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Group Transfer Polymerization Catalyzed by Mercury Compounds

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Group Transfer Polymerization Catalyzed by Mercury Compounds turopaiscnes Patentamt 1� European Patent Office © Publication number: 0 266 062 Office europeen des brevets A1 © EUROPEAN PATENT APPLICATION Q) number: 87308549.2 C08F Application © Int. CI.4: 4/42 , C08F 4/72 © Date of filing: 2&09.87 © Priority: 29.09.86 US 912118 © Applicant: E.I. DU PONT DE NEMOURS AND COMPANY ® Date of publication of application: 1007 Market Street 04.05.88 Bulletin 88/18 Wilmington Delaware 19898(US) © Designated Contracting States: © Inventor: Dicker, Ira Bernard AT BE CH DE ES FR GB GR IT LI LU NL SE 1016 Jeffrey Road Wilmington Delaware 19810(US) © Representative: Jones, Alan John et al CARPMAELS & RANSFORD 43 Bloomsbury Square London, WC1A 2RA(GB) & Group transfer polymerization catalyzed by mercury compounds. Mercury compounds which are useful as co-catalysts in Group Transfer Polymerization are disclosed. IN D a D a. JJ .erox Copy Centre 0 266 062 Group Transfer Polymerization Catalyzed by Mercury Compounds BACKGROUND OF THE INVENTION Field of the Invention 5 This invention relates to Group Transfer Polymerization of acrylates catalyzed by selected mercury compounds. 70 Background United States Patents 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,605,716; 4,656,233; and 4,681,918, and EP-A-0 145 263, EP-A-0 188 539, and EP-A-87305069.4, referred to hereinafter as "the aforesaid patents and patent applications", disclose processes for polymerizing an 75 acrylic or maleimide monomer to a "living" polymer in the presence of an initiator, which is a tetracoor- dinate organosilicon, organotin or organogermanium compound having at least one initiating site, and a co- catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selection oxyanion. Such polymerization processes have become known in the art as Group Transfer Polymerization (Webster et al., J. Am. Chem.Soc, 105: 5706 (1983)). 20 Preferred monomers for use in Group Transfer Polymerization are selected from acrylic and maleimide monomers of the formula CH2=C(Y)X and CH====CH I.I Ofe=C C=='0 , and mixtures thereof, \ / N wherein: X is -CN, -CH = CHC(0)X' or -C(0)X'; Y is -H, -CH3, -CN or -C02R, provided, however, when X is -CH = CHC(0)X', Y is -H or -CH3; 35 X' is -OSi(R1)3, -R, -OR or -NR'R"; each R\ independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic- aromatic radical containing up to 20 carbon atoms or -H, provided that at least one R1 group is not -H; is: (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical 40 containing up to 20 carbon atoms; (b) a polymeric radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under 45 polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) 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' wherein R' is as defined below; and each of R' and R" is independently selected from Cm alkyi. Preferred initiators are selected from tetracoordinate organsilicon, organotin and organogermanium compounds of the formulas (Q'bMZ, (Q')2M(Z1)2 and [Z1(Q')2M]20 wherein: 50 each Q', independently, is selected from R1, OR1, SR1 and N(R!)2; Ri is as defined above for the monomer; Z is an activating substituent selected from the group consisting of 0 266 062 R 0 I I 2 'CN, -C-CN, -C--CX , L 2 u 0 R II II I c- L- c- @C- I Z'' J ' I • -N=C=C-K , -OC=-C-R -OC— ~CR* "2 I, X2 R Z ' OC====-CR , -SR' , -0P(NR'R" )2 , -OP(ORA)2, -(chJ -uh-luskh1^ and mixtures thereof; R', R", R and R1 are as defined above for the monomer; JO Z1 is -OC-C-R ; la I, X2R3 TV is -ushh1)^ -H , -UH or -NR R ; R6is (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; *5 (b) a polymeric radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or so (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites; and each of R2 and R3 is independently selected from -H and hydrocarbyl, defined as for R6 above, subparagraphs (a) to (e); R', R" and R1 are as defined above for the monomer; Z' is as defined above for the monomer; m is 2, 3 or 4; >5 n is 3, 4 or 5; R2 and R3 taken together are 0 266 062 R20 1 « w 2wJ provided Z is -C-CX or -OC=C(R )(R ); f r. X2 and either R2 or R3 taken together are 15 20 R20 fIP, II T O provided Z is -C-CX or -OC=C(R )(R ); and 25 M is Si, Sn, or Ge., provided, however, when Z is 30 -OC== -C- or lcH2jn LcH2)i 35 M is Sn or Ge. Preferred co-catalysts are selected from a source of bifluoride ions HF2", or a source of fluoride, cyanide or azide ions, or a source of oxyanions, said oxyanions being capable of forming a conjugate acid having a pKa (DMSO) of about 5 to about 24, preferably about 6 to about 21 , more preferably 8 to 1 8, or a suitable Lewis acid, for example, zinc chloride, bromide or iodide, boron trifluoride, an alkyiaiuminum oxide or an alkyiaiuminum chloride, or a suitable Lewis base, for example, a Lewis base of the formula selected from (R4)3M' and 45 N wherein: 50 M' is P or As; X1 is 1 1 - N -or - C H, provided, however, when the monomer is a nitrile, X1 is 55 1 each R4, independently, is: (a) a C n.12 alkyl, C4.12 cycloalkyl, C6-i2aralkyl or di(Ci.4 alkyl)amino group; 4 0 266 062 (D) a group ot (a) wherein two or three of the alkyl, cycloalkyl and/or aralkyl groups are joined together by means of one or more carbon-carbon bonds; (c) a group of (a) or (b) wherein the alkyl, cycloalkyl and/or aralkyl groups contain within aliphatic segments thereof one or more hetero atoms selected from 0, N and S; or 5 (d) a group of (a), (b) or (c) wherein the alkyl, cycloalkyl and/or aralkyl groups contain one or more substituents that are unreactive under polymerizing conditions; and each R5 is -CHaCHror -CH2CH2- containing one or more alkyl or other substituents that are unreactive under polymerizing conditions. Additional details regarding Group Transfer Polymerization can be obtained from the aforesaid patents and patent applications, the disclosures of which are hereby incorporated by reference. 70 Razuvaev et al., Vysokomol.Soedin.(B), 25(2): 122-125 (1983) disclose polymerization of methyl methacrylate and/or styrene initiated by a mixture of silicon tetrachloride and alkyls of mercury, tin or lead, at 20-50 °C. Sakurai et al., Tetrahedron Lett., 21_:2325-2328 (1980) disclose mercuric iodide catalyzed isomerization of (trimethylsilylmethyl)chloromethyl ketone to (1-chloromethyl ethenyl)oxytrimethylsilane. Burlachenko et al., Zhur, Obshchei Khim.,43(8):1 724-1 732 (1973) disclose isomerization of cis-ketene 7510 silyl acetals into the trans-isomer catalyzed by triethylsilyl bromide and mercuric bromide. Litvinova et al., abstract of Dokl. Akad. Nauk. SSSR, 173(3):578-580 (1967); CA 67: 32720j, disclose the mercuric iodide- catalyzed rearrangement of triethylacetonylsilane to (isopropenyloxy)triethylsilane. Baukov et al., abstract of Dokl. Akad. Nauk SSR, 157(1 ):1 19-1 21 (1964); CA 61_: 8333f, disclose the mercuric iodide-catalyzed rearrangement of (1-methoxy-1-ethenyloxy)triethylsilane to methyl 2-triethyl- 20 silylacetate. Satchell et al., Qtr. Rev. Chem Soc, 25:171 (1971) disclose that mercuric halides are very weakly acidic Lewis acids. The present invention provides mercury containing catalysts which can be used in Group Transfer Polymerization of selected acrylic monomers. There is no suggestion in any of the foregoing references that 25 such or similar mercury containing compounds would be useful as catalysts in Group Transfer Polymeriza- tion. SUMMARY OF THE INVENTION ?0 The present invention provides a Group Transfer Polymerization process comprising contacting under polymerizing conditions at least one acrylic monomer of the formula CH2 = CHC(0)X' with a tetracoordinate organosilicon initiator and co-catalyst. The process is further characterized in that the co-catalyst is a mercury compound of the formula R7Hgl or Hgl_2, ?5 wherein the formulas, L is I or CIO*; X' is -OSi(R1)3, -R, -OR or -NR'R"; each R1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic- aromatic radical containing up to 20 carbon atoms or -H, provided that at least one R1 group is not -H; to R is: (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; (b) a polymeric radical containing at least 20 carbon atoms; (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments »5 thereof; (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or (e) a radical of (a), (b), (c) or (d) containing one or more reactive substituents of the formula -Z'(0)C- CH = CH2 wherein Z' is 0 or NR'; and each of R' and R" is independently selected from CM alkyl; and ;o R7 is a hydrocarbyl radical having 1 to 10 carbon atoms.
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