Cross-linkable monomers and polymers and the use thereof
View Patent ↗The invention relates to novel cross-linkable monomers that may be polymerized with ethylenically unsaturated comonomers to form cross-linkable copolymers. Said copolymers may particularly be used in the form of aqueous dispersions as formaldehyde-free adhesives or as coatings with good water resistance. The cross-linkable monomer is a compound in acid or salt form comprising an anion of the formula (I) and one or more cations for producing electrical neutrality, where R 1 and R 2 represent, independently of one another, hydrogen alkyl, cycloalkyl, aryl, aralkyl, —COOR 5 , —COO − cat + or —CON(R 6 R 7 ), R 6 and R 7 represent, independently of one another, hydrogen, alkyl, or aryl, cat 4 represents a monovalent cation, and one of the groups R 1 or R 2 may also represent a group —X—R 4 —CR 5 (OH)(SO 3 —), wherein X, R 4 , and R 5 assume one of the meanings listed below, R 3 represents hydrogen, alkyl, or aryl, X is selected from the group of direct C—C bond, —O—, —CH 2 —O—, —CH 2 —NR 8 —, —COO— or —CONR 8 —, R 8 represents hydrogen, alkyl, or aryl, R 4 represents alkylene, polyoxyalkylene, cycloalkylene, or arylene, and R 5 represents hydrogen, alkyl, cycloalkyl, or aryl.
1. A copolymer comprising at least one monomer derived from a compound in acid or salt form and at least one further monomer which can undergo free radical copolymerization therewith,
wherein the at least one monomer derived from a compound in acid or salt form contains an anion of the formula (I) and one or more cations for producing electroneutrality:
in which:
R 1 and R 2 , independently of one another, are hydrogen, alkyl, cycloalkyl, aryl, aralkyl, —COOR 5 , —COO − Cat + , —CON(R 6 R 7 ), or —X—R 4 —CR 5 (OH)(SO 3 − );
R 4 is alkylene, polyoxyalkylene, or cycloalkylene;
R 5 is hydrogen, alkyl, cycloalkyl or aryl;
R 3 , R 6 and R 7 , independently of one another, are hydrogen, alkyl or aryl;
Cat + is a monovalent cation;
X is selected from the group consisting of —O—, —CH 2 —NR 8 —, —COO— or —CONR 8 —; and
R 8 is hydrogen, alkyl or aryl,
wherein the at least one further monomer comprises an ethylene, a propylene, a styrene, an acrylate, a methacrylate, a vinyl ester of a saturated carboxylic acid, a butadiene or from mixtures of two or more of these monomers and
wherein the at least one monomer of formula (I) is present in an amount of up to 10% by weight, based on the total weight of the monomers.
2. The copolymer as defined in claim 1 , wherein the further monomer capable of free radical polymerization is selected from the group consisting of alpha-olefins, aliphatic hydrocarbons having two or more conjugated double bonds, vinyl esters of saturated carboxylic acids, esters of ethylenically unsaturated mono-or dicarboxylic acid, alkenyl-aromatics, and combinations thereof.
3. The copolymer as defined in claim 1 , wherein the at least one monomer of formula (I)is present in an amount of from 0.01 to 5% by weight, based on the total weight of the monomers.
4. The copolymer as defined in claim 1 , wherein R 1 and R 2 , independently of one another, are hydrogen, alkyl, —COOR 5 or —COO − Cat + and wherein R 3 is hydrogen or alkyl.
5. The copolymer as defined in claim 4 , wherein one of the radicals R 1 or R 2 is —COOR 5 or —COO − Cat + .
6. The copolymer as defined in claim 4 , wherein R 1 and R 2 , independently of one another, are hydrogen, methyl, —COOR 5a or —COO − Cat+ and wherein at least and one of the radicals R 1 or R 2 is —COOR 5a or —COO − Cat+, R 5a being hydrogen or C 1 -C 6 -alkyl, and wherein R 3 is hydrogen or methyl.
7. The copolymer as defined in claim 1 , wherein one of the radicals R 1 or R 2 is an —X—R 4 —CR 5 (OH)(SO 3 − ) group.
8. The copolymer as defined in claim 1 , wherein X is selected from the group consisting of —O—, —CO—NR 8 —, or —COO—.
9. The copolymer as defined in claim 1 , wherein R 4 is alkylene.
10. The copolymer as defined in claim 9 , wherein R 4 is an unsubstituted C 1 -C 6 -alkylene.
11. The copolymer as defined in claim 1 , wherein R 5 is hydrogen or alkyl.
12. The copolymer as defined in claim 1 , wherein the anion of formula (I) is an anion of the formula (IVa) or (IVb)
13. A composition containing the copolymer as defined in claim 1 , wherein the composition is in the form of an aqueous dispersion.
14. The composition as defined in claim 13 , wherein the copolymer is a polyvinyl ester which contains at least 50% by weight of vinyl acetate monomer units and structural units derived from compounds of the formula (I).
15. The composition as defined in claim 13 , wherein the composition comprises at least one protective colloid.
16. The composition as defined in claim 13 , wherein the composition comprises at least one external crosslinking agent.
17. The composition as defined in claim 13 , wherein the composition comprises at least one polyaldehyde or polyhydrazine.
18. The composition as defined in claim 13 , wherein the composition contains Lewis acids in the form of acidic salts of complexable metal ions selected from the group consisting of aluminum chloride, aluminum nitrate, zirconium oxychloride, titanium sulfate, acidic salts with polyvalent complexable cations, and combinations thereof.
19. The composition as defined in claim 13 , wherein the composition has a pH of from 2.5 to 4.5.
20. A cured composition produced by applying and drying the composition as defined in claim 13 .
21. A redispersible dispersion powder formed from the composition as defined in claim 13 .
22. A copolymer comprising at least one monomer derived from a compound in acid or salt form and at least one further monomer which can undergo free radical copolymerization therewith,
wherein the at least one monomer derived from a compound in acid or salt form contains an anion of the formula (I) and one or more cations for producing electroneutrality:
in which:
R 1 and R 2 , independently of one another, are hydrogen, alkyl, cycloalkyl, aryl, aralkyl, —COOR 5 , —COO − Cat + , —CON(R 6 R 7 ), or —X—R 4 —CR 5 (OH)(SO 3 − );
R 4 is alkylene, polyoxyalkylene, cycloalkylene or arylene;
R 5 is hydrogen, alkyl, cycloalkyl or aryl;
R 3 , R 6 and R 7 , independently of one another, are hydrogen, alkyl or aryl;
Cat + is a monovalent cation;
X is selected from the group consisting of —O—, —CH 2 —NR 8 —, —COO— or —CONR 8 —; and
R 8 is hydrogen, alkyl or aryl,
wherein the at least one further monomer comprises an ethylene, a propylene, a styrene, an acrylate, a methacrylate, a vinyl ester of a saturated carboxylic acid, a butadiene or from mixtures of two or more of these monomers and
wherein the at least one monomer of formula (I) is present in an amount of up to 10% by weight, based on the total weight of the monomers.