Controlled radical polymerization process for (meth)acrylic...

C - Chemistry – Metallurgy – 08 – F

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402/387, 402/520

C08F 4/80 (2006.01) C08F 4/00 (2006.01)

Patent

CA 2209061

This process is characterized by the fact that block, solution, emulsion or suspension polymerization or copolymerization is conducted, at temperatures as low as 0°C, of at least one of the said monomers in the presence of a an initiation system containing at least one radical-generating compound and at least one catalyst made up of a metal complex MAa(L)n where: M=Fe, Ru or Os; A=halogen or pseudo-halogen; the Ls, identical or different, each represent a ligand, which can be a chiral ligand, chosen among PRR'R'', P(OR)(OR')(OR''), NRR'R'', ORR', SRR', SeRR', AsRR'R'', SbRR'R'', where each R, R', R'' independently represents an alkyl group in C1-C14, eventually substituted, or an aromatic group, eventually substituted, with at least two of these ligands having the possibility of being linked to each other by one or more bivalent radicals : a is an integer between 1 and 3; n is an integer between 1 and 3; and in the absence of activators; the chloride systems of 1-phenylethyl/RuC12-PPh3 and benzyl chloride /FeC12-(EtO)3P (Ph=phenyl; Et=ethyl) being excluded in the case of styrene polymerization.

Ce procédé est caractérisé par le fait que l'on polymérise ou copolymérise en masse, solution, émulsion ou suspension, à une température pouvant descendre jusqu'à 0°C, au moins un desdits monomères en présence d'un système d'amorçage comprenant au moins un composé générateur de radicaux et au moins un catalyseur constitué par un complexe de métal MAa(L)n où : M = Fe, Ru ou Os ; A = halogène ou pseudo-halogène ; les L, identiques ou différents, représentent chacun un ligand, pouvant être un ligand chiral, qui est choisi parmi PRR'R", P(OR)(OR')(OR"), NRR'R", ORR', SRR', SeRR', AsRR'R", SbRR'R", où chaque R, R', R" représente indépendamment un groupe alkyle en C1-C14, éventuellement substitué, ou un groupe aromatique éventuellement substitué, au moins deux de ces ligands pouvant être reliés entre eux par un ou plusieurs radicaux bivalents : a est un entier compris entre 1 et 3 ; n est un entier compris entre 1 et 3 ; et en l'absence d'activateurs; les systèmes chlorure de 1-phényléthyle/RuCl2-PPh3 et chlorure de benzyle/FeCl2-(EtO)3P (Ph = phényle ; Et = éthyle) étant exclus dans le cas de la polymérisation du styrène.

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