US 4,791,161 AGranted

Cationic latices of copolymers based on conjugated dienes

AssigneeRhone-Poulenc Specialites Chimiques

InventorFrederic Leising

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Abstract

The present invention provides a cationic latex of copolymers based on conjugated dienes, formed by the steps of preparing an aqueous dispersion of particles by reacting at least one unsaturated tertiary nitrogen compound not capable of being hydrolyzed in an acid or alkaline medium with an aqueous emulsion reaction medium, containing cationic species, of at least one non-ionic monomer capable of being copolymerized with the non-hydrolyzable unsaturated nitrogen compound to form synthetic polymers and at least one substance which generates cationic species capable of chemically binding with the synthetic polymers; the non-ionic monomer being converted to polymer in the reaction in a degree of up to at least about 30%; and polymerizing, in the aqueous dispersion, at least one conjugated diene or a mixture of conjugated dienes and at least one non-ionic monomer in the presence of an initiator selected from the group consisting of an uncharged initiator and a cationic charge-generating initiator.

Claims27

Dependent claims

A cationic latex of at least one copolymer based on at least one conjugated diene, formed by the steps of:

(A) preparing a pH independent cationic aqueous dispersion of particles at least substantially free from anionic species by reacting
(i) at least one unsaturated tertiary nitrogen compound, selected from the group consisting of
(a) an N-(.omega.-dialkylaminoalkyl)amide of an unsaturated carboxylic acid, having the formula:
##STR4## where R.sub.1 is a hydrogen atom or a C.sub.1 -C.sub.4 alkyl group, R.sub.2 is a C.sub.1 -C.sub.12 alkylene group, and R.sub.3 and R'.sub.3 are either C.sub.1 -C.sub.6 alkyl groups, or phenyl groups optionally substituted by a C.sub.1 -C.sub.9 alkyl radical,
(b) an unsaturated amino-ester having the formula:
##STR5## wherein R'.sub.1 is a C.sub.1 -C.sub.5 alkyl group, R'.sub.2 is a linear or branched alkylene group with at least two carbon atoms, and R".sub.3 and R'".sub.3, which may be identical, are either a C.sub.1 -C.sub.6 alkyl group, optionally substituted by a hydroxyl radical, or a phenyl group, optionally substituted by a C.sub.1 -C.sub.9 alkyl radical, wherein the total number of carbon atoms contained in the radicals R'.sub.2, R".sub.3, and R'".sub.3 is greater than 8, and
(c) a heterocyclic nitrogen compound with a nitrogen or carbon atom substituted by a vinyl group, with
(ii) a cationic aqueous emulsion mixture at least substantially free from anionic species and containing:
(a) at least one non-ionic monomer selected from the group consisting of vinylaromatic compounds, vinyl esters, ethylenic nitriles, ethylenic carboxylic acid esters, dialkyl esters of ethylenic di-carboxylic acids, ethylenic amides, and the N-substituted derivatives of ethylenic amides;
(b) at least one unsaturated salt of a polycoordinated onium of a group 5a or 6a element capable of polymerizing with said monomer;
(c) a cationic or non-ionic polymerization initiator;
and
(d) a cationic or non-ionic emulsifier,
and wherein for every 100 parts by weight of said non-ionic monomer of (ii)(a) used, about 2 to 10 parts by weight of said unsaturated salt of polycoordinated onium of a group 5a or 6a element is present, and a total of about 4 to 15 parts by weight of said salt and said unsaturated nitrogen compound taken together is used,
said nonionic monomer being converted to polymer in said reaction in a degree of up to at least about 30%;
and
(B) polymerizing, in said aqueous dispersion, at least one conjugated diene or a mixture of said conjugated diene and at least one non-ionic monomer in the presence of a cationic or non-ionic polymerization initiator to form said cationic latex of copolymer.

14 more elements

A process for making a cationic latex of at least one copolymer based on at least one conjugated diene, comprising the steps of:

(a) preparing a pH independent cationic aqueous dispersion of particles free or at least substantially free from anionic species by reacting:
(i) at least one unsaturated tertiary nitrogen compound selected from the group consisting of
(A) an N-(.omega.-dialkylaminoalkyl) amide of an unsaturated carboxylic acid, having the formula:
##STR6## where R.sub.1 is a hydrogen atom or a C.sub.1 -C.sub.4 alkyl group, R.sub.2 is a C.sub.1 -C.sub.12 alkylene group, and R.sub.3 and R'.sub.3 are either C.sub.1 -C.sub.6 alkyl groups, or phenyl groups optionally substituted by a C.sub.1 -C.sub.9 alkyl radical,
(B) an unsaturated amino-ester having the formula:
##STR7## wherein R'.sub.1 is a C.sub.1 -C.sub.5 alkyl group, R'.sub.2 is a linear or branched alkylene group with at least two carbon atoms, and R".sub.3 and R'".sub.3, which may be identical, are either a C.sub.1 -C.sub.6 alkyl group, optionally substituted by a hydroxyl radical, or a phenyl group, optionally substituted by a C.sub.1 -C.sub.9 alkyl radical, wherein the total number of carbon atoms contained in the radicals R'.sub.2, R".sub.3, and R'".sub.3 is greater than 8, and
(C) a heterocyclic nitrogen compound with a nitrogen or carbon atom substituted by a vinyl group, with
(ii) a cationic aqueous emulsion mixture at least substantially free from anionic species and containing cationic species, of
(A) at least one non-ionic monomer selected from the group consisting of vinylaromatic compounds, vinyl esters, ethylenic nitriles, ethylenic carboxylic acid esters, dialkyl esters of ethylenic dicarboxylic acids, ethylenic amides, and the N-substituted derivatives of ethylenic amides;
(B) at least one unsaturated salt of a polycoordinated onium of a group 5a or 6a element capable of copolymerizing with said monomer;
(C) a cationic or non-ionic polymerization initiator;
and
(D) a cationic or non-ionic emulsifier, and
wherein for every 100 parts by weight of said non-ionic monomer of (ii)(A) used, about 2 to 10 parts by weight of said unsaturated salt of polycoordinated onium of a group 5a or 6a element is present, and a total of about 4 to 15 parts by weight of said salt and said unsaturated nitrogen compound taken together is used, and
(b) polymerizing in said aqueous dispersion, at least one conjugated diene or a mixture of said conjugated diene and at least one non-ionic monomer in the presence of a cationic or non-ionic polymerization initiator.

12 more elements

A cationic latex of at least one copolymer based on at least one conjugated diene, formed by the steps of:

(A) preparing a pH independent cationic aqueous dispersion of particles by reacting (i) at least one unsaturated tertiary nitrogen compound not capable of being hydrolyzed in an acid or alkaline medium, with (ii) a cationic aqueous emulsion reaction mixture containing:
(a) at least one non-ionic monomer capable of being copolymerized with said unsaturated nitrogen compound to form a synthetic polymer(s),
(b) at least one unsaturated salt of a polycoordinated onium of a group 5a or 6a element capable of copolymerizing with said monomer(s),
(c) a cationic or non-ionic polymerization initiator;
and
(d) a cationic or non-ionic emulsifier;
said non-ionic monomer(s) being converted to polymer(s) in said reaction in a degree of up to at least about 30%;
and
(B) polymerizing in said aqueous dispersion at least one conjugated diene or a mixture of said conjugated diene and at least one non-ionic monomer in the presence of a cationic or non-ionic polymerization initiator to form said cationic latex of copolymer(s).

6 more elements

Dependencies are inferred from the claim text.