Alternierende Mischpolymerisate und Verfahren zu ihrer Herstellung

摘要

1,137,117. Alternating copolymers. SUMITOMO CHEMICAL CO. Ltd. 25 July, 1966 [26 July, 1965; 30 July, 1965; 2 June, 1966], No. 33405/66. Heading C3P. New copolymers are derived from (A) a non- conjugated unsaturated compound of the formula wherein R1 is an R4-, R4O-, R4S-, or R5R6N- group; Z is an oxygen or sulphur atom; Y is an oxygen or sulphur atom or -NR7 group; R2 is an ethylenically unsaturated hydrocarbon radical having 2 to 20 carbon atoms, which may be substituted; R3 is an organocyclic residue having 1 to 20 carbon atoms; R4, R5, R6 and R7 are hydrocarbon radicals having 1 to 20 carbon atoms, which may be substituted, or hydrogen, and (B) a conjugated compound of the formula wherein R1 and R11 are hydrocarbon radicals having 1 to 20 carbon atoms, which may be halogen-substituted, halogen atoms, or hydrogen atoms, while at least one of R1 and R11 is hydrogen; Q is a nitrile or group, where Y1 is Z2H, Z2R, Z2Me, NR1R11, R, a halogen atom or a hydrogen atom; Z1 and Z2 are oxygen or sulphur, R is a hydrocarbon or substituted hydrocarbon radical of 1 to 20 carbon atoms, R1, R11 are hydrogen or hydrocarbon or substituted hydrocarbon radicals of 1 to 20 carbon atoms including the case where R1 and R11 are mutually bonded other than at the nitrogen atom; and Me is a monovalent metal of Group I of Mendeleev's Periodic Table, or an ammonium group and Me1 is a divalent metal of Group II. They are prepared using a catalyst comprising either (1) MR111nX 3-n where M is Al or B, R111 is a hydrocarbon or substituted hydrocarbon group, X is a halogen atom, n is from 1 to 2, or a mixture of at least two of (A) MR111nX 3-n , (B) M1RIV and (C) M11X1 3 , where M, M1, M11 are Al or B, R111 and RIV are hydrocarbon or substituted hydrocarbon radicals, X and X1 are halogen atoms, or (2) a two-component catalyst comprising (a) an organo-compound of a metal of Group IIB, IIIB,IVB of the Mendeleev Periodic Table, and (b) a halogeno compound of a metal of Groups IIIB and IVB, wherein at least one metal in components (a) and (b) is Al or B, and (a) must be contacted with (b) in the presence of at least the conjugated compound (B). Optionally an activator such as oxygen or an organic peroxide is included in the copolymerization process. The copolymerization may be carried out in bulk or in solution. Many specific monomers, catalysts and peroxides are specified. In the examples, the following monomer and catalyst components are used :- (1) Methyl acrylate/vinyl acetate/Al 2 Et 3 Cl 3 (2) Methyl acrylate/vinyl acetate/AlEtCl 2 (3) Methyl acrylate/vinyl acetate/AlEt 3 /SnCl 4 (4) Acrylonitrile/vinyl acetate/Al 2 Et 3 Cl 3 (5) Acrylonitrile/vinyl acetate/AlEt 3 /SnCl 4 (6) Acrylonitrile/vinyl acetate/AlEt 3 /SnCl 4 / benzoyl peroxide (7) Methyl thiol acrylate/vinyl acetate/AlEt 3 / BF 3 (8) Methyl acrylate/vinyl stearate/Al 2 Et 3 Cl 3 (9) Methyl acrylate/vinyl benzoate/Al 2 Et 3 Cl 3 (10) Methyl acrylate/vinyl formate/Al 2 Et 3 Cl 3 (11) Methyl acrylate/allyl acetate/Al 2 Et 3 Cl 3 (12) Methyl acrylate/allyl laurate/Al 2 Et 3 Cl 3 (13) Methyl methacrylate/vinyl acetate/Al 2 - Et 3 Cl 3 (14) n-Butylcrotonate/vinyl acetate/Al 2 Et 3 - Cl 3 (15) Acrylonitrile/N - vinylpyrrolidone/Al 2 - Et 3 Cl 3 (16) Methyl acrylate/N lvinylpyrrolidone/ Al 2 Et 3 Cl 3 (17) Methyl methacrylate/N - vinylpyrrolidone/Al 2 Et 3 Cl 3 (18) Acrylonitrile/N - ethyl - N1 - vinyl urea/ AlEtBr 2 (19) Acrylonitrile/N-vinyl ethyl carbamate/ Al 2 Et 2 Cl 3 (20) Methyl acrylate/N-vinyl acetamide/Al- EtCl 2 (21) Acrylonitrile/S - vinyl - N,N - diethylthiolcarbamate/BEtCl 2 .