US 5,854,364 AGranted

Process for the controlled radical polymerization or copolymerization of (meth)acrylic, vinyl, vinylidene and diene monomers, and (co)polymers obtained

AssigneeElf Atochem S.A.

InventorsThierry Senninger, Laurent Sanchez, Vincent Darcos, Dominique Lastecoueres, Jean-Baptiste Verlhac

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Abstract

At least one of the monomers is polymerized or copolymerized in bulk, solution, emulsion or suspension, at a temperature which may be as low as 0.degree. C., in the presence of at least one radical-generator compound and at least one metal complex catalyst of formula Ma.sub.a (L).sub.n (M=Cu, Ag or Au; A=Hal, pseudohalogen or carboxylate; L=ligands of M chosen from those of formula ##STR1## R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 =H, C.sub.1 -C.sub.10 alkyl, aromatic or heteroaromatic; Z.sup.1, Z.sup.2 and Z.sup.3 =one of the following: ##STR2## (R.sup.7 to R.sup.18 =H, C.sub.1 -C.sub.10 alkyl, aromatic or heteroaromatic; R.sup.19 and R.sup.20 =H, Hal, C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10 alkoxy or --(CR.sup.21 R.sup.22)rNR.sup.23 R.sup.24, where R.sup.21, R.sup.22, R.sup.23 and R.sup.24 =H,C.sub.1 -C.sub.10 alkyl, aromatic or heteroaromatic, and r=integer from 1 to 10; it being possible also for not more than two from among Z.sup.1, Z.sup.2 and Z.sup.3 each to represent H; o, p and q=integer from 1 to 10 and may also be 0 except if the associated residue Z.sup.1, Z.sup.2 or Z.sup.3, respectively, is --NR.sup.19 R.sup.20 ; a=1 or 2; n=1, 2 or 3.

A process for the controlled radical polymerization or copolymerization of (meth)acrylic and/or vinyl and/or vinylidene and/or diene monomers, characterized in that least one of the said monomers is polymerized or copolymerized in bulk, solution, emulsion or suspension at in the presence of an initiator system comprising:

at least one radical-generator compound;
and
at least one catalyst consisting essentially of a metal complex represented by formula (I) below:
MA.sub.a (L).sub.n (I)
in which:
M represents Cu, Ag or Au;
A represents a halogen, a pseudohalogen or a carboxylate group;
the groups L are ligands of the metal M which are chosen independently from those represented by formula (II) below:
##STR29## in which:
Y represents N or P;
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 each independently represent a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, an aromatic group or a heteroaromatic group;
Z.sup.1, Z.sup.2 and Z.sup.3 each independently represent one of the following:
##STR30## --NR.sup.19 R.sup.20 where:
the radicals R.sup.7 to R.sup.18 each independently represent a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, an aromatic group or a heteroaromatic group;
and
R.sup.19 and R.sup.20 each independently represent a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 alkyl radical, a C.sub.1 -C.sub.10 alkoxy radical or a radical --(CR.sup.21 R.sup.22).sub.r NR.sup.23 R.sup.24, where R.sup.21, R.sup.22, R.sup.23 and R.sup.24 each independently represent a hydrogen atom, a C.sub.1 -C.sub.10 alkyl group, an aromatic group or a heteroaromatic group, and r is an integer from 1 to 10;
it being also possible for not more than two from among Z.sup.1, Z.sup.2 and Z.sup.3 each to represent a hydrogen atom;
o, p and q each independently represent an integer from 1 to 10, and may also represent 0 except if the associated residue Z.sup.1, Z.sup.2 or Z.sup.3, respectively, represents --NR.sup.19 R.sup.20 ;
a is 1 or 2;
n is 1, 2 or 3.

17 more elements

Abstract

Claims20