US 8,013,062 B2Granted

Method of producing and using materials which are reinforced against impact and which contain block copolymers that are obtained by means of controlled radical polymerization in the presence of nitroxides

AssigneeArkema France

InventorsAnne-Valerie Ruzette, Florence Chauvin, Olivier Guerret, Denis Bertin, Bruno Vuillemin, Ludwik Leibler, Pierre Gerard, Yannick Ederle

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Abstract

The invention relates to the production and use of block copolymers which are obtained by means of controlled radical polymerization in the presence of nitroxides for the purpose of reinforcing fragile polymer matrices. The invention offers advantages such as (i) simplicity of copolymer synthesis and use and (ii) fine dispersion of the copolymer molecules in the fragile matrix, which ensures both the transparency of the material and high reinforcement against impact. More specifically, the invention relates to the radical synthesis of block copolymers comprising at least three blocks, which include one block having a glass transition temperature of less than 0° C. and a thermoplastic end block having a glass transition temperature of more than 0° C., thereby guaranteeing compatibility with the fragile matrix to be reinforced against impact.

Claims22

Dependent claims

A process for the preparation of a transparent and impact-resistant polymer material comprising a brittle matrix (I) having a glass transition temperature of greater than 0° C. in which is dispersed a block copolymer (II) of formula B-(A)n, n being between 2 and 20, with a polydispersity of between 1.5 and 3, B being a polymer block with a glass transition temperature of less than 0° C. and with a polydispersity index of less than 2 and A being a polymer block with a glass transition temperature of greater than 0° C., A being compatible with the matrix, wherein the block copolymer (II) is obtained by controlled radical polymerization in the presence of a nitroxide, comprising

(1) preparing the first block B by mixing the monomer(s) with an alkoxyamine of formula:
where R′ and R, which are identical or different, optionally connected so as to form a ring, are alkyl groups having between 1 and 40 carbon atoms optionally substituted by hydroxyl, alkoxy or amino groups;
where RL is a monovalent group with a molar mass of greater than 16 g/mol;
and
where Z is a polyvalent radical carrying end functional groups of styrol or acryloyl,
adding a nitroxide, and
carrying out the polymerization at temperatures ranging from 60 to 250° C., pressures ranging from 0.100 bar to 80 bar,
(2) diluting the first block B obtained in the mixture of monomers intended to form the block A compatible to the brittle matrix which is desired to see reinforced against impact,
adding between 0 and 100 molar equivalents of a radical polymerization initiator,
carrying out the polymerization at temperatures ranging from 60 to 250° C., and pressures ranging from 0.100 bar to 80 bar, the conversion of the monomer being from 10 to 100%, and
separating the polymer obtained from the residual monomers by evaporation under vacuum at temperatures ranging up to 250° C.,
(3) mixing the product obtained in step (2) with the brittle matrix which it is desired to see reinforced against impact, optionally in the presence of other additives, and
wherein the relative lengths of the first block B and the block A are selected such that n*Mn(A)/(n*Mn(A)+Mn(B)) is between 0.5 and 0.95, wherein, Mn(A) is the number-average molecular mass of the block A, Mn(B) is the number-average molecular mass of the first block B, and n is the number of polymer blocks A in the block copolymer obtained in step (2).

10 more elements

(1) preparing the first block B by mixing the monomer(s) with an alkoxyamine of formula:
where R′ and R, which are identical or different, optionally connected so as to form a ring, are alkyl groups having between 1 and 40 carbon atoms optionally substituted by hydroxyl, alkoxy or amino groups;
where RL is a monovalent group with a molar mass of greater than 16 g/mol;
and
where Z is a polyvalent radical carrying end functional groups of styrol or acryloyl,
adding a nitroxide, and
carrying out the polymerization at temperatures ranging from 60 to 250° C., pressures ranging from 0.100 bar to 80 bar,
(2) diluting the first block B obtained in the mixture of monomers intended to form the block A compatible to the brittle matrix which is desired to see reinforced against impact,
adding between 0 and 100 molar equivalents of a radical polymerization initiator,
carrying out the polymerization at temperatures ranging from 60 to 250° C., and pressures ranging from 0.100 bar to 80 bar, the conversion of the monomer being from 10 to 100%, and
separating the polymer obtained from the residual monomers by evaporation under vacuum at temperatures ranging up to 250° C.,
(3) diluting the product obtained step (2) in a mixture of monomers selected from the group consisting of styrene, MMA, epoxides, mixtures of diols and of diacid, or precursors of polyamides to obtain a diluted product and then polymerizing the diluted product;
and
wherein A represents from 50% to 95% by weight of the total weight of the block copolymer (II) and the number-average molar mass of A is between 10,000 to 106 g/mol.

11 more elements

(1) preparing the first block B by mixing the monomer(s) with an alkoxyamine of formula:
where R′ and R, which are identical or different, optionally connected so as to form a ring, are alkyl groups having between 1 and 40 carbon atoms optionally substituted by hydroxyl, alkoxy or amino groups;
where RL is a monovalent group with a molar mass of greater than 16 g/mol;
and
where Z is a polyvalent radical carrying end functional groups of styrol or acryloyl,
adding a nitroxide, and
carrying out the polymerization at temperatures ranging from 60 to 250° C., pressures ranging from 0.100 bar to 80 bar,
(2) diluting the first block B obtained in the mixture of monomers intended to form the block A compatible to the brittle matrix which is desired to see reinforced against impact,
adding between 0 and 100 molar equivalents of a radical polymerization initiator,
carrying out the polymerization at temperatures ranging from 60 to 250° C., and pressures ranging from 0.100 bar to 80 bar, the conversion of the monomer being from 10 to 100%, and
separating the polymer obtained from the residual monomers by evaporation under vacuum at temperatures ranging up to 250° C.,
(3) diluting the product obtained step (2) in a mixture of monomers selected from the group consisting of styrene, MMA, epoxides, mixtures of diols and of diacid, or precursors of polyamides to obtain a diluted product and then polymerizing the diluted product, and
wherein the relative lengths of the first block B and the block A are selected such that n*Mn(A)/(n*Mn(A)+Mn(B)) is between 0.5 and 0.95, wherein, Mn(A) is the number-average molecular mass of the block A, Mn(B) is the number-average molecular mass of the first block B, and n is the number of polymer blocks A in the block copolymer obtained in step (2).

10 more elements

(1) preparing the first block B by mixing the monomer(s) with an alkoxyamine of formula:
where R′ and R, which are identical or different, optionally connected so as to form a ring, are alkyl groups having between 1 and 40 carbon atoms optionally substituted by hydroxyl, alkoxy or amino groups;
where RL is a monovalent group with a molar mass of greater than 16 g/mol;
and
where Z is a polyvalent radical carrying end functional groups of styrol or acryloyl,
adding a nitroxide, and
carrying out the polymerization at temperatures ranging from 60 to 250° C., pressures ranging from 0.100 bar to 80 bar,
(2) diluting the first block B obtained in the mixture of monomers intended to form the block A compatible to the brittle matrix which is desired to see reinforced against impact,
adding between 0 and 100 molar equivalents of a radical polymerization initiator,
carrying out the polymerization at temperatures ranging from 60 to 250° C., and pressures ranging from 0.100 bar to 80 bar, the conversion of the monomer being from 10 to 100%, and
separating the polymer obtained from the residual monomers by evaporation under vacuum at temperatures ranging up to 250° C.,
(3) mixing the product obtained in step (2) with the brittle matrix which it is desired to see reinforced against impact, optionally in the presence of other additives;
and
wherein A represents from 50% to 95% by weight of the total weight of the block copolymer (II) and the number-average molar mass of A is between 10,000 to 106 g/mol.

11 more elements

Dependencies are inferred from the claim text.

Facts

Application: 10/502,216Filed 21 Jan 2003
Priority: FR 02 0081422 Jan 2002
Published: US 2006/0063891 A123 Mar 2006
Granted: 6 Sep 2011
Term ends: Not estimatedThe source records don’t support an estimate.

Classification5 codes

C08L 53/00
Compositions of block copolymers containing at least one sequence of a polymer
C08F 293/00
Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable
C08L 101/00
Compositions of unspecified macromolecular compounds
C08L
Compositions of macromolecular compounds