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Catalyst for Group Transfer Polymerization

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Catalyst for Group Transfer Polymerization Europaisches Patentamt 19 European Patent Office Office europeen des brevets © Publication number: 0 407 414 B1 EUROPEAN PATENT SPECIFICATION @ Date of publication of patent specification © int. ci.5 : C08F 4/42, C08F 20/00, 27.01.93 Bulletin 93/04 C08F 22/40 (2j) Application number : 89903556.2 (22) Date of filing : 15.03.89 (86) International application number : PCT/US89/00972 @ International publication number : WO 89/09236 05.10.89 Gazette 89/24 (54) CATALYST FOR GROUP TRANSFER POLYMERIZATION. (30) Priority: 01.04.88 US 176808 (73) Proprietor : E.I. DU PONT DE NEMOURS AND COMPANY 1007 Market Street (43) Date of publication of application Wilmington Delaware 19898 (US) 16.01.91 Bulletin 91/03 (72) Inventor : DICKER, Ira, Bernard (45) Publication of the grant of the patent : 1016 Jeffrey Road 27.01.93 Bulletin 93/04 Wilmington, DE 19810 (US) @ Designated Contracting States : (74) Representative : Jones, Alan John et al BE DE FR GB IT NL CARPMAELS & RANSFORD 43 Bloomsbury Square London, WC1A 2RA (GB) © References cited : EP-A- 0 083 018 EP-A- 0 145 263 EP-A- 0 190 631 US-A- 4 581 428 US-A- 4 588 795 CO o Note : Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been LU filed until the opposition fee has been paid (Art. 99(1) European patent convention). Jouve, 18, rue Saint-Denis, 75001 PARIS EP 0 407 414 B1 Description BACKGROUND OF THE INVENTION 5 Field of the Invention This invention relates to Group Transfer Polymerization catalyzed by selected silanes, preferably in the presence of a suitable mercury compound and/or Lewis acid. 10 Background United States Patents 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,598,161; 4,605,716, 4,622,372; 4,656,233; 4,659,782; 4,659,783; 4,681,918; 4,695,607; 4,711,942; 4,732,955 referred to hereinafter as "the aforesaid patents", disclose processes for polymerizing an acrylic or maleimide monomer 15 to a "living" polymer in the presence of: (i) an initiator which is a tetracoordinate organosilicon, organotin or organogermanium compound having at least one initiating site; and (ii) a co-catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion. Such polymerization processes have become known in the art as Group 20 Transfer Polymerization (webster et al.,1. Am. Chem.Soc. 105: 5706 (1 983)). 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 25 | | 0--CO" C--0 , \ / N I 30 * and mixtures thereof, wherein: X is -CN, -CH=CHC(0)X' or -C(0)X'; 35 Y is -H, -CH3, -CN or -C02R, provided, however, when X is -CH=CHC(0)X', Y is -H or -CH3; 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 ali- phatic-aromatic radical containing up to 20 carbon atoms or -H, provided that at least one R1 group is not -H; R is: 40 (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical con- taining 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 poly- 45 merizing conditions; or (e) a radical of (a), (b), (c) or (d) containing one or more reactive substituents of the formula -Z'(0)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 C^ alkyl. Preferred initiators are selected from tetracoordinate organosilicon, organotin and organogermanium corn- so pounds of the formulas (Q')3MZ, (Q')2M(Z1)2 and [Z1(Q')2M]20 wherein: each Q', independently, is R1, OR1, SR1 or N(R1)2; R1 is as defined above for the monomer; Z is an activating substituent selected from the group consisting of 2 EP 0 407 414 B1 0 n -CN, -C-CN, -c — cx , I, 15 -N-C-C-R -OC--C-R -OO ■CR' I 20 X2 R Z' CH. 25 -OC-—-CR2r,r. , -SR' , -OP(NR'R"), , -OPfOR1),, 30 -OP[OSi(R1)3]2 and mixtures thereof; R', R", R and R1 are as defined above for the monomer; Z1 is 35 -OC-C-R ; 1 ' X2RJ2 J 40 X2 is -OSi (R1)3, -R6, -OR6 or -NR'R"; R6is (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical con- taining up to 20 carbon atoms; (b) a polymeric radical containing at least 20 carbon atoms; 45 (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 poly- merizing conditions; or (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, sub- 50 paragraphs (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; n is 3, 4 or 5; 55 R2 and R3 taken together are 3 EP 0 407 414 B1 5 provided Z is 10 -c-cx2 15 or -OC=C(R2 )(RJ); X2 X2 and either R2 or R3 taken together are 30 provided Z is 35 40 or -OC-C(R2 ) (R3 ) ; t X* 45 and M is Si, Sn, or Ge, provided, however, when Z is 50 -0O----CR2 55 or 4 EP 0 407 414 B1 0 R2 »• t c c- I Nch2� M is Sn or Ge. w 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 alkylaluminum oxide or an alkylalumi- num chloride, or a selected Lewis base. 15 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. Razuvaev et al., Vysokomol . Soed i n . (B) , 25(2):122-125 (1983) disclose polymerization of methyl metha- crylate 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 (tri- 20 methylsilylmethyl)chloromethyl ketone to (1-chloromethyl ethenyl)oxytrimethylsilane. Burlachenkoetal., Zhur, Obshchei Khim.,43(8):1724-1732 (1973) disclose isomerization of cis-ketene 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); CA67: 32720j, disclose the mercuric iodide-catalyzed re- arrangement of triethylacetonylsilane to (isopropenyloxy)triethylsilane. 25 Baukovetal., abstract of Dokl. Akad. Nauk. SSSR, 157(1):119-121 (1964); CA61; 8333f, disclose the mer- curic iodide-catalyzed rearrangement of [(1-methoxy-1-ethenyl)oxy]triethylsilane to methyl 2-triethylsilylace- tate. Satchell et al., Qtr. Rev. Chem Soc, 25:171 (1971) disclose that mercuric halides are very weakly acidic Lewis acids. 30 Weber, "Silicon Reagents for Organic Synthesis", New York, 1 983, Chapter 3, pp 21-39 describes prepa- ration and reactions of trimethylsilyl iodide, bromide and trifluoromethanesulfonate (triflate). These reagents are used as catalysts for cleaving chemical bonds in organic compounds and as silylating agents. They are often used in conjunction with organic bases such as pyridine. A more extensive survey of reactions catalyzed by trimethylsilyl triflate and trimethylsilyl esters of "Naf ion" perf luorsulfonic acid resin is provided by Noyori et 35 al., Tetrahedron, 37 (23), 3899 (1981). U. S. 3,478,007 discloses polymerization of unsaturated cyclic hydrocarbons using aluminun chloride and a trialkylsilicon halide as catalyst; AICI3 and trimethylsilyl chloride are exemplified. Toshima et al., Kogyo Kagaku Zasshi 72(4), 984 (1969) discloses polymerization of styrene catalyzed by trimethylsilyl chloride and mercuric chloride. 40 The above publications do not suggest the use of trialkylsilyl halides with or without added Lewis acids or mercuric compounds as catalysts for Group Transfer polymerization. United States Patent 4,732,955, supra, discloses Group Transfer Polymerization of one or more acrylate or acrylamide monomers in the presence of a mercury compound of the formula R7Hgl, wherein R7 is a Ci_i0 hydrocarbyl radical, or HgL2, wherein L is I or CI04. 45 The present invention provides an improved Group Transfer Polymerization process wherein the catalyst is a selected non-polymerization-initiating silane or a mixture thereof with a suitable mercury compound and/or Lewis acid. SUMMARY OF THE INVENTION 50 The present invention resides in a Group Transfer Polymerization (GTP) process comprising contacting under polymerizing conditions at least one monomer selected from acrylic and maleimide monomers with (i) a tetracoordinate organosilicon, -tin or -germanium compound having at least one initiating site, and (ii) a cat- alyst which is a suitable Lewis acid or mercury compound, the process further characterized in that the catalyst 55 consists essentially of: (a) about 10 to 100 mol % of a silane of the formula (R1)3Si-Z2 wherein: each R1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed 5 EP 0 407 414 B1 aliphatic-aromatic radical containing up to 20 carbon atoms or -H, provided that at least one R1 group is not -H; and Z2 is selected from I, Br, CI, CF3S03, CF3C02, CI04 and S04; and (b) 0 to about 90 mol % of at least one of a defined Lewis acid or mercury compound, provided, however, 5 when Z2 is other than I, at least 0.5 mole % of said Lewis acid or mercury compound selected from R7Hgl, Hgl2 and Hg(CI04)2 is present.
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