0.5 mL sample of polyme~ ~olution (A) wa~
withdcawn, after which 5.0 mL (46.7 mmol) of methyl methaccylate was added at a rate of 1.0 mL~min. A
~imilar, but u6ually slightly lower, maximum temperature accompanied the re~ulting exotherm. One h from the maximum exotherm temperatu~e, a second 0.5 m~
~ample of polymer lB) was withdrawn and a third 5.0 mL
(46.7 mmol) of methyl methacryla~e wa~ added at 1.0 mL/min. The third 0.5 mL ~ample of polymer ~C) was withdrawn either one h f~om the peak exotherm temperature or 16 h later (the next morning).
fourth 5.0 mL (46.7 mmol) of methyl methacrylate was Z0 added (all at once) after the 16 h wait. If no exotherm followed thi~ addi~ion. an acetonitrile solution of 0.01 mmol of the "ate" catalyst wa6 added and the total polymer ~olution was quenehed with methanol after an additional two h. The polymel wa~
Z5 precipitated ~rom hexaneO dried at ~0/20 mm and a final polymer sample (Fl was taken. The four polymer samples were then analyzed by GPC.
Catalysts employed and the reEul~6 obtained are given i~ Table 1. In Exa~ple~ 12, 14, 15 and 46, ~ 30 molar amount~ of biacetate. bibenzoate, aceta~e and acetic acid are shown. The bibenzoate/benzoic acid catalyst of Example 46 was prepared 1n ei~u by adding to a 601ution of tetrabutylammonium benzoate about 1.7 mole6 of ben~oic acid per mole of benzoate sal~. The catalyst6 of Examples 45 and 46 ~ere di~solved in toluene in~tead of acetonitrile.

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x ~Z56646 ExamPle 47 Polymerization of Methaccylate Monomers Catalyzed bv Variou~ Tetra~n-butrl)ammonium Oxyanion Salts A fluoei~ated methacrylate (5 g)'of the formula CH2~CH(CH3)C02CH~CH2R~ wherein Rf i~ perfluoroalkyl of 1 to 20 carbon atoms, or a mixture thereof, ~a~ mixed wi~h ~TS initiator (0.2 mL, 1 mmol): to this mixture was added 8 solution (0.2 mL) of the tetza(n-butyl)ammonium 6alt di~solved i~
trifluoromethylbenzene (TFB)(O.Ol mol of ~alt in 10 g of TFB). Hea~ generated by the polymerization, and ! the rate at which cloudiness developed in the polymerizing 6y6tem, were u~ed to rate catalyst effectiveness, a~ shown in Table Z wherein effectivene~s increases on a scale of O ~no detectable polymerization) to 10.
Salts ~ere prepared by known methods, most generally by reacting ~he conjugate acid~ with tetra~n-butyl)ammonium(TBA) hydroxide.
The TBA ~alts of adipic and boric acid~
! eroduced little or no poly~erization of the fluorinated methacrylate monomer. Howevec. when that monomer wa6 replaced with 2-ethylhexyl methacrylate.
vigorou~ polymecization wa~ observed with these salt6. It wa6 al80 found ~hat the base tetra(n-butyl)ammonium hydeoxide catalyzed polymerization of 2-ethylhexyl methacrylate but ~ot the fluorinated methacrylate monomer.
-~- The TBA salts of R~C02H, for exampla, - 30 CF3C02H, and of p-toluenesulfonic acid produced little or no polymeri~ation; the pKa of the~e acids is below 5 and the salt~ are out~ide this invention.

~S~i6~6 le 2 Coni~g~ e~ ati~

Aceti~ 10 Pivalic 7 Valeric Hexanoic 0 Octanoic 7 2-Ethyl Hexanoic B
~enzoic 4 o-~oluic 5 I Adipic o Rf C~2H o RfCH2C2H 2 p-Tol~enesulfonic o ( ~8Yl~cH2CH2C)_ ) 2P02H

RfcH2cH2s~H2~H2co2~ 6 ~3~O4 0 Phenol 3 ! o-Phenoxybenzoic : .p-Anisic 2 p-Toluic 2 ExamPle ~8 Polymerization of MMA i~ the Presence of 2-Methylphenyla~etonitrile as Chain Tran~fer ~ent Catalyzed bY 3-Chlorobenzoate Thi6 example corresponds to ~xample 9 in _ 30commonly assigned Canadian application of W.R. Hertler et al (supra).
To a 801utio~ of 0.1 ~L l0O5 m~ol) of ~T~ and 20 ~L of 0.46 ~ tetrabutylammoniu~ m-chlo~obenzoate/
acetonitrile in 30 ~ of tetrahydcofuran ~a~ added a solution of ~59 mg ~0.466 mL, 3.5 mmol) af 2-methyl-phenylacetonitrile in 10.8 mL (100 mmol) of methyl me~hac ylate. After the monomer chain tran~fer agent had been added. a 610w exothe~m began and the ~emperature gradually ro~e 22 and then 610wly f 211.
NMR analysifi ~howed 94% convecsion to polymer.
Precipitation with aqueou~ methanol gave 9.6 g of poly(methyl methacrylate). GPC: M~ 4420, ~
- 10,700, D 2~42 ttheor. Mn ~or no chain ~ranfifer 18,900: for initiation only by 2-~ethylphenylaceto-nitrile 2816). U.V.u k258=0.054 corresponding to a M~ of 3190 per phenyl group.

BEST MODE FOR CARRY~MG OUT THE INVENTION
The best mode presently co~templated for ' carryinq out the invention i~ illustrated by Example6 ¦ 2-8, 10, 12~20, 22-29, 31-37 and 40-48, provided, however, it is to be understood that the best mode will depend o~ a variety of factors, ~hich will be obviou~ to the ~killed artisan who reads this 6pecifi-cation. Por example, as is evident from Example 47, Table 2, the oxyanions vary in their activity as a catalyst. For some applications, paeticularly commercial applica~ions, it is essential to take in~o ! 25 con~ideration such factors a8 polymerization I temperatu~e, solvent ~edium, reactor size and type, i initiator, monomer(s), polyme~ization rate de~ired, conversion, yield, recycling capabilities and polymer proces~ing. The point to be made i8 that, referring again to Table 2, ~he most active oxyanion catalysts are not nece~arily the best cataly6ts for each and every applicatlon. Selectio~ o~ cataly~t, therefore, will depend on the ~ole which the catalyst will play in the overall scheme of the polyme~ization to be carlied out. Moreover, as can be seen from Table 1 ~7 ~25~

(E~xample~ 12 ~o 46}, cataly~t selection inf luences ~ertain propertie6~ such as ololecular weight and polydi~per~ity ~D), of ll:he polymer pcoduced. and the life sparl of "living" end of the polymer ~hain~.

!

3û

Claims (52)

CLAIMS:

1. Polymerization process comprising contacting under polymerizing conditions at least one polar, acrylic type alpha-olefinic monomer with (i) a tetracoordinate organosilicon, organotin or organogermanium polymerization initiator having at least one initiating site, and (ii) a catalyst which is a salt comprising a suitable cation and an oxyanion which can form a conjugate acid having a pKa (DMSO) of about 5 to about 24.

2. Process of Claim 1 wherein the polar monomer is 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 H or a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, provided that at least one R1 group is not H;

R is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms, or a polymeric radical containing at least 20 carbon atoms, any of said radicals optionally containing one or more ether oxygen atoms within aliphatic segments thereof, optionally containing one or more functional substituents that are unreactive under polymerizing conditions, and optionally containing one or more reactive substituents of the formula -Z'(O)C-C(Y1)-CH2 wherein Y1 is H or CH3 and Z' is O or NR'; and each of R' and R" is independently selected from C1-4 alkyl.

3. Process of Claim 2 wherein the initiator is selected from the group consisting of (R1)3MZ, (R1)2M(Z1)2 and O[M(R1)2Z1]2 wherein:
R1 is as defined for the monomer;
z is an activating substituent selected from the group consisting of -CN, , , -SR, OP(NR'R")2, -OP(OR1)2, -OP[OSi(R1)3]2 and mixtures thereof;
Z1 is the activating substituent ;

R, R1, R', R", X' and Z' are as defined above for the monomer;
each of R2 and R3 is independently selected from H and hydrocarbyl, defined as for R above;
m is 2, 3 or 4;
n is 3, 4 or 5; and M is Si, Sn or Ge, provided, however, when Z is M is Sn or Ge, (a) at least one of any R, R2 and R3 in the initiator optionally containing one or more initiating substituents of the formula -Z2-M(R1)3 wherein M and R1 are as defined above;

Z2 is an activating diradical selected from the group consisting of , and mixtures thereof, wherein R2, R3, X', Z', m and n are as defined above, provided, however, when Z2 is , M is Sn or Ge, (b) R2 and R3 taken together are if Z is or -C?=C(R2)(R3) and/or z2 is -Z'-?-C(R2)(R3)-, and (c) X' and either R2 or R3 taken together are if Z is or -O?=C(R2)(R3) and/or Z2 is .

4. Process of Claim 1 wherein the conjugate acid has a pKa (DMSO) of 6<pKa<21.

5. Process of Claim 1 wherein the conjugate acid has a pKa (DMSO) of 8<pKa<18.

6. Process of Claim 3 wherein the conjugate acid has a pKa (DMSO) of 6<pKa<21.

7. Process of Claim 3 wherein the conjugate acid has a pKa (DMSO) of 8<pKa<18.

8. Process of Claim 1 wherein the conjugate acid is of the formula [Q(x1OH)p]q wherein Q, of valence p, is CN, N(O), P(O), PH(O), R4 or R34 Si;
each R4, indepsndently, is C1-20 hydrocarbyl or a polymeric radical containing at least 20 carbon atoms;
X1 is C(O), S(O) or a single bond; and each of p and q is an integer and is at least 1.

9. Process of Claim 8 wheesin X1 is C(O).

10. Process of Claim 9 wherein Q is CN or N(O) and each of p and q is 1.

11. Process of Claim 9 wherein Q is R4 and q is 1 or 2.

12. Process of Claim 11 wherein R4 is C1-20 hydrocarbyl.

13. Process of Claim 12 wherein R4 is C1-8 alkyl, phenyl or substituted phenyl and q is 1 or 2.

14. Process of Claim 8 wherein X1 is a single bond.

15. Process of Claim 14 wherein Q is R4 which is phenyl or substituted phenyl and q is 1 or 2.

16. Process of Claim 8 wherein X1 is S(O) and Q
is R4.

17. Process of Claim 16 wherein R4 is C1-20 hydrocarbyl.

18. Process of Claim 17 wherein R4 is phenyl or substituted phenyl and q is 1 or 2.

19. Process of Claim 1 wherein the oxyanion is a monooxyanion.

20. Process of Claim 1 wherein the oxyanion is bioxyanion.

21. Process of Claim 1 wherein the oxyanion is a mixture comprising mono- and bioxyanions.

22. Process of Claim 21 wherein the mixture contains a conjugate acid having a pKa (DMSO) of about 5 to about 24.

23. Process of Claim 19 wherein the oxyanion is a carboxylate.

24. Process of Claim 23 wherein the oxyanion is acetate, benzoate or substituted benzoate.

25. Process of Claim 24 wherein the substituted benzoate is a chlorobenzoate.

26. Process of Claim 20 wherein the bioxyanion is biacetate, bibenzoate or substituted bibenzoate.

27. Process of Claim 19 wherein the oxyanion is a phenolate or substituted phenolate.

28. Process of Claim 20 wherein the bioxyanion is a biphenolate or bi(substituted phenolate).

29. Process of Claim 1 wherein the oxyanion is a sulfinate.

30. Process of Claim 29 wherein the oxyanion is an aryl- or substituted aryl sulfinate.

31. Process of Claim 1 wherein the oxyanion is a nitrite or cyanate.

32. Process of Claim 1 wherein the suitable cation is a quaternary ammonium, tris(dialkylamino)-sulfonium or an alkali or alkaline earth metal cation.

33. Process of Claim 32 wherein the cation is a tetraalkylammonium cation.

34. Process of Claim 33 wherein the cation is tetrabutylammonium.

35. Process of Claim 32 wherein the cation is tris(dimethylamino)sulfonium.

36. Process of Claim 24 wherein the suitable cation is tetraalkylammonium.

37. Process of Claim 36 wherein the cation is tetrabutylammonium.

38. Process of Claim 37 wherein the oxyanion salt is tetrabutylammonium acetate.

39. Process of Claim 25 wherein the oxyanion salt is tetrabutylammonium m-chlorobenzoate.

40. Process of Claim 26 wherein the suitable cation is tetraalkylammonium.

41. Process of Claim 40 wherein the cation is tetrabutylammonium.

42. Process of Claim 27 wherein the suitable cation is tetraalkylammonium.

43. Process of Claim 42 wherein the cation is tetrabutylammonium.

44. Process of Claim 28 wherein the suitable cation is tetraalkylammonium.

45. Process of Claim 44 wherein the cation is tetrabutylammonium.

46. Process of Claim 21 wherein the mixture comprises mono- and bicarboxylates.

47. Process of Claim 21 wherein the mixture comprises mono- and biphenolates or mono- and bi(substituted phenolates).

48. Process of preparing the mixture of Claim 21 wherein a suitable monooxyanion salt is reacted in situ with one or more conjugate acids having a pKa (DMSO) of about 5 to about 24.

4g. Process of Claim 48 wherein one equivalent of salt is reasted with 0.1 to about 2 equivalents of conjugate acid.

50. Process of Claim 1 wherein the polymer produced is "living" and contains the silicon, germanium or tin of the initiator at "living" ends.

51. Process of Claim 3 wherein the polymer produced is "living" and contains the silicon, germanium or tin of the initiator at "living" ends.

52. Process of Claim 20 wherein the bioxyanion is admixed with a conjugate acid having a pka (DMSO) of about 5 to about 24.