Processes to produce water-dispersible polyester stabilized fluoroalkyl compositions
View Patent ↗A process is provided to produce an aqueous dispersion wherein the aqueous dispersion enhances the water and oil repellency of materials. The process comprises: 1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, water, and optionally an ethylenically unsaturated monomer to form a pre-emulsion; and 2) polymerizing the pre-emulsion in a polymerization zone in the presence of an initiator to produce the aqueous dispersion. In another embodiment, a process to produce an aqueous dispersion is provided. The process comprises: 1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, water, and optionally an ethylenically unsaturated monomer to form a pre-emulsion; 2) shearing the pre-emulsion to produce a mini-emulsion; and 3) polymerizing the miniemulsion in a polymerization zone to produce the aqueous dispersion.
1. A process to produce a pre-emulsion, said process comprising contacting at least one fluoroalkyl monomer, at least one nonionic water-dispersible polyester, water, and optionally at least one ethylenically unsaturated monomer, wherein the amount of said fluoroalkyl monomer is that which is sufficient to produce a polymer containing from about 50 to about 100 weight percent fluoroalkyl monomer repeating units based on the total weight of monomer utilized; wherein the fluoroalkyl monomer is represented by the formula Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, R is a hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
2. A process according to claim 1 wherein the amount of said water-dispersible polyester solids in said aqueous dispersion range from about 1% to about 20% by weight based on the weight of said aqueous dispersion.
3. A process to produce a mini-emulsion, said process comprising: 1) contacting at least one fluoroalkyl monomer, at least one nonionic water-dispersible polyester, water and optionally an ethylenically unsaturated monomer to form a pre-emulsion; and 2) shearing said pre-emulsion to produce said miniemulsion, wherein the amount of said fluoroalkyl monomer is that which is sufficient to produce a polymer containing from about 50 to about 100 weight percent fluoroalkyl monomer repeating units based on the total weight of monomer utilized; wherein the fluoroalkyl monomer is represented by the formula Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, R is a hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22.
4. A process according to claim 3 wherein the amount of said water-dispersible polyester solids in said aqueous dispersion range from about 1% to about 20% by weight based on the weight of said aqueous dispersion.
5. A process to produce an aqueous dispersion, said process comprising:
1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, water, and optionally an ethylenically unsaturated monomer to form a pro-emulsion, wherein the amount of said fluoroalkyl monomer is that which is sufficient to produce a polymer containing from about 50 to about 100 weight percent fluoroalkyl monomer repeating units based on the total weight of monomer utilized; wherein the fluoroalkyl monomer is represented by the formula Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, R is a hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22;
2) polymerizing said pre-emulsion in an emulsion polymerization zone in the presence of an initiator to produce said aqueous dispersion.
6. A process according to claim 5 wherein the amount of water-dispersible polyester solids in said aqueous dispersion range from about 1% to about 20% by weight based on the weight of said aqueous dispersion.
7. A process according to claim 5 wherein said polymerization occurs at a temperature in the range of 20° C. to 155° C.
8. A process according to claim 7 wherein said polymerization occurs at a temperature in the range of 40° C. to 85° C.
9. A process according to claim 5 wherein the amount of initiator ranges from about 0.2 to about 1% by weight based on the total amount of monomer.
10. A process according to claim 5 wherein said contacting is conducted in the presence of at least one compound selected from the group consisting of reducing agents, catalysts, chain transfer agents, crosslinking agents, solvents, reactive surfactants, and Water-dispersible/water-soluble polymers.
11. A process according to claim 10 wherein said reducing agent is at least one selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium thiosulfate, ascorbic acid isoascorbic acid, and mixtures thereof.
12. A process according to claim 10 wherein said reducing agent is added to said polymerization zone in an amount ranging from about 04% to about 2% based on the total weight of the monomers.
13. A process according to claim 10 wherein said catalyst is at least one selected from the group consisting ferrous sulfate heptahydrate, chelated forms of ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.
14. A process according to claim 10 wherein said catalyst is added to said polymerization zone in an amount ranging from about 0.0001% to about 0.05% based on the total weight of the monomers.
15. A process according to claim 10 wherein said chain transfer agent is at least one selected from the group consisting of butyl mercaptan, mercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, octyl mercaptan, N-dodecyl mercaptan, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate, carbon tetrabromide, bromoform, bromotrichloromethane, sodium hypophosphite, and mixtures thereof.
16. A process according to claim 10 wherein the amount of said chain transfer agent ranges from about 0.1 to about 1% by weight based on the total amount of monomer.
17. A process according to claim 10 wherein said crosslinking agent is an external or internal crosslinking agent.
18. A process according to claim 17 wherein said external crosslinking agent is at least one selected from the group consisting of poly(oxyethylene) (meth)acrylates, N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, hydroxylethyl (meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, and glycidyl(meth)acrylate.
19. A process according to claim 10 wherein the amount of said external crosslinking agent ranges from about 0.1 to about 5% by weight based on the total amount of monomer.
20. A process according to claim 17 wherein said crosslinking agent is an internal crosslinking agent.
21. A process according to claim 20 wherein said internal crosslinking agent is at least one selected from the group consisting of diallylmaleate, divinylbenzene, triethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1,3butyleneglycol diacrylate, 1,4butanediol diacrylate, 1,6hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol (200) diacrylate, ethoxylated bisphenol A diacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.
22. A process according to claim 17 wherein the amount of said internal crosslinking agent ranges from about 0.1 to about 5% by weight based on the total amount of monomer.
23. A process according to claim 10 wherein said water-soluble organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol, tripropylene glycol, ethanol, and mixtures thereof.
24. A process according to claim 10 wherein the amount of said water-soluble organic solvent is not more than about 30 parts by weight based on 100 parts by weight of the total amount of monomer.
25. A process according to claim 10 wherein said reactive surfactant is a compound having isopropenylphenyl or allyl groups.
26. A process according to claim 10 wherein said reactive surfactant is a polyoxyethylene alkyl phenyl ether sulfate having one of the following formula:
wherein R is nonyl or octyl, n is an integer from 15 to 15, and m is an integer from 15 to 40.
27. A process to produce an aqueous dispersion, said process comprising:
1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, water, and optionally an ethylenically unsaturated monomer to form a pro-emulsion, wherein the amount of said fluoroalkyl monomer is that which is sufficient to produce a polymer containing from about 50 to about 100 weight percent fluoroalkyl monomer repeating units based on the total weight of monomer utilized; wherein the fluoroalkyl monomer is represented by the formula Rf-Q-OCOCR═CH 2 ; wherein Q is a bivalent organic group, R is a hydrogen atom or methyl group; wherein Q is selected from the group consisting of —(CH 2 ) p+q —; —(CH 2 ) p CONH(CH 2 ) q —; —(CH 2 ) p OCONH(CH 2 ) q —; —(CH 2 ) p SO 2 NR′(CH 2 ) q —; —(CH 2 ) p NHCONH(CH 2 ) q —; or —(CH 2 ) p CHOH—(CH 2 ) q —; wherein R′ is a hydrogen or an alkyl group, and each of p and q is an integer of at least 0, provided that p+q is an integer of from 1 to 22;
2) shearing said pro-emulsion to produce a mini-emulsion;
3) polymerizing said miniemulsion in an emulsion polymerization zone to produce said aqueous dispersion.
28. A process according to claim 27 wherein the amount of water-dispersible polyester solids in said aqueous dispersion range from about 1% to about 20% by weight based on the weight of said aqueous dispersion.
29. A process according to claim 27 wherein said polymerization occurs at a temperature in the range of about 20° C. to about 155° C.
30. A process according to claim 29 wherein said polymerization occurs at a temperature in the range of 40° C. to 85° C.
31. A process according to claim 27 wherein the amount of initiator ranges from about 0.2 to about 1% by weight based on the total amount of monomer.
32. A process according to claim 27 wherein said contacting is conducted in the presence of at least one compound selected from the group consisting of reducing agents, catalysts, chain transfer agents, crosslinking agents, solvents, reactive surfactants, and water-dispersible/water-soluble polymers.
33. A process according to claim 32 wherein said reducing agent is at least one selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, sodium thiosulfate, ascorbic acid isoascorbic acid, and mixtures thereof.
34. A process according to claim 32 wherein said reducing agent is added to said emulsion polymerization zone in an amount ranging from about 0.1% to about 2% based on the total weight of the monomers.
35. A process according to claim 32 wherein said catalyst is selected from the group consisting ferrous sulfate heptahydrate, chelated forms of ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.
36. A process according to claim 32 wherein said catalyst is added to said polymerization zone in an amount ranging from 0.0001% to about 0.05% based on the total weight of the monomers.
37. A process according to claim 32 wherein said chain transfer agent is at least one selected from the group consisting of butyl mercaptan, mercaptopropionic acid, 2-ethylhexyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, octyl mercaptan, N-dodecyl mercaptan, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate, carbon tetrabromide, bromoform, bromotrichloromethane, sodium hypophosphite, and mixtures thereof.
38. A process according to claim 32 wherein the amount of said chain transfer agent ranges from about 0.1 to about 1% by weight based on the total amount of monomer.
39. A process according to claim 32 wherein said crosslinking agent is an external or internal crosslinking agent.
40. A process according to claim 39 wherein said external crosslinking agent is at least one selected from the group consisting of poly(oxyethylene) (meth)acrylates, N-butoxymethyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, hydroxylethyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, and glycidyl(meth)acrylate.
41. A process according to claim 39 wherein the amount of said external crosslinking agent ranges from about 0.1 to about 5% by weight based on the total amount of monomer.
42. A process according to claim 39 wherein said crosslinking agent is an internal crosslinking agent.
43. A process according to claim 42 wherein said internal crosslinking agent is diallylmaleate, divinylbenzene, triethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1,3butyleneglycol diacrylate, 1,4butanediol diacrylate, 1,6hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol (200) diacrylate, ethoxylated bisphenol A diacrylate, tris(2-hydroxyethyl)isocyanurate trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.
44. A process according to claim 42 wherein the amount of said internal crosslinking agent ranges from about 0.1 to about 5% by weight based on the total amount of monomer.
45. A process according to claim 32 wherein said water-soluble organic solvent is at least one selected from the group consisting of acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol, tripropylene glycol, ethanol, and mixtures thereof.
46. A process according to claim 32 wherein the amount of said water-soluble organic solvent is not more than 30 parts by weight based on 100 parts by weight of the total amount of monomer.
47. A process according to claim 32 wherein said reactive surfactant is a compound having isopropenylphenyl or allyl groups.
48. A process according to claim 32 wherein said reactive surfactant is a polyoxyethylene alkyl phenyl ether having one of the following formula:
wherein R is nonyl or octyl, n is an integer from 15 to 15, and m is an integer from 15 to 40.