Processes to produce water-dispersible polyester stabilized, acid-treated, fluoroalkyl compositions

1. A process to produce an acid-treated aqueous dispersion, said process comprising contacting a polymer water-dispersible polyester, water, and at least one acid-generating compound; and wherein said polymer comprises repeating units from at least one fluoroalkyl monomer and optionally, at least one ethylenically unsaturated monomer.

2. A process according to claim 1 wherein the amount of said acid-generating compound ranges from about 0.01% to about 0.4% by weight based on the weight of said acid-treated aqueous dispersion.

3. A process according to claim 1 wherein the amount of polymer ranges from about 10% to about 50% by weight based on the weight of said acid-treated aqueous dispersion.

4. A process according to claim 1 wherein the amount of said water-dispersible polyester solids in said acid-treated aqueous dispersion range from about 1% to about 20% based on the weight of the acid-treated aqueous dispersion.

5. A process to produce an acid-treated aqueous dispersion, said process comprising:

1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, and optionally an ethylenically unsaturated monomer to produce a mixture; 2) polymerizing said mixture in a polymerization zone to produce an aqueous dispersion 3) contacting said mixture or aqueous dispersion with at least one acid-generating compound to produce said acid-treated aqueous dispersion.

6. A process to produce an acid-treated aqueous dispersion, said process comprising:

1) contacting at least one fluoroalkyl monomer, at least one nonionic water-dispersible polyester, and optionally an ethylenically unsaturated monomer to form a pre-emulsion 2) polymerizing said pre-emulsion in a polymerization zone in the presence of an initiator to produce an aqueous dispersion; 3) contacting said pre-emulsion or aqueous dispersion with at least one acid-generating compound to produce said acid-treated aqueous dispersion.

7. A process according to claim 6 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.

8. A process according to claim 6 wherein the amount of said water-dispersible polyester solids range from about 1 to about 20% by weight based on the weight of said acid-treated aqueous dispersion.

9. A process according to claim 6 wherein said polymerization is conducted in an emulsion polymerization zone in the presence of at least one initiator under emulsion polymerization conditions.

10. A process according to claim 9 wherein said polymerization occurs at a temperature m the range of about 20.degree. C. to about 155.degree. C.

11. A process according to claim 10 wherein said polymerization occurs at a temperature m the range of about 40.degree. C. to about 85.degree. C.

12. A process according to claim 9 wherein the amount of said initiator ranges from about 0.2 to about 1% by weight based on the total amount of monomer.

13. A process according to claim 6 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, external crosslinking agents, internal crosslinking agents, solvents, reactive surfactants, and water-dispersible/water-soluble polymers.

14. A process according to claim 13 wherein said reducing agents Is at least one selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium formadehyde sulfoxylate, sodium thiosulfate, ascorbic acid isoascorbic acid, and mixtures thereof.

15. A process according to claim 13 wherein said reducing agent is added to said polymerization zone in an amount ranging from about 0.1 to about 2% by weight based on the total weight of the monomer.

16. A process according to claim 13 wherein said catalyst is at least one selected from the group consisting of ferrous sulfate heptahydrate, chelated froms of ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.

17. A process according to claim 13 wherein said catalyst is added to said polymerization zone in an amount ranging from about 0.0001% to about 0.05% by weight based on the total weight of the monomer.

18. A process according to claim 13 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.

19. A process according to claim 13 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.

20. A process according to claim 13 wherein said external crosslinking agent is 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.

21. A process according to claim 13 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.

22. A process according to claim 11 wherein said internal crosslinking agent is at least one selected from the group consisting of diallylmaleate, divinylbenzene, triethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1,3 butyleneglycol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol 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.

23. A process according to claim 13 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.

24. A process according to claim 13 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.

25. A process according to claim 13 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.

26. A process according to claim 13 wherein said reactive surfactant is at least one compound having isopropenylphenyl or allyl groups.

27. A process according to claim 13 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, end m is an integer from 15 to 40.

28. A process according to claim 13 wherein the amount of said reactive surfactant ranges from about 0.25% to about 5% by weight based on the total weight of the monomer.

29. A process to produce an acid-treated aqueous dispersion, said process comprising:

1) contacting at least one fluoroalkyl monomer, at least one water-dispersible polyester, and optionally an ethylenically unsaturated monomer to form a pre-emulsion 2) shearing said pre-emulsion to produce a mini-emulsion; 3) polymerizing said miniemulsion in a polymerization zone to produce said aqueous dispersion; and 4) contacting said pre-emulsion, miniemulsion, or aqueous dispersion with at least one acid-generating compound to produce said acid-treated aqueous dispersion.

30. A process according to claim 29 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.

31. A process according to claim 29 wherein the amount of said water-dispersible polyester solids range from about 1% to about 20% by weight based on the weight of said aqueous dispersion.

32. A process according to claim 29 wherein said polymerization is conducted in an emulsion polymerization zone in the presence of at least one initiator under emulsion polymerization conditions.

33. A process according to claim 29 wherein said polymerization occurs at a temperature in the range of 20.degree. C. to 155.degree. C.

34. A process according to claim 33 wherein said polymerization occurs at a temperature in the range of 40.degree. C. to 85.degree. C.

35. A process according to claim 32 wherein the amount of said initiator ranges from about 0.2 to about 1% by weight based on the total amount of monomer.

36. A process according to claim 29 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, external crosslinking agents, internal crosslinking agents, solvents, reactive surfactants, and water-dispersible/water-soluble polymers.

37. A process according to claim 36 wherein said reducing agent is at least one selected from the group consisting of sodium sulfite, sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium formadehyde sulfoxylate, sodium thiosulfate, ascorbic acid isoascorbic acid, and mixtures thereof.

38. A process according to claim 36 wherein said reducing agent is added to said polymerization zone in an amount ranging from about 0.1% to about 2% by weight based on the total weight of the monomer.

39. A process according to claim 36 wherein said catalyst is at least one selected from the group consisting ferrous sulfate heptahydrate, chelated froms of ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.

40. A process according to claim 36 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 monomer.

41. A process according to claim 36 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.

42. A process according to claim 36 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.

43. A process according to claim 36 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.

44. A process according to claim 36 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.

45. A process according to claim 36 wherein said internal crosslinking,g agent is diallylmaleate, divinylbenzene, triethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate, 1,3 butyleneglycol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol 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 trimethylol propane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.

46. A process according to claim 36 wherein the amount of said internal crosslinking agent ranges from about 0.1 to about 5% by weight based ante total amount of monomer.

47. A process according to claim 36 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.

48. A process according to claim 36 wherein the amount of said water-soluble organic solvent is not more tan about 30 parts by weight based on 100 parts by weight of the total amount of monomer.

49. A process according to claim 36 wherein said reactive surfactant is a compound having isopropenylphenyl or allyl groups.

50. A process according to claim 36 wherein said reactive surfactant is a polyoxyethylene alkyl phenyl ether sulfate having one of the following formula:

wherein It is nonyl or octyl, n is an integer from 15 to 15, and m is an integer from 15 to 40.

51. A process according to claim 36 wherein the amount of said reactive surfactant ranges from about 0.25% to about 5% by weight based on the total weight of monomer.

52. A process to produce an acid-treated aqueous dispersion, said process comprising:

1) contacting at least one fluoroalkyl monomer, at least one ethylenically unsaturated monomer having up to 12 carbon atoms, water, at least one nonionic water-dispersible polyester, at least one external crosslinking agent, and at least one reactive surfactant to produce a pre-emulsion; 2) shearing said pre-emulsion to produce a mini-emulsion; 3) adding said pit-emulsion to an emulsion polymerization reactor; 4) contacting at least one water-dispersible polyester with water to produce a polyester/water mixture and routing said polyester/water mixture to said emulsion polymerization reactor, 5) contacting at least one initiator and water to produce an initiator solution and routing said initiator solution to said emulsion polymerization reactor to produce a reaction mixture; 6) polymerizing said reaction mixture to produce said aqueous dispersion; and 7) contacting said aqueous dispersion with at least one acid-generating compound to produce said acid-treated aqueous dispersion.

53. A process according to claim 52 wherein said acid-generating compound is an acid or acid salt.

54. A process according to claim 52 wherein said acid-generating compound is at least one selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, acetic acid, hydroxy acetic acid, citric acid, sulfonic acid and their respective salts formed by ammonia, amines, aminoalcohols, and alkali metal and alkaline earth metal hydroxides.

55. A process according to claim 54 wherein said acid-generating compound is sulfonic acid.

56. A process according to claim 55 wherein said acid-generating compound is para-toluene sulfonic acid.

57. A process to produce an acid-treated aqueous dispersion, said process comprising:

1) contacting a mixed fluoroacrylate monomer stream, lauryl methacrylate, water, polyethylene glycol polyester, n-methyol acrylamide, and polyoxyethylene alkyl propenylphenyl ether sulfate to produce a pre-emulsion; wherein said mixed fluoroacrylate monomer stream comprises 2-(perfluoroallkyl)ethyl acrylate; 2) shearing said pre-emulsion to produce a mini-emulsion 3) adding said pre-emulsion to an emulsion polymerization reactor; 4) contacting a polyethylene glycol polyester dispersion with water to produce a polyester/water mixture and routing said polyester/water mixture to said emulsion polymerization reactor; 5) contacting at least one initiator and water to produce ma initiator solution and muting said initiator solution to said emulsion polymerization reactor to produce a reaction mixture; 6) polymerizing said reaction mixture to produce said aqueous dispersion and; 7) contacting said aqueous dispersion with sulfonic acid to produce said acid-treated aqueous dispersion.

58. A process according to 57 wherein said sulfonic acid is para-toluene sulfonic acid.

59. A process to produce an aqueous dispersion, said process comprising: 1) contacting at least one fluoroalkyl monomer, at least one ethylenically unsaturated monomer having up to 12 carbon atoms, water, at least one water-dispersible polyester, at least one internal crosslinking agent, at least one external crosslinking agent, at least one reactive surfactant, and at least one chain transfer agent to produce a pre-emulsion; 2) shearing said pre-emulsion to produce a mini-emulsion; 3) contacting at least one water-dispersible polyester with water to produce a polyester/water mixture and routing said polyester/water mixture to an emulsion polymerization reactor; 4) contacting at least one initiator and water to produce an initiator solution; 5) adding a portion of said initiator feed to said emulsion polymerization reactor; 6) charging said miniemulsion and initiator solution to said emulsion polymerization reactor over a period of about 1 to about 10 hours under polyermization conditions to produce said aqueous dispersion; and 7) contacting said aqueous dispersion with at least one acid-generating compound to produce said acid-treated aqueous dispersion.

60. A process according to claim 59 wherein said acid-generating compound is an acid or acid salt.

61. A process according to claim 54 wherein said acid-generating compound is selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid, acetic acid, hydroxy acetic acid, citric acid, sulfonic acid and their respective salts formed by ammonia, amines, aminoalcohols, and alkali metal and alkaline earth metal hydroxides.

62. A process according to claim 61 wherein said acid-generating compound is sulfonic acid.

63. A process according to claim 61 wherein said acid-generating compound is para-toluene sulfonic acid.

64. A process to produce an aqueous dispersion, said process comprising: 1) contacting a mixed fluoroacrylate monomer stream, lauryl methacrylate, water, polyethylene glycol polyester, n-methyol acrylamide, diallylmaleate, n-dodecylmercaptan, and polyoxyethylene alkyl propenylphenyl ether sulfate to produce a pre-emulsion; wherein said mixed fluoroacrylate monomer stream comprises 2-(perfluoroallkyl)ethyl acrylate; 2) shearing said pre-emulsion to produce a mini-emulsion; 3) contacting a polyethylene glycol polyester dispersion with water to produce a polyester/water mixture and routing said polyester/water mixture to an emulsion polymerization reactor; 4) contacting at least one initiator and water to produce an initiator solution; 5) adding a portion of said initiator feed to said emulsion polymerization reactor; 6) charging said miniemulsion and initiator solution to said emulsion polymerization reactor over a period of about 1 to about 10 hours under polymerization conditions to produce said aqueous dispersion; and 7) contacting said aqueous dispersion with sulfonic acid to produce said acid-treated aqueous dispersion.

65. A process according to claim 64 wherein said acid-generating compound is paratoluene sulfonic acid.