Verfahren zur Herstellung von Copolymeren aus Estern ungesaettigter Saeuren

摘要

Esters of unsaturated acids of the type R1-(CH=CR2)n-COOR3 in which R1 and R2 are the same or different and are hydrogen atoms or alkyl, aryl or cycloalkyl radicals containing from 1 to 10 carbon atoms, R3 is an alkyl, aryl or cycloalkyl radical having from 1 to 10 carbon atoms and "n" is 1 or 2, R2 being hydrogen when n=2, are copolymerized with esters of unsaturated acids with unsaturated alcohols, of the type: R4-(CH=CR5)m-COO(CH2)p-CR6=CR7-X in which R4, R5, R6 and R7 are the same or different and are hydrogen atoms or alkyl, aryl or cycloalkyl radicals containing from 1 to 10 carbon atoms, X is a hydrogen atom or a halogen atom, "m" is 1 or 2, "p" is a whole number between 0 and 6, R5 being a hydrogen atom when "m"=2. The polymerization is carried out at a temperature from -100 DEG C. to +20 DEG C. in the presence of an anionic catalyst selected from (a) a metallorganic compound of a Group I metal (Mendelaeeff); (b) a metallorganic compound of a Group II metal; (c) a compound containing metal-to-nitrogen bonds, and having the formula Me1rMe11[N(R1R11)]sXt in which R1 and R11 are the same or different and are alkyl, cycloalkyl, aryl or alkylaryl groups having up to 10 carbon atoms or form a heterocyclic ring with the nitrogen atom, Me1 is an alkaline metal, Me11 is a Group I, II or III metal, X is hydrogen or a halogen atom, "i" is zero or a whole number and "s+t" (each being a whole number, but "t" may be zero) is equal to the sum of the valencies of Me1 and Me11 and (d) a complex obtained by coupling compounds (a), (b) or (c) with Lewis bases. Lists of monomers and catalysts are given. In the examples: (1) methyl sorbate is copolymerized with allyl sorbate, methallyl sorbate, 4-pentenyl sorbate, allyl acrylate, 3-chloro-allyl-acrylate, 4-pentenyl acrylate, allyl methacrylate or methylallyl crotonate using as catalyst a butyl lithium solution, Li[N(C2H5)2], magnesium phenyl bromide, a complex of butyl lithium and tetrahydrofuran, or a complex of butyl lithium and tributyl amine; (2) methyl acrylate is copolymerized with allyl sorbate, methallyl sorbate, 4-pentyl sorbate, allyl acrylate, 4-pentenyl acrylate, 3-chloroallyl acrylate, methallyl crotonate or allyl methacrylae using butyl lithium or Li[N (C2H5)2] as catalyst; (3) methyl methacrylate is copolymerized with 3-chloro-allylacrylate or allyl methacrylate using butyl lithium; (4) a terpolymer is formed by copolymerizing butyl -b -styrylacrylate, methyl sorbate and allyl methacrylate using butyl lithium. The copolymers may be vulcanized.