Copolymerizable emulsifiers and emulsion polymerization processes using the same
View Patent ↗Processes for the production of polymers by emulsion polymerization of olefinically unsaturated monomers, in which olefinically unsaturated esters corresponding to formula (I): HOOC—CH═CH—COO—(BO) z (PO) y (EO) x R 1 (I) in which R 1 is an alkyl group or alkenylphenol group containing 8 to 24 carbon atoms, BO is a butylene oxide unit, PO is a propylene oxide unit and EO is an ethylene oxide unit and the indices x, y and z independently of one another stand for 0 or for numbers of 1 to 50, with the proviso that at least one of the indices x, y and z is not 0, the carboxyl group of the compounds (I) being completely or partly present in neutralized form and the C═C double bond being cis- or trans-configured; are used as copolymerizable emulsifiers.
1. A process for preparing a polymer emulsion by emulsion polymerization, comprising:
(a) providing an aqueous emulsion, the emulsion comprising:
(i) a major amount, based on the polymerizable components of the emulsion, of at least one substantially water-insoluble olefinically unsaturated monomer;
(ii) from about 1% to about 6% by weight of a water-soluble monomer, based on the combined weight of the monomers (i) and (ii), selected from the group consisting of acrylonitrile, methacrylonitrile, C1-C8 semiesters of maleic acid, C1-C8 semiesters of fumaric acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, acrylamide, N-methylolacrylamide and combinations thereof;
(iii) at least one copolymerizable emulsifier; and
(iv) water,
wherein the copolymerizable emulsifier comprises at least one olefinically unsaturated ester of formula (I):
HOOC—CH═CH—COO—(BO) z (PO) y (EO) x —R 1 (I)
wherein R 1 represents an alkyl group or alkenylphenol group having from 8 to 24 carbon atoms, BO represents a butylene oxide unit, PO represents a propylene oxide unit and EO represents an ethylene oxide unit and each of x, y and z independently represents a number of from 0 to 50, with the proviso that at least one of x, y and z is not 0, and wherein the carboxylic acid group is completely or partly neutralized; and
(b) emulsion polymerizing at least a portion of said aqueous emulsion (a) to form a polymer emulsion.
2. The process according to claim 1 , wherein x and y each independently represent a number of from 1 to 20 and z represents zero.
3. The process according to claim 1 , wherein x represents a number of from 3 to 5 and y and z represent zero.
4. The process according to claim 1 , wherein R 1 represents an alkyl group having from 8 to 14 carbon atoms.
5. The process according to claim 2 , wherein R 1 represents an alkyl group having from 8 to 14 carbon atoms.
6. The process according to claim 3 , wherein R 1 represents an alkyl group having from 8 to 14 carbon atoms.
7. The process according to claim 1 , wherein the copolymerizable emulsifier is present in an amount of from 0.1 to 25% by weight based on the combined weight of monomers (i) and (ii).
8. The process according to claim 2 , wherein the copolymerizable emulsifier is present in an amount of from 0.1 to 25% by weight based on the combined weight of monomers (i) and (ii).
9. The process according to claim 4 , wherein the copolymerizable emulsifier is present in an amount of from 0.1 to 25% by weight based on the combined weight of monomers (i) and (ii).
10. The process according to claim 5 , wherein the copolymerizable emulsifier is present in an amount of from 0.1 to 25% by weight based on the combined weight of monomers (i) and (ii).
11. The process according to claim 1 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
12. The process according to claim 2 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
13. The process according to claim 4 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
14. The process according to claim 5 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
15. The process according to claim 7 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
16. The process according to claim 9 , wherein the at least one substantially water-insoluble olefinically unsaturated monomer comprises a compound selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof.
17. A process for preparing a polymer emulsion by emulsion polymerization, comprising:
(a) providing an aqueous emulsion, the emulsion comprising:
(i) a major amount, based on the polymerizable components of the emulsion, of at least one substantially water-insoluble olefinically unsaturated monomer selected from the group consisting of aromatic vinyl compounds, olefins, diolefins, esters of acrylic or methacrylic acid with linear or branched C 1-18 alcohols, vinyl esters of C 2-12 acids, vinyl alkyl ethers containing C 1-8 alkyl groups, and mixtures thereof;
(ii) from about 1% to about 6% by weight of a water-soluble monomer, based on the combined weight of the monomers (i) and (ii), selected from the group consisting of acrylonitrile, methacrylonitrile, C1-C8 semiesters of maleic acid, C1-C8 semiesters of fumaric acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, acrylamide, N-methylolacrylamide and combinations thereof;
(iii) at least one copolymerizable emulsifier; and
(iv) water,
wherein the copolymerizable emulsifier is present in an amount of from 0.1 to 25% by weight based on the combined monomers (i) and (ii), and wherein the copolymerizable emulsifier comprises at least one olefinically unsaturated ester of formula (Ia):
HOOC—CH═CH—COO-(EO) x —R 1 (Ia)
wherein R 1 represents an alkyl group having from 8 to 14 carbon atoms, EO represents an ethylene oxide unit and x represents a number of from 3 to 5, and wherein the carboxylic acid group is completely or partly neutralized; and
(b) emulsion polymerizing at least a portion of said aqueous emulsion (a) to form a polymer emulsion.
18. The process of claim 1 , wherein said water-soluble monomers are selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, and combinations thereof.
19. The process of claim 17 , wherein said water-soluble monomers are selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, N-methylolacrylamide, and combinations thereof.