Method for preparing high-solid, low-viscosity latex using selective hydrophilic macromolecule-RAFT reagent

文档序号：395306 发布日期：2021-12-14 浏览：17次中文

阅读说明：本技术 使用选择性亲水大分子-raft试剂制备高固体、低粘度胶乳的方法 (Method for preparing high-solid, low-viscosity latex using selective hydrophilic macromolecule-RAFT reagent ) 是由周黎昌 D·李 T·陈 F·特雷齐 S·马吉姆达 H·贾马斯比 A·特兰 P-E·迪菲于 2020-04-14 设计创作，主要内容包括：提供了制备水性聚合物分散体的方法及其组合物,这些组合物具有高固体含量(例如50％)和低粘度。该方法使用式(I)的选择性亲水大分子-RAFT试剂,并且基本上不含表面活性剂。该方法可用于制造具有良好稳定性的胶乳聚合物,其可广泛用于涂料(例如,建筑涂漆、石头涂漆、工业涂料、木材涂料等)、粘合剂、密封剂和胶粘剂组合物。(Methods of preparing aqueous polymer dispersions and compositions thereof having high solids content (e.g., 50%) and low viscosity are provided. The method uses a selective hydrophilic macro-RAFT agent of formula (I) and is substantially free of surfactant. The method can be used to make latex polymers with good stability that can be widely used in coatings (e.g., architectural paints, stone paints, industrial paints, wood coatings, etc.), adhesives, sealants, and adhesive compositions.)

1. A method for preparing an aqueous polymer dispersion, the method comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

b. reacting the initial composition from step (a) under suitable conditions to produce a seed composition, wherein the seed composition comprises a polymer formed from the selective hydrophilic macro-RAFT agent of formula (I) and the at least one first monomer; and

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming the aqueous polymer dispersion under conditions suitable to react the seed composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the first monomer comprises a styrene monomer, an acrylic monomer, a vinyl ester monomer, or a mixture thereof;

wherein the second monomer comprises a vinyl ester monomer;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

Saturated or unsaturated, optionally substituted heterocycles (iii), it being possible for these radicals and rings (i), (ii) and (iii) to be substitutedSubstituted phenyl, substituted aromatic or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

x corresponds to Z¹¹Or alternatively x is 0, in which case Z¹¹Represents phenyl, alkenyl or alkynyl, optionally substituted by: optionally substituted alkyl; an acyl group; an aryl group; alkenyl or alkynyl; optionally substituted, saturated, unsaturated or aromatic carbon-based rings; optionally substituted, saturated or unsaturated heterocyclic ring; alkoxycarbonyl or aryloxycarbonyl (-COOR); a carboxyl group (COOH); acyloxy (-O)₂CR); carbamoyl (-CONR)₂) (ii) a Cyano (-CN); an alkylcarbonyl group; an alkylaryl carbonyl group; an arylcarbonyl group; an arylalkyl carbonyl group; a phthalimide group; a maleimide group; a succinimide group; an amidino group; guanidino; hydroxyl (-OH); amino (- -NR)₂) (ii) a Halogen; an allyl group; an epoxy group; alkoxy (-OR), S-alkyl; s-aryl; hydrophilic or ionic groups, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and is

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

2. The method of claim 1, further wherein the aqueous polymer dispersion is formed using polymerization-induced self-assembly of a latex polymer composition.

3. The process according to claim 1, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

4. The process according to claim 1, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 4000cps, less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

5. The process according to claim 1, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

6. The method of claim 1, wherein the at least one first monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

7. The method of claim 1, wherein the at least one second monomer is vinyl acetate monomer.

8. The method according to claim 1, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

9. The method according to claim 1, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

10. A composition comprising a latex polymer composition obtained by a free radical emulsion polymerization process comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming the aqueous polymer dispersion under conditions suitable to react the seed composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the first monomer comprises a styrene monomer, an acrylic monomer, a vinyl ester monomer, or a mixture thereof;

wherein the second monomer comprises a vinyl ester monomer or a mixture thereof;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxy (-OH), guanidino₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

11. The composition according to claim 10, further wherein the aqueous polymer dispersion is formed using polymerization-induced self-assembly of a latex polymer composition.

12. The composition according to claim 10, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

13. The composition according to claim 10, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

14. The composition according to claim 10, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3.

15. The composition according to claim 10, wherein the at least one first monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

16. The composition according to claim 10, wherein the at least one second monomer is a vinyl acetate monomer.

17. The composition according to claim 10, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

18. The composition according to claim 10, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

19. A coating composition comprising the latex polymer composition made according to the method of claim 1.

20. The coating composition of claim 19, wherein the coating composition is an industrial coating or a wood coating.

21. The coating composition according to claim 19, wherein the coating composition is a paint composition.

22. The coating composition of claim 21, having good scrub resistance, preferably at least 300 scrub resistance according to ASTM test method, more preferably at least about five times as high as surfactant-based latex.

23. The coating composition according to claim 21, which has good adhesion, preferably to a variety of substrates such as glass and metal.

24. The coating composition of claim 21, which is resistant to water whitening.

25. The coating composition of claim 21, which is water resistant.

26. The coating composition according to claim 21, wherein the paint composition is an architectural paint composition or a stone paint composition.

27. The coating composition according to claim 21, wherein the composition has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

28. The coating composition according to claim 21, wherein the composition has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

29. The coating composition according to claim 21, wherein the composition has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

30. An adhesive composition comprising the latex polymer composition of the method of claim 1.

31. An adhesive composition comprising the latex polymer composition made according to the method of claim 1.

32. A sealant composition comprising the latex polymer composition made according to the method of claim 1.

33. A method for preparing an aqueous polymer dispersion, the method comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming the aqueous polymer dispersion under conditions suitable to react the seed composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the first monomer is selected from the group consisting of: methyl methacrylate monomers, butyl acrylate monomers, and mixtures thereof;

wherein the second monomer comprises an acrylic monomer;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinylPerimide group, amidino group, guanidino group, hydroxyl group (-OH), amino group (-NR)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

34. The method of claim 33, further wherein the aqueous polymer dispersion is formed under conditions suitable for polymerization-induced self-assembly of a latex polymer composition.

35. The process according to claim 33, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

36. The process according to claim 33, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3.

37. The process according to claim 33, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3.

38. The method of claim 33, wherein the at least one acrylic monomer is selected from the group consisting of: acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, and mixtures thereof.

39. The method of claim 33, wherein the at least one first monomer comprises a methyl methacrylate/butyl acrylate ratio of about 40: 60 to about 60: 40.

40. The method of claim 33, wherein the at least one first monomer is selected from the group consisting of methyl methacrylate/butyl acrylate in a ratio of about 50: 50.

41. The method of claim 33, wherein the at least one first monomer is selected from butyl acrylate/methyl methacrylate copolymers.

42. The method according to claim 33, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

43. The method according to claim 33, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

44. A composition comprising a latex polymer composition obtained by a free radical emulsion polymerization process comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming an aqueous polymer dispersion under conditions suitable to react the seed composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the first monomer is selected from the group consisting of: methyl methacrylate monomers, butyl acrylate monomers, and mixtures thereof;

wherein the second monomer comprises an acrylic monomer;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹denotes C, N, O, S orP，

Z¹²The expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

x corresponds to Z¹¹Or alternatively x is 0, in which case Z¹¹Represents phenyl, alkenyl or alkynyl, optionally substituted by: optionally substituted alkyl; an acyl group; an aryl group; alkenyl or alkynyl; optionally substituted, saturated, unsaturated or aromatic carbon-based rings; optionally substituted, saturated or unsaturated heterocyclic ring; alkoxycarbonyl or aryloxycarbonyl (mono COOR); a carboxyl group (COOH); acyloxy (-O)₂CR); carbamoyl (-CONR)₂) (ii) a Cyano (-CN); an alkylcarbonyl group; an alkylaryl carbonyl group; an arylcarbonyl group; an arylalkyl carbonyl group; a phthalimide group; a maleimide group; a succinimide group; an amidino group; guanidino; hydroxyl (-OH); amino (-NR)₂) (ii) a Halogen; an allyl group; an epoxy group; alkoxy (-OR), S-alkyl; s-aryl; hydrophilic or ionic groups, e.g. alkali metal salts of carboxylic acids, sulfonic acidsAlkali metal salts of (a), polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and is

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

45. The composition according to claim 44, further wherein the aqueous polymer dispersion is formed under conditions suitable for polymerization-induced self-assembly of a latex polymer composition.

46. The composition according to claim 44, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

47. The composition according to claim 44, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

48. The composition according to claim 44, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

49. The composition according to claim 44, wherein the at least one acrylic monomer is selected from the group consisting of: acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, and mixtures thereof.

50. The composition according to claim 44, wherein the at least one first monomer comprises methyl methacrylate/butyl acrylate in a ratio of about 40: 60 to about 60: 40.

51. The composition according to claim 44, wherein the at least one first monomer is selected from the group consisting of methyl methacrylate/butyl acrylate in a ratio of about 50: 50.

52. The composition of claim 44, wherein the seed composition consists of butyl acrylate/methyl methacrylate copolymer.

53. The composition according to claim 44, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

54. The composition according to claim 44, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

55. A coating composition comprising the latex polymer composition of the method of claim 33.

56. The coating composition of claim 55, wherein the coating composition is an industrial coating or a wood coating.

57. The coating composition according to claim 55, wherein the coating composition is a paint composition.

58. The coating composition of claim 57 having good scrub resistance, preferably at least 300 scrub resistance according to ASTM test method, more preferably at least about five times as high as surfactant-based latex.

59. The coating composition of claim 57, which has good adhesion, preferably to a variety of substrates such as glass and metal.

60. The coating composition of claim 57 which is resistant to water whitening.

61. The coating composition of claim 57 which is water resistant.

62. The coating composition according to claim 57, wherein the paint composition is an architectural paint composition or a stone paint composition.

63. The coating composition according to claim 57, wherein the composition has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

64. The coating composition according to claim 57, wherein the composition has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

65. The coating composition according to claim 57, wherein the composition has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly LVT viscometer at 30rpm and spindle 3.

66. An adhesive composition comprising the latex polymer composition of the method of claim 33.

67. An adhesive composition comprising the latex polymer composition made according to the method of claim 33.

68. A sealant composition comprising the latex polymer composition made according to the method of claim 33.

69. A method for preparing an aqueous polymer dispersion, the method comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming the aqueous polymer dispersion under conditions suitable to react the seed composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the at least one first monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof;

wherein the at least one second monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

x corresponds to Z¹¹Or alternatively x is 0, in which case Z¹¹Represents phenyl, alkenyl or alkynyl, optionally substituted by: optionally substituted alkyl; an acyl group; an aryl group; alkenyl or alkynyl; optionally substituted, saturated, unsaturated or aromatic carbon-based rings; optionally substituted, saturated or unsaturated heterocyclic ring; alkoxycarbonyl or aryloxycarbonyl (-COOR); a carboxyl group (COOH); acyloxy (-O)₂CR); carbamoyl (-CONR)₂) (ii) a Cyano (-CN); an alkylcarbonyl group; an alkylaryl carbonyl group; an arylcarbonyl group; an arylalkyl carbonyl group; a phthalimide group; a maleimide group; a succinimide group; an amidino group; guanidino; hydroxyl (-OH); amino (- -NR)₂) (ii) a Halogen; an allyl group; an epoxy group; alkoxy (-OR), S-alkyl; s-aryl; hydrophilic or ionic groups, e.g. alkali metal salts of carboxylic acids, of sulfonic acids, of polyoxyalkylenesHydrocarbon (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and is

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

70. The method of claim 69, wherein the at least one first monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof.

71. The method of claim 69, wherein the at least one second monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof.

72. The method according to claim 69, wherein the styrene or acrylic monomers are selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

73. The method according to claim 69, wherein the vinyl ester monomers are selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

74. The method according to claim 69, wherein the acrylic monomers are selected from the group consisting of: acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters.

75. The method according to claim 69, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

76. The method according to claim 69, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

77. The method of claim 69, further wherein the aqueous polymer dispersion is formed under conditions suitable for polymerization-induced self-assembly of a latex polymer composition.

78. The process according to claim 69, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

79. The process according to claim 69, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

80. The process according to claim 69, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

81. A composition comprising a latex polymer composition obtained by a free radical emulsion polymerization process comprising:

a. providing an initial composition comprising:

i. from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); and

from about 0.1 to about 30 parts of at least one first monomer;

from about 0.05 to about 0.5 parts of a free radical initiator; and

(iii) water, in the presence of a catalyst,

c. combining the seed composition from step (b) with:

i. about 0.05 to about 0.8 parts of at least one initiator; and

from about 0.1 to about 99 parts of at least one second monomer,

forming an aqueous polymer dispersion under conditions suitable to react the first polymer composition with the at least one second monomer;

wherein the at least one first monomer and the at least one second monomer are different,

wherein the at least one first monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof;

wherein the at least one second monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof;

wherein the process is substantially free of surfactant; and is

Wherein the selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl)Arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

A represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

82. The composition according to claim 81, wherein the at least one first monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof.

83. The composition according to claim 81, wherein the at least one second monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof.

84. The composition according to claim 81, wherein the styrene or acrylic monomers are selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

85. The composition according to claim 81, wherein the vinyl ester monomers are selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof.

86. The composition according to claim 81, wherein the acrylic monomers are selected from the group consisting of: acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters.

87. The composition according to claim 81, wherein the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 3 parts.

88. The composition according to claim 81, wherein the selective hydrophilic macro-RAFT agent of formula (I) is selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, and PDMA-Xa.

89. The composition according to claim 81, further wherein the aqueous polymer dispersion is formed under conditions suitable for polymerization-induced self-assembly of a latex polymer composition.

90. The composition according to claim 81, wherein the latex polymer composition formed in step (c) has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

91. The composition according to claim 81, wherein the latex polymer composition formed in step (c) has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

92. The composition according to claim 81, wherein the latex polymer composition formed in step (c) has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3.

93. A coating composition comprising the latex polymer composition of the method of claim 69.

94. The coating composition of claim 93, wherein the coating composition is an industrial coating or a wood coating.

95. The coating composition of claim 93, wherein the coating composition is a paint composition.

96. The coating composition of claim 95, having good scrub resistance, preferably at least 300 scrub resistance according to ASTM test method, more preferably at least about five times as high as surfactant-based latex.

97. The coating composition of claim 95, which has good adhesion, preferably to a variety of substrates such as glass and metal.

98. The coating composition of claim 95, which is resistant to water whitening.

99. The coating composition of claim 95, which is water resistant.

100. The coating composition according to claim 95, wherein the paint composition is an architectural paint composition or a stone paint composition.

101. The coating composition of claim 95, wherein the composition has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

102. The coating composition of claim 95, wherein the composition has a solids content of at least 40% and a viscosity of less than 3000cps, preferably less than 1500cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

103. The coating composition of claim 95, wherein the composition has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

104. An adhesive composition comprising the latex polymer composition of the method of claim 69.

105. An adhesive composition comprising the latex polymer composition made according to the method of claim 69.

106. A sealant composition comprising the latex polymer composition made according to the method of claim 69.

Technical Field

The present application relates to a method of preparing an aqueous polymer dispersion and compositions thereof. The process uses hydrophilic precursors (or other chain transfer agents or "CTAs") having xanthate moieties, particularly selective hydrophilic macro-RAFT agents of formula (I), in a two-stage emulsion polymerization without the need for emulsifying surfactants. The process can be used to make improved latex polymers with good stability that can be used in a wide variety of coatings (e.g., architectural paints, stone paints, industrial paints, wood coatings, etc.), adhesives, sealants, and adhesive compositions. In a preferred embodiment, a high solids latex composition is provided having a low viscosity, such as for use in a paint or coating composition.

Background

Latexes are colloidal dispersions of polymer particles in water produced by emulsion polymerization. Latices are used in a wide range of applications and offer considerable advantages for industrial synthesis. They represent an attractive alternative to solvent-based formulations.

Typically, surfactants are used to prepare seeds for the emulsion polymer latex, and as such, surfactants play a decisive role in the formation of the emulsion polymer latex. However, once the latex has been formed, the surfactant remaining in the formulation can be detrimental in the end application or coating. Surfactants can have negative effects on latex compositions, including with respect to water sensitivity, adhesion, impact on paint films (leaching, efflorescence, surface tension defects, etc.) and low to zero foaming. For example, one disadvantage of having residual surfactant in the formulation is surfactant blooming or surfactant whitening. Surfactant blooming or whitening occurs when the film is in contact with water and the surfactant migrates. This can lead to hazing of the film, an undesirable characteristic.

It is also believed that excess surfactant results in low water resistance for the final coating application. Post-polymerization mobility of surfactants is yet another problem associated with the use of surfactants during emulsion polymerization of latexes. For example, the surfactant may migrate from the surface of the latex particle to the liquid-air interface or from the surface of the formed latex film. It is desirable to minimize the adverse effects of surfactants in aqueous emulsion polymer latex applications.

Disclosure of Invention

The present application describes a process for preparing aqueous polymer dispersions having a high solids content (e.g. 50%) and low viscosity by a two-stage process using a selective hydrophilic macromolecule-RAFT agent of formula (I). The process can be used to make latex polymers with good stability that are widely used as coatings (e.g., architectural, stone, industrial, wood, etc.), adhesives, sealants, and adhesive compositions.

Latexes as described herein are made without the use of surfactants, but by inducing molecular self-assembly of polymeric emulsifier particles made from RAFT.

It has been surprisingly found that emulsion polymerization of hydrophobic monomers can be carried out directly using water-soluble macro-RAFT/MADIX reagents under batch initial conditions. Under such conditions, the amphiphilic block copolymer forms and self-assembles into self-stable particles during polymerization by polymerization-induced self-assembly (PISA). This approach solves the problems encountered during attempts to implement RAFT/MADIX in the initial emulsion, such as loss of molecular weight control, loss of colloidal stability and/or formation of intractable oily layers. The PISA process allows the synthesis of latex without the use of low molecular weight surfactants, avoiding the problems caused by these products.

Latex is an example of an emulsion polymer of a water-based polymer dispersion. Latex paint is used in a variety of applications: including interior and exterior applications, as well as flat, semi-gloss, and gloss applications. Latex is a stable dispersion (colloidal emulsion) of microparticles of rubber or plastic polymers in an aqueous medium. The latex may be natural or synthetic.

Latex preparation in the absence of surfactants is enabled by the alternative use of hydrophilic macromolecular chain transfer agents, such as PISA (polymerization induced self-assembly) used in the process of preparing latex. Thus, latexes prepared by using these hydrophilic compounds in place of traditional surfactants show, among other benefits, improvements in water resistance, scrub resistance, and/or stain resistance.

In one embodiment, the present application relates to a method for preparing an aqueous polymer dispersion, the method comprising providing an initial composition, reacting the initial composition to form seeds having a first monomer and a selective hydrophilic macro-RAFT agent of formula (I), and subsequently performing a subsequent reaction with a second monomer. Specifically, the method comprises providing an initial composition comprising: (i) from about 0.5 to about 6 parts of a selective hydrophilic macro-RAFT agent of formula (I); (ii) from about 0.1 to about 30 parts of at least one first monomer; (iii) about 0.05 to about 0.5 parts of a free radical initiator; and (iv) water. Reacting the initial composition under suitable conditions to produce a seed composition, wherein the seed composition comprises a polymer formed from the selective hydrophilic macro-RAFT agent of formula (I) and at least one first monomer. Combining a seed composition with: (i) about 0.05 to about 0.8 parts of at least one initiator; and (ii) from about 0.1 to about 99 parts of at least one second monomer under conditions suitable to react the seed composition with the at least one second monomer to form an aqueous polymer dispersion. In the method, the at least one first monomer and the at least one second monomer are different, and the method is substantially free of surfactant.

In one embodiment, the first monomer comprises a styrene monomer, an acrylic monomer, a vinyl ester monomer, or a mixture thereof; and the second monomer comprises a vinyl ester monomer. For example, the at least one first monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof, and at least one second monomer is a vinyl acetate monomer.

In another embodiment, the first monomer is selected from the group consisting of: methyl methacrylate monomers, butyl acrylate monomers, and mixtures thereof; and the second monomer comprises an acrylic monomer. For example, the at least one acrylic monomer is selected from the group consisting of: acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, and mixtures thereof. Preferably, the at least one first monomer comprises a methyl methacrylate/butyl acrylate ratio of about 40: 60 to about 60: 40, or the at least one first monomer is selected from a methyl methacrylate/butyl acrylate ratio of about 50: 50. In another aspect, the at least one first monomer is selected from butyl acrylate/methyl methacrylate copolymers.

In another embodiment, the at least one first monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof; and the second monomer is selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof. Preferably, the at least one first monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof. In one aspect, the at least one second monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof. In another aspect, the styrene or acrylic monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof. In one aspect, the vinyl ester monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof. In another aspect, the acrylic monomer is selected from the group consisting of: acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters.

A selective hydrophilic macromolecule-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹² (I)

wherein:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

-optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

-a saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

-a saturated or unsaturated, optionally substituted heterocyclic ring (iii), these groups and rings (i), (ii) and (iii) possibly substituted by substituted phenyl, substituted aromatic groups or by the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH),acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

x corresponds to Z¹¹Or alternatively x is 0, in which case Z¹¹Represents phenyl, alkenyl or alkynyl, optionally substituted by: optionally substituted alkyl; an acyl group; an aryl group; alkenyl or alkynyl; optionally substituted, saturated, unsaturated or aromatic carbon-based rings; optionally substituted, saturated or unsaturated heterocyclic ring; alkoxycarbonyl or aryloxycarbonyl (-COOR); a carboxyl group (COOH); acyloxy (-O)₂CR); carbamoyl (-CONR)₂) (ii) a Cyano (-CN); an alkylcarbonyl group; an alkylaryl carbonyl group; an arylcarbonyl group; an arylalkyl carbonyl group; a phthalimide group; a maleimide group; a succinimide group; an amidino group; guanidino; hydroxyl (-OH); amino (-NR)₂) (ii) a Halogen; an allyl group; an epoxy group; alkoxy (-OR), S-alkyl; s-aryl; hydrophilic or ionic groups, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and a represents a mono-, di-or triblock polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

Preferably, the selective hydrophilic macro-RAFT agent is present in an amount of about 0.5 to about 6 parts, or about 0.5 to about 3 parts. The selective hydrophilic macro-RAFT agent of formula (I) may be selected from the group consisting of: PAA-Xa, PAM-PAA-Xa, PDMA-Xa, and mixtures thereof.

Preferably, polymerization induced self-assembly of the latex polymer composition is used to form the aqueous polymer dispersion.

According to this process, the resulting latex polymer composition has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly (Brookfield) model LVT viscometer at 30rpm and spindle 3. In another aspect, the latex polymer composition has a solids content of at least 40% and a viscosity of less than 4000cps, less than 3000cps, less than 1500cps, and less than 1000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3. In another aspect, the latex polymer composition has a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

The present application also relates to a latex polymer composition comprising a latex obtained by the above free radical emulsion polymerization process.

In certain embodiments, the present application relates to an adhesive composition comprising a latex polymer composition. In other embodiments, the present application relates to an adhesive composition comprising a latex polymer composition or a sealant composition comprising a latex polymer composition.

In a preferred embodiment, the present application relates to a coating composition comprising a latex polymer composition made according to the method. For example, the coating composition may be an industrial coating or a wood coating, and preferably, the coating composition is a paint composition, preferably an architectural paint composition or a stone paint composition. Preferably, the paint composition will have good block resistance. In addition, such coating compositions preferably have good scrub resistance, preferably at least 300 scrub resistance according to ASTM test methods, more preferably at least about five times as high as surfactant-based latexes. In another aspect, the coating composition will have good adhesion characteristics, preferably good adhesion to a variety of substrates such as glass and metal. In another aspect, the coating composition of claim will be water-whitening and/or water-resistant.

In certain aspects, the coating composition will have a low viscosity and a high solids content. For example, the coating composition may preferably have a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a Bohler fly model LVT viscometer at 30rpm and spindle 3. In another aspect, the coating composition may preferably have a solids content of at least 40% and a viscosity of less than 4000cps, less than 3000cps, less than 2000cps, less than 1500cps, or less than 1000cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3. In another aspect, the coating composition may preferably have a solids content of at least 50% and a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3.

Preferably, the latex produced according to the present application will have good mechanical stability, electrolyte (CaCl)₂) Stability, freeze thaw stability, adhesion, and low to zero foam.

Latex paint formulations typically contain additives, such as at least one pigment. In a preferred embodiment of the present invention, the latex paint formulation comprises at least one pigment selected from the group consisting of: TiO 2₂、CaCO₃Clay, alumina, silica, magnesia, sodium oxide, potassium oxide, talc, barytes, zinc oxide, zinc sulfite, and mixtures thereof. More preferably, at least one pigment comprises TiO₂Calcium carbonate or clay.

In addition to the above components, the aqueous coating composition may further comprise one or more additives selected from the group consisting of: dispersants, defoamers, biocides, mildewcides, colorants, waxes, fragrances, and co-solvents.

The compositions of the present invention may be free of one or more of anionic, cationic, nonionic, zwitterionic and/or amphoteric surfactants.

These and other features and advantages of the present invention will become more readily apparent to those skilled in the art after considering the following detailed description which describes both the preferred and alternative embodiments of the invention.

Detailed Description

As used herein, the term "alkyl" means a saturated straight, branched, or cyclic hydrocarbon group including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl, and 2-ethylhexyl.

As used herein, the term "aryl" means a monovalent unsaturated hydrocarbon group comprising one or more six-membered carbocyclic rings in which the unsaturation may be represented by three conjugated double bonds, which may be substituted on one or more carbons of the ring by hydroxy, alkyl, alkenyl, halogen, haloalkyl or amino groups, including but not limited to phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, aminophenyl and tristyrylphenyl.

As used herein, the term "alkylene" means a divalent saturated straight or branched chain hydrocarbon group, such as, for example, methylene, dimethylene, and trimethylene.

As used herein, the term "(C)_r-C_s) "in reference to an organic group, where r and s are each an integer, means that the group may contain from r carbon atoms to s carbon atoms per group.

As used herein, the term "(meth) acrylate" refers collectively and alternatively to both acrylate and methacrylate, and the term "(meth) acrylamide" refers collectively and alternatively to both acrylamide and methacrylamide, thus, for example, "(meth) butyl acrylate" means butyl acrylate and/or butyl methacrylate.

As used herein, "molecular weight," when referring to a polymer or any portion thereof, means the weight average molecular weight ("Mw") of the polymer or portion. The Mw of a polymer is a value measured by Gel Permeation Chromatography (GPC), light scattering (DLS or alternatively MALLS), viscometry, or a variety of other standard techniques using an aqueous or organic eluent (e.g., dimethylacetamide, dimethylformamide, etc.), depending on the composition of the polymer. The Mw of a portion of a polymer is a value calculated from the amounts of monomers, polymers, initiators, and/or transfer agents used to make up the portion according to known techniques.

As used herein, each of the terms "monomer", "polymer", "homopolymer", "copolymer", "linear polymer", "branched polymer", "block copolymer", "graft copolymer", and the like has the meaning assigned thereto by the basic glossary of terms in polymer science (IUPAC Recommendations [ IUPAC Recommendations ]1996), Pure apply. chem. [ Pure application chemistry ], volume 68, phase 12, page 2287-.

As used herein, the indication that a group may be "optionally substituted" or "optionally further substituted" generally means that, unless explicitly or otherwise further limited by the context of such reference, such group may be substituted with one or more inorganic or organic substituents (e.g., alkyl, alkenyl, aryl, aralkyl, alkaryl, heteroatoms, or heterocyclic groups), or with one or more functional groups capable of coordinating to a metal ion (such as hydroxyl, carbonyl, carboxyl, amino, imino, amido, phosphonic acid, sulfonic acid, or arsenate, or inorganic and organic esters thereof (such as, for example, sulfates or phosphates), or salts thereof).

As used herein, "part," "part by weight," or "pbw" when referring to a named compound refers to the amount of the named compound (excluding, for example, any relevant solvents).

As used herein, the indication that a composition is "substantially free" of a particular material means that the composition contains no more than an insubstantial amount of the material, and "insubstantial amount" means an amount that does not measurably affect the desired property of the composition.

As used herein, the term "surfactant" means a compound that reduces surface tension when dissolved in water.

As used herein, suitable polymerizable functional groups include, for example, acryloyl (acrylo), methacryloyl, acrylamido, methacrylamido, diallylamino, allyl ether, vinyl ether, α -alkenyl, maleimido, styryl, and α -alkylstyrene groups.

As used herein, the term "macromolecular CTA" means a structure according to the following formula (I).

Latex (emulsion polymer) is commonly and widely used in paint and coating, adhesive, sealant and elastomer applications. A typical preparation for the industrial production of latex polymers involves the use of monomers from styrene, butyl acrylate, and ethylhexyl acrylate to vinyl acetate to gaseous monomers such as ethylene, plus typical initiators such as ammonium persulfate and the like, and surfactants to stabilize the latex particles in the range from 40nm to 500nm (typically 80-250 nm).

The amount of surfactant used to make the latex may range between 1% and 3% based on the total amount of monomers. Surfactants are used not only to control particle size but also to provide shear stability and therefore play a crucial role in the preparation of the latex and the long-term storage stability of the latex.

However, it is sometimes desirable to minimize surfactant levels to obtain films of latex that can provide excellent water resistance along with adhesion to substrates is more important than such use of surfactants. Thus, the importance of eliminating or reducing surfactants becomes critical and becomes more critical in paint films (with low or high PVC) because the presence of surfactants tends to reduce the aesthetic appearance of the paint film (blistering, leaching, cratering, etc.).

Especially for latex polymers based on copolymers of vinyl acetate or copolymers of styrene acrylate, the use of surfactants has been minimized or attempts have been made to use polymerizable surfactants in order to improve the water resistance of the latex film and the water resistance of the paint film. In both cases, the results are unsatisfactory in obtaining good water resistance or other performance characteristics.

In one embodiment, using macromolecular CTA (hydrophilic precursor with xanthate moiety) as described herein in emulsion polymerization of latex, latex polymers of vinyl acetate with other comonomers and also styrene with other comonomers have been prepared in particular to produce stable latexes with particle size ranging from 80-200 nm. Films of latex polymers exhibit unexpectedly exceptional water resistance as measured by various water resistance test methods (i.e., water drop, water immersion, and water vapor tests). For example, films of the latex prepared with the macromolecular CTA above were tested by water immersion testing (by soaking the film of latex in water for up to 8 days and monitoring for whitening (whiteness) or any other film defects) and by water vapor methods for one hour compared to films of commercial latex and latex produced using standard surfactants.

Latex films based on commercial latex and latex films prepared in the laboratory using surfactants whiten after 24 hours and the whitening (whiteness) of the films gradually becomes deeper over time, while latex films based on copolymers of vinyl acetate or styrene acrylic acid show no tendency to whiten even after soaking the films in water for 8 days.

Latexes of copolymers based on vinyl acetate and copolymers of comonomers with styrene prepared using macromolecular CTA show enhanced shear, freeze-thaw and electrolyte stability compared to surfactant-based latexes, and films of latexes show enhanced adhesion to metal substrates.

The above latex of the present invention, prepared using a macromolecular CTA containing a xanthate moiety, can be easily scaled for commercial purposes. The preparation of seeds of the above latex polymers (vinyl acetate copolymers and or styrene copolymers), which are part of the preparation of the high solids latex, is also desirable.

The use of the described macromolecular CTAs, as well as a range of macromolecular CTAs with available specialty monomers, allows tailoring of latexes of various properties and multifunctional properties, and thereby extends the applications beyond just paint and coating applications, including but not limited to coatings, adhesives, sealants, elastomer applications, and the like.

The latexes of the invention comprise, in dispersion, a water-insoluble polymer obtained from a monomer comprising ethylenic unsaturation. Monomers as mentioned herein may be used as ethylenically unsaturated monomers involved in the production of the latex. Latex with modified surface characteristics, which can be obtained using a process comprising the addition of a water-soluble amphiphilic copolymer to an aqueous dispersion of a water-insoluble polymer or copolymer obtained from monomers with ethylenic unsaturation.

In one embodiment, the latex can be used as a binder in a variety of applications in the fields of painting, paper coatings, and building materials.

In one embodiment, the non-surfactant copolymer may be obtained by selection of monomers, for example, the styrene/BA copolymer is non-surfactant. Non-surfactant block copolymers may also be obtained by increasing the molecular weight or by decreasing the fraction of hydrophobic monomers in the copolymer.

In general, the aforementioned water-soluble amphiphilic block copolymers can be obtained by any polymerization process known as "living" or "controlled", such as, for example: by xanthate controlled radical polymerization, according to the teaching of application WO 98/58974; controlled free radical polymerization by dithioesters, according to the teaching of application WO 97/01478; polymerization using nitroxide precursors, according to the teaching of application WO 99/03894; controlled free radical polymerization by dithiocarbamates, according to the teaching of application WO 99/31144; and/or Atom Transfer Radical Polymerization (ATRP), according to the teaching of application WO 96/30421.

The term "macromolecular CTA" or selective hydrophilic macromolecular-RAFT agent of formula (I) is defined as follows:

(R¹¹)x-Z¹¹-C(＝S)-Z¹²-[A]-R¹²(I)

in this formula:

Z¹¹the representation of C, N, O, S or P is shown,

Z¹²the expression S or P is used to indicate that,

R¹¹and R¹²Which may be the same or different, represent:

optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

A saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

(ii) a saturated or unsaturated, optionally substituted heterocyclic ring (iii),these groups and rings (i), (ii) and (iii) may be substituted with substituted phenyl, substituted aromatic groups or the following groups: alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

x corresponds to Z¹¹Or alternatively of

x is 0, in this case, Z¹¹Represents phenyl, alkenyl or alkynyl, optionally substituted by: optionally substituted alkyl; an acyl group; an aryl group; alkenyl or alkynyl; optionally substituted, saturated, unsaturated or aromatic carbon-based rings; optionally substituted, saturated or unsaturated heterocyclic ring; alkoxycarbonyl or aryloxycarbonyl (-COOR); a carboxyl group (COOH); acyloxy (-O)₂CR); carbamoyl (-CONR)₂) (ii) a Cyano (-CN); an alkylcarbonyl group; an alkylaryl carbonyl group; an arylcarbonyl group; an arylalkyl carbonyl group; a phthalimide group; a maleimide group; a succinimide group; an amidino group; guanidino; hydroxyl (-OH); amino (-NR)₂) (ii) a Halogen; an allyl group; an epoxy group; alkoxy (-OR), S-alkyl; s-aryl; hydrophilic or ionic groups, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts); and is

A represents a mono, di or tri block polymer, preferably a represents a mono, di or tri block polymer comprising at least a hydrophilic first block and optionally a hydrophobic or hydrophilic second block.

According to one advantageous variant of the invention, the compounds of the formula (I) are such that Z¹¹Is an oxygen atom and Z¹²Is a sulfur atom. Thus, these compounds are functionalized with xanthates at the chain ends.

As regards the polymer a, it more particularly corresponds to at least one of the three formulae below:

in these formulae:

va, V ' a, Vb, V ' b, Vc and V ' c, which may be the same or different, represent: H. an alkyl group or a halogen, in which,

xa, X ' a, Xb, X ' b, Xc and X ' c, which may be identical OR different, represent H, halogen OR a group R, OR, OCOR, NHCOH, OH, NH2, NHR, N (R)₂、(R)₂N⁺O^-、NHCOR、CO₂H、CO₂R、CN、CONH₂CONHR or CONR₂Wherein R, which may be the same or different, is selected from alkyl, aryl, aralkyl, alkaryl, alkenyl and organosilyl groups, optionally perfluorinated and optionally substituted with one or more carboxyl, epoxy, hydroxyl, alkoxy, amino, halogen or sulphonic groups,

l, m and n, which may be identical or different, are greater than or equal to 1,

x, y and z may be the same or different, equal to 0 or 1.

More particularly, the polymer a is obtained by using at least one ethylenically unsaturated monomer chosen from hydrophilic monomers.

Examples of such monomers that may be particularly mentioned include at least one of the following: (i) ethylenically unsaturated monocarboxylic and dicarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid; (ii) monoalkyl esters of dicarboxylic acids of the mentioned type with alkanols preferably containing 1 to 4 carbon atoms, and also N-substituted derivatives thereof, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate; (iii) unsaturated carboxylic acid amides such as acrylamide or methacrylamide; (iv) ethylenic monomers containing a sulfonic acid group and ammonium or alkali metal salts thereof, such as vinylsulfonic acid, vinylbenzenesulfonic acid, α -acrylamidomethylpropanesulfonic acid, or 2-sulfoethylene methacrylate; (v) (vii) vinylphosphonic acid, and (vi) vinylsulphonate and salts thereof.

A proportion of hydrophobic monomers may be incorporated into the polymer composition provided that the solubility/dispersibility conditions previously mentioned and the conditions under which gelled or ungelled micelles are not formed remain effective.

Examples of hydrophobic monomers which may be mentioned in particular include styrene or derivatives thereof, butadiene, chloroprene, (meth) acrylates, vinyl esters and vinyl nitriles.

The term "(meth) acrylate" denotes acrylic acid and methacrylic acid with hydrogenated or fluorinated C₁-C₁₂And preferably C₁-C₈Esters of alcohols. Among the compounds of this type that may be mentioned are: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate.

Vinyl nitriles more particularly include those containing from 3 to 12 carbon atoms, such as, in particular, acrylonitrile and methacrylonitrile.

It should be noted that styrene may be replaced in whole or in part by derivatives such as alpha-methylstyrene or vinyltoluene.

Other ethylenically unsaturated monomers which may be used alone or as mixtures or which are copolymerizable with the above monomers are, in particular: vinyl esters of carboxylic acids, such as vinyl acetate, vinyl versatate or vinyl propionate; a vinyl halide; vinylamine amides, especially vinylformamide or vinylacetamide; ethylenically unsaturated monomers which contain secondary, tertiary or quaternary amino groups, or nitrogen-containing heterocyclic groups, such as, for example, vinylpyridine, vinylimidazole, aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides, for example dimethylaminoethyl acrylate or methacrylate, di-tert-butylaminoethyl acrylate or methacrylate, dimethylaminomethylacrylamide or dimethylaminomethylmethacrylamide. It is also possible to use zwitterionic monomers, such as, for example, sulfopropyl (dimethyl) aminopropyl acrylate.

According to a particularly advantageous embodiment, the polymer a is a mono-block or di-block polymer.

It should furthermore be noted that the polymer a more particularly has a number-average molar mass of less than 20,000 and preferably less than 10,000. In one embodiment, polymer a has a number average molar mass between about 1,000 and about 7,000. These molar masses were measured by size exclusion chromatography using polyethylene glycol as a standard.

In one embodiment, the polymer a or macromolecular CTA has a weight average molecular weight of less than 30,000, typically less than 15,000. In one embodiment, the polymer a or macromolecular CTA has a weight average molecular weight between about 1,500 and about 10,000.

According to a second embodiment of the invention, the monoblock, diblock or triblock polymer used is a polymer corresponding to the formula:

and/or:

in these formulae:

x represents an atom selected from the group consisting of N, C, P and Si,

R²²represents:

optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl (i), or

A saturated or unsaturated, optionally substituted or aromatic carbon-based ring (ii), or

(ii) a saturated or unsaturated, optionally substituted or aromatic heterocycle (iii) which is substituted with the phenyl, substituted aromatic groups which rings (i), (ii) and (iii) may be substituted or with the following groups:

alkoxycarbonyl or aryloxycarbonyl (-COOR), carboxyl (-COOH), acyloxy (-O)₂CR), carbamoyl (-CONR)₂) Cyano (-CN), alkylcarbonyl, alkylarylcarbonyl, arylcarbonyl, arylalkylcarbonyl, phthalimido, maleimido, succinimido, amidino, guanidino, hydroxy (-OH), amino (-NR), guanidino, hydroxyl (-OH)₂) Halogen, allyl, epoxy, alkoxy (-OR), S-alkyl, S-aryl, organosilyl, hydrophilic OR ionic groups such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO OR PPO) chains and cationic substituents (quaternary ammonium salts),

r represents an alkyl group or an aryl group,

Z、R²¹ⁱand R²³Which may be the same or different, are selected from:

a hydrogen atom, and a nitrogen atom,

optionally substituted alkyl, acyl, aryl, alkenyl or alkynyl,

a saturated or unsaturated, optionally substituted or aromatic carbon-based ring,

a saturated or unsaturated, optionally substituted heterocyclic ring,

hydrophilic or ionic groups, such as alkali metal salts of carboxylic acids, alkali metal salts of sulfonic acids, polyalkylene oxide (PEO or PPO) chains and cationic substituents (quaternary ammonium salts);

n＞0，

i ranges from 1 to n and,

p is equal to 0, 1 or 2 depending on the valence of X, and if X ═ C, Z is not S-alkyl or S-aryl; when i ═ n, the group R¹ⁱNot S-alkyl or S-aryl, and

a represents a mono-block, di-block or tri-block polymer as defined herein.

In order to obtain a water-soluble amphiphilic copolymer comprising a hydrophilic block and a hydrophobic block, the method comprises forming the first block according to the following steps:

(1) contacting:

at least one ethylenically unsaturated monomer,

a source of at least one free radical, and

at least one compound of formula (I) as described herein;

(2) forming a second block by repeating step 1 using: monomers of different nature, and polymers from step 1 in place of the precursor compounds of formula (I); and

(3) optionally, at least partially hydrolyzing the obtained copolymer.

During step 1, a first block of polymer is synthesized, which is predominantly hydrophilic or hydrophobic (depending on the nature and amount of monomers used). During step 2, other blocks of the polymer are synthesized.

The ethylenically unsaturated monomers may be selected from the group consisting of hydrophilic, hydrophobic and hydrolysable monomers as defined herein in proportions suitable to obtain block copolymers wherein the blocks exhibit the characteristics defined above.

According to this process, if all the successive polymerizations are carried out in the same reactor, it is generally preferred to consume all the monomers used in the subsequent step before the start of the polymerization, and therefore before the introduction of new monomers, of the subsequent step. However, it may happen that the hydrophobic or hydrophilic monomers of the previous step are still present in the reactor during the polymerization of the subsequent block. In this case, these monomers generally make up no more than 5 mol% of all the monomers and they participate in the polymerization by helping to introduce hydrophobic or hydrophilic units into the subsequent block.

Water-soluble amphiphilic copolymers comprising a hydrophilic block and a hydrophobic block can be obtained from a single type of hydrophobic hydrolysable monomer. In this case, step 2 is no longer necessary, but partial hydrolysis of the polymer is crucial.

Using the same method, a copolymer comprising n blocks can be obtained by repeating the preceding steps 1 and 2, but replacing the compound of formula (I) by a copolymer comprising n-1 blocks.

In one embodiment, the copolymer obtained by the above process generally exhibits a polydispersity index of at most 2, typically at most 1.5. It may be desirable to mix with the latex block, the polydispersity of which is controlled. In this case, it is possible to mix a precise proportion of several water-soluble amphiphilic copolymers comprising hydrophilic and hydrophobic blocks, each block having a well-defined molecular weight.

In one embodiment, described herein is a method of making an aqueous coating composition by mixing together at least one latex polymer derived from at least one monomer and a macromolecular CTA as described herein and at least one pigment. Preferably, the latex polymer is in the form of a latex polymer dispersion. The additives discussed above may be added to the latex polymer, the pigment, or a combination thereof in any suitable order to provide these additives in the aqueous coating composition. For paint formulations, the aqueous coating composition preferably has a pH of from 7 to 10. Preferably, the paint exhibits improved block and stain resistance. In one embodiment, the coating composition may be optionally thickened to about 85-125 KU. In another embodiment, the coating composition may be thickened to greater than 85 KU. In yet another embodiment, the coating composition may be thickened to about 90-120 KU.

Physical properties that may be considered in formulating latexes and latex paints/coatings include, but are not limited to, viscosity versus shear rate, ease of application to a surface, spreadability, and shear thinning.

When a hydrolyzable hydrophobic monomer is used, hydrolysis may be performed using a base or an acid. The base may be selected from alkali metal or alkaline earth metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide, ammonia and amines, such as triethylamine. The acid may be selected from sulfuric acid, hydrochloric acid and p-toluenesulfonic acid. It is also possible to use cation-or anion-type ion exchange resins or ion exchange membranes. The hydrolysis is generally carried out at a temperature between 5 ℃ and 100 ℃, preferably between 15 ℃ and 90 ℃. Preferably, after hydrolysis, the block copolymer is washed, for example by dialysis with water or using a solvent such as an alcohol. It can also be precipitated by lowering the pH to below 4.5.

The hydrolysis may be carried out on a mono-block polymer, which will subsequently be associated with other blocks, or on the final block polymer.

The latexes of the invention comprise, in dispersion, a water-insoluble polymer obtained from a monomer comprising ethylenic unsaturation. All monomers mentioned in the context of the definition of water-soluble amphiphilic copolymer can be used as monomers comprising ethylenic unsaturation involved in the latex production. Accordingly, reference may be made to this section of the specification to select useful monomers containing ethylenic unsaturation.

Monomers typically used in emulsion polymerization to make latexes for latex painting include, but are not limited to, monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and blends thereof, acrylic acid, methacrylic acid, styrene, vinyl toluene, vinyl acetate, vinyl esters of higher carboxylic acids than acetic acid (e.g., vinyl versatate), acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, and the like, and mixtures thereof. This is further discussed in the section entitled "latex monomers" below.

In one embodiment, the latex monomers fed to the reactor to prepare the polymeric latex binder preferably include at least one acrylic monomer selected from the group consisting of: acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters. In addition, these monomers may include styrene, vinyl acetate, or ethylene. These monomers may also include one or more monomers selected from the group consisting of: styrene, (alpha) -methylstyrene, vinyl chloride, acrylonitrile, methylAcrylonitrile, ureido methacrylate, vinyl acetate, vinyl esters of branched tertiary monocarboxylic acids (e.g., the vinyl esters commercially available under the trademark VEOVA from Shell Chemical Company or sold as EXXAR new vinyl esters by ExxonMobil Chemical Company), itaconic acid, crotonic acid, maleic acid, fumaric acid, and ethylene. And may also include C₄-C₈Conjugated dienes such as 1, 3-butadiene, isoprene or chloroprene. Monomers commonly used in the manufacture of acrylic paint coatings are butyl acrylate, methyl methacrylate, ethyl acrylate and the like. Preferably, the monomers include one or more monomers selected from the group consisting of: n-butyl acrylate, methyl methacrylate, styrene, and 2-ethylhexyl acrylate.

The latex polymer is typically selected from the group consisting of: pure acrylic (including acrylic acid, methacrylic acid, acrylate esters, and/or methacrylate esters as the main monomers); styrene acrylics (including styrene and acrylic acid, methacrylic acid, acrylates, and/or methacrylates, as the primary monomers); vinyl acrylics (including vinyl acetate and acrylic, methacrylic, acrylate, and/or methacrylate esters as primary monomers); and acrylated ethylene vinyl acetate copolymers (including ethylene, vinyl acetate and acrylic acid, methacrylic acid, acrylates, and/or methacrylates as primary monomers).

In one embodiment, the latex polymer comprises:

(a) a first monomer comprising a styrene monomer, an acrylic monomer, a vinyl ester monomer, or a mixture thereof; and

(b) a second monomer comprising a vinyl ester monomer.

For example, the at least one first monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof, and at least one second monomer is a vinyl acetate monomer.

In another embodiment, the latex polymer comprises:

(a) a first monomer selected from the group consisting of: methyl methacrylate monomers, butyl acrylate monomers, and mixtures thereof; and

(b) a second monomer comprising an acrylic monomer.

For example, the at least one acrylic monomer is selected from the group consisting of: acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, and mixtures thereof. Preferably, the at least one first monomer comprises a methyl methacrylate/butyl acrylate ratio of about 40: 60 to about 60: 40, or the at least one first monomer is selected from a methyl methacrylate/butyl acrylate ratio of about 50: 50. In another aspect, the at least one first monomer is selected from butyl acrylate/methyl methacrylate copolymers.

In another embodiment, the latex polymer comprises:

(a) at least one first monomer selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof; and

(b) a second monomer selected from the group consisting of: styrene monomers, acrylic monomers, vinyl ester monomers, and mixtures thereof.

Preferably, the at least one first monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof. In one aspect, the at least one second monomer is selected from the group consisting of: styrene, acrylic acid, vinyl ester monomers and mixtures thereof. In another aspect, the styrene or acrylic monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof. In one aspect, the vinyl ester monomer is selected from the group consisting of: styrene, butyl acrylate, methacrylic acid, vinyl acetate, and mixtures thereof. In another aspect, the acrylic monomer is selected from the group consisting of: acrylic acid, acrylic acid esters, methacrylic acid, and methacrylic acid esters.

In typical acrylic paint compositions, the polymer is composed of one or more esters of acrylic or methacrylic acid, typically of, for exampleHigh T of about 50/50 by weight_gA mixture of monomers (e.g., methyl methacrylate) and low Tg monomers (e.g., butyl acrylate) along with a small proportion (e.g., about 0.5% to about 2% by weight) of acrylic or methacrylic acid. Vinyl-acrylic paints generally comprise vinyl acetate and butyl acrylate and/or 2-ethylhexyl acrylate and/or vinyl versatate. In vinyl-acrylic paint compositions, at least 50% of the polymer formed is composed of vinyl acetate, the remainder being esters selected from acrylic or methacrylic acid. Styrene/acrylic polymers are typically similar to acrylic polymers, with styrene replacing all or part of its methacrylate monomers.

The latex polymer dispersion preferably comprises from about 30% to about 75% solids and an average latex particle size of from about 70nm to about 650 nm. The latex polymer is preferably present in the aqueous coating composition in an amount of from about 5% to about 60% by weight, and more preferably from about 8% to about 40% by weight (i.e., weight percent of dry latex polymer based on the total weight of the coating composition).

Aqueous coating compositions are stable fluids that can be applied to a wide variety of materials, such as, for example, paper, wood, concrete, metal, glass, ceramic, plastic, gypsum, and roofing substrates such as asphalt coatings, roofing felts, foamed polyurethane insulation; or to a previously painted, primed, abraded or weathered substrate. The aqueous coating compositions of the present invention can be applied to these materials by a variety of techniques well known in the art, such as, for example, brushing, rolling, mopping, air-assisted or airless spraying, electrostatic spraying, and the like.

Liquid carrier

In one embodiment, the compositions of the present invention (e.g., paints or stains) comprise a selected polymer and a liquid carrier.

In one embodiment, the liquid carrier is an aqueous carrier comprising water, and the treatment solution is in the form of a solution, emulsion, or dispersion of the materials and additives. In one embodiment, the liquid carrier comprises water and a water-miscible organic liquid. Suitable water-miscible organic liquids include saturated or unsaturated mono-and polyhydric alcohols, such as, for example, methanol, ethanol, isopropanol, cetyl alcohol, benzyl alcohol, oleyl alcohol, 2-butoxyethanol and ethylene glycol; and alkyl ether glycols such as, for example, ethylene glycol monoethyl ether, propylene glycol monoethyl ether and diethylene glycol monomethyl ether.

As used herein, the terms "aqueous medium" and "aqueous medium" are used herein to refer to any liquid medium in which water is the major component. Thus, the term includes water per se as well as aqueous solutions and dispersions.

In one embodiment, the latex polymer composition is in the form of an aqueous polymer dispersion, typically having a solids content of up to about 60 wt%, and more typically from about 20 wt% to about 50 wt%, based on the total weight of the polymer dispersion. In a preferred embodiment, the composition has a high solids content while having a low viscosity. For example, according to the process, the resulting latex polymer composition has a viscosity of less than 4000cps, preferably less than 2000cps, wherein the viscosity is measured using a boehler fly model LVT viscometer at 30rpm and spindle 3. In another aspect, the latex polymer composition has a solids content of at least 40% and a viscosity of less than 4000cps, less than 3000cps, less than 2000cps, less than 1500cps, or less than 1000cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3. In another aspect, the latex polymer composition has a solids content of at least 50% and a viscosity of less than 4000cps, less than 3000cps, less than 2000cps, less than 1500cps, or less than 1000cps, wherein the viscosity is measured using a bohler fly model LVT viscometer at 30rpm and spindle 3.

Experiment of

Example 1

Deionized water (340g) and a macromolecular CTA, PAA-Xa (polyacrylic xanthate, 40.14% solids) (11.68g) [ 1.5% based on total monomers ] were added under a slow continuous nitrogen purge to a suitable reactor equipped with stirring, heating and cooling means for emulsion polymerization. The pH of the CTA solution was adjusted to pH 6 to 6.2 with ammonia (29%) (a total of 3.05g ammonia was used). The temperature of the reactor was raised to a constant temperature of 68 ℃ with continuous stirring. A monomer mixture (15.625g) [ 5.0% of the total 312.5g of monomers prepared by mixing vinyl acetate (250g), butyl acrylate (62.5g) in a VA/BA ratio of 80/20 ] was then added to the reactor.

After one minute, a solution of ammonium persulfate [ one third of the total solution of ammonium persulfate (0.957g) in deionized water (30g) ] was added. The seeds were kept at 68 ℃ for 60 minutes. No observable color change (bluish); however, a slight exotherm of 1 ℃ to 2 ℃ was significant. A small sample was taken to check particle size. The continuous addition of the remaining monomer mixture (296.875g) and initiator ammonium persulfate solution was then set to completion within 3 hours. A small sample was taken to check for solids.

The reactor was held at 68 ℃ for another hour. At this point the solids content was checked and if the reaction was complete, the reactor was cooled to below 40 ℃ and the resulting latex was filtered through a 136 μm polyester filter.

The resulting polymer dispersion had a solids content of 44.9%, a viscosity of 2344cps, and an average particle size of 147.1 d.nm.

Example 2

After one minute, a solution of ammonium persulfate [ one-half of the total solution of ammonium persulfate (1.29g) in deionized water (30g) ] was added. The seeds were kept at 70 ℃ for 10 minutes, then the temperature was increased to 83 ℃ and kept at 83 ℃ for 50 minutes. A small sample was taken to check particle size. After which the temperature was lowered to 70 ℃. The continuous addition of the monomer mixture of vinyl acetate (239.4g) and butyl acrylate (59.85g) and initiator ammonium persulfate solution was then set to completion within 3 hours. A small sample was taken to check for solids.

The reactor was held at 70 ℃ for another hour. At this point the solids content was checked and if the reaction was complete, the reactor was cooled to below 40 ℃ and the resulting latex was filtered through a 136 μm polyester filter.

The resulting polymer dispersion had a solids content of 45.15%, a viscosity of 400cps, and an average particle size of 175.9 d.nm.

Example 3

Deionized water (352g) and macromolecular CTA, PAA-Xa (polyacrylic xanthate, 40.14% solids) (11.77g) [ 1.5% based on total monomers ] were added to a suitable reactor equipped with stirring, heating and cooling means for emulsion polymerization under a slow continuous nitrogen purge. The pH of the CTA solution was adjusted to pH 6 to 6.2 with ammonia (29%) (a total of 3.05g ammonia was used). The temperature of the reactor was raised to a constant temperature of 70 ℃ with continuous stirring. The monomer butyl acrylate (15.76g) [ 5.0% of total monomer ] was then added to the reactor. After one minute, a solution of ammonium persulfate [ one-half of the total solution of ammonium persulfate (1.29g) in deionized water (30g) ] was added. The seeds were kept at 70 ℃ for 10 minutes, then the temperature was increased to 83 ℃ and kept at 83 ℃ for 50 minutes. A small sample was taken to check particle size. After which the temperature was lowered to 70 ℃. The continuous addition of the monomer mixture of vinyl acetate (239.4g) and butyl acrylate (59.85g) and initiator ammonium persulfate solution was then set to completion within 3 hours. A small sample was taken to check for solids.

The resulting polymer dispersion had a solids content of 44.55%, a viscosity of 152cps, and an average particle size of 180 d.nm.

Example 4

Deionized water (352g) and macromolecular CTA, PAA-Xa (polyacrylic xanthate, 40.14% solids) (11.77g) [ 1.5% based on total monomers ] were added to a suitable reactor equipped with stirring, heating and cooling means for emulsion polymerization under a slow continuous nitrogen purge. The pH of the CTA solution was adjusted to pH 6 to 6.2 with ammonia (29%) (a total of 3.05g ammonia was used). The temperature of the reactor was raised to a constant temperature of 70 ℃ with continuous stirring. A monomer mixture of methyl methacrylate (7.88g) and butyl acrylate (7.88g) [ 5.0% of total monomers ] was then added to the reactor. After one minute, a solution of ammonium persulfate [ one-half of the total solution of ammonium persulfate (1.29g) in deionized water (30g) ] was added. The seeds were kept at 70 ℃ for 10 minutes, then the temperature was increased to 83 ℃ and kept at 83 ℃ for 50 minutes. A small sample was taken to check particle size. After which the temperature was lowered to 70 ℃. The continuous addition of the monomer mixture of vinyl acetate (239.4g) and butyl acrylate (59.85g) and initiator ammonium persulfate solution was then set to completion within 3 hours. A small sample was taken to check for solids.

The resulting polymer dispersion had a solids content of 45.45%, a viscosity of 223cps, and an average particle size of 159.4 d.nm.

Examples 5a to 5h

The latexes of examples 5a-5h were prepared by following the same procedure described above, and the characteristics of these latexes are listed in table 1.

Comparative example 1

Deionized water and macromolecular CTApAA-Xa (polyacrylic acid xanthate, 40.37% solids) [ 1.1% based on total monomers ] were mixed under high speed stirring and neutralized to a pH of 6.20 using ammonium hydroxide solution (20% solution). The mixture was added to a suitable reactor equipped with stirring, heating and cooling means, and a slow continuous nitrogen purge for emulsion polymerization. With continuous stirring, the temperature of the reactor was raised and a monomer mixture [ monomers prepared by mixing vinyl acetate and butyl acrylate ] was added to the reactor. Once the temperature of the reactor has stabilized, a solution of ammonium persulfate is added to the reactor. A blue coloration was observed within five minutes.

The seeds were kept at constant temperature for 30 minutes. A small sample was taken to check particle size. The remaining monomer along with the macromolecular CTA feed [ 1.4% of the total monomer prepared by mixing pAA-Xa (40.37% solids) and deionized water was fed continuously over 3 hours with ammonium hydroxide set to completion over 1 hour 30 minutes.

The resulting polymer dispersion had a solids content of 42.57%, a viscosity of 6700cps, an average particle size of 159.3d.nm and a pH of 5.62.

Comparative example 2

Deionized water (295.2g) and macromolecular CTAPAM-PAA-XA (copolymer, 34.20% solids) (6.0g) [ 1.00% based on total monomers ] were mixed with high speed stirring and neutralized to a pH of 6.09 using ammonium hydroxide solution (20% solution). The mixture was added to a suitable reactor equipped with stirring, heating and cooling means, and a slow continuous nitrogen purge for emulsion polymerization. The temperature of the reactor was raised to 68 ℃ with continuous stirring. A monomer mixture (13.0g) [ 6.5% of the total 200g of monomers prepared by mixing vinyl acetate (160.0) and butyl acrylate (40g) ] was added to the reactor at 68 ℃. Once the temperature of the reactor had stabilized at 68 ℃, a solution of ammonium persulfate [ 0.08% based on total monomers prepared by dissolving ammonium persulfate (0.18g) in deionized water (2.23g) ] was added to the reactor. A blue coloration was observed within five minutes.

The seeds were kept at 68 ℃ for 40 minutes. A small sample was taken to check particle size. The remaining monomer (187.0g) was fed continuously over 3 hours and 40 minutes.

When the monomer addition was complete, a small sample of the aqueous polymer dispersion was obtained to calculate the solids content. If the solids content has reached the theoretical solids, the reaction is cooled to about 40 ℃ and the resulting latex is filtered through a 136 μm polyester filter. If the solids content does not reach the theoretical solids, the aqueous polymer dispersion is reacted further until the theoretical solids are reached.

For this particular comparative example, the latex polymer dispersion was further heated at a temperature of 68 ℃ for one hour before it was cooled to 40 ℃ and the resulting latex was filtered using a 136 μm polyester filter.

The resulting polymer dispersion had a solids content of 39.97%, a viscosity of 3340cps, an average particle size of 140.2d.nm and a pH of 5.16.

Comparative example 3

Deionized water (210.0g) was added to a suitable reactor equipped with stirring, heating and cooling devices for emulsion polymerization under a slow continuous nitrogen purge. The temperature of the reactor was raised to 70.0 ℃ with continuous stirring. Monomer pre-emulsion (11.56g) [ 2.5% of total 462.5g monomer pre-emulsion prepared by mixing deionized water (110.0g), sodium trideceth sulfate (16.45g) (1.5% based on total monomers), Abex 2535(6.58g) (1.0% based on total monomers), sodium bicarbonate (0.49g), vinyl acetate (259.91g), butyl acrylate (65.8g), and acrylic acid (3.29g) ] was added to the reactor at 70.0 deg.C (the pre-emulsion was stable prior to addition), followed by ammonium persulfate solution (7.2g) [ 20% of total ammonium persulfate (1.0g) dissolved in deionized water (35.0g) ].

The seeds were kept for 15 minutes. A small sample was taken to check particle size. The continuous addition of the remaining monomer pre-emulsion (450.9g) and the remaining initiator solution (28.8g) was set to be complete within 3 hours. The latex was cooled after the solid conversion had reached 100%. The resulting latex was filtered using a 150 μm polyester filter.

The resulting polymer dispersion had a solids content of 47.25%, a viscosity of 105cps, an average particle size of 185.2d.nm and a pH of 5.3.

TABLE 1 latex characterization

The latex characteristics in table 1 clearly show that the latex prepared by this novel and unique process has much lower viscosity compared to comparative examples 1 and 2. As shown in examples 5f and 5g, this unique process therefore allows the preparation of latexes with high solids while still maintaining a relatively low viscosity.

Example 6

Paint formulation:

latex samples prepared from examples 1 to 4 and comparative example 3 were made into architectural paint. The paint formulations are given in table 2 below.

TABLE 2 paint formulation 72 PVC

72 PVC	Example 1	Example 2	Example 3	Example 4	Comparative example 3
						Raw materials
Pigment grinding
						Water (W)	270.0	270.0	270.0	270.0	270.0
Natrosol Plus 330	2.0	2.0	2.0	2.0	2.0
						AMP-95	1.0	1.0	1.0	1.0	1.0
Rhodoline 226/35	8.0	8.0	8.0	8.0	8.0
						Rhodoline WA200	3.0	3.0	3.0	3.0	3.0
Rhodoline 688	2.0	2.0	2.0	2.0	2.0
						Tiona 595	100.0	100.0	100.0	100.0	100.0
Minex 4	125.0	125.0	125.0	125.0	125.0
						CaCO3#10 white	125.0	125.0	125.0	125.0	125.0

72 PVC	Example 1	Example 2	Example 3	Example 4	Comparative example 3
						Optiwhite MX	110.0	110.0	110.0	110.0	110.0
Diafil 525	25.0	25.0	25.0	25.0	25.0
						Dilution control
Water (W)	122.0	123.0	120.5	123.5	134.0
						Polymer and method of making same	180.4	178.9	181.8	178.2	167.6
Texanol	6.0	6.0	6.0	6.0	6.0
						Rhodoline 4188	0.0	0.0	0.0	0.0	0.0
Rhodoline 688	22..0	2.0	2.0	2.0	2.0
						AMP-95	1.0	1.0	1.0	1.0	1.0
Acrysol TT-935	6.1	7.5	8.9	7.4	11.1
						Water (W)	64.1	62.4	61.3	62.8	58.9
Total of	1152.6	1151.9	1152.6	1151.9	1151.6

TABLE 3 paint formulation 50 PVC

TABLE 4.72 Dry paint Performance characteristics of PVC paints

72 PVC	Example 1	Example 2	Example 3	Example 4	Comparative example 3
						Glossiness 60 degree	2.2	2.2	2.2	2.2	2.1
Opacity	97.21	97.47	97.31	97.7	97.24
						Adhesion (Room temperature)	10	10	10	10	10
Adhesion (baking oven)	10	10	10	10	10
						Scrub, (Brush, no pad, non-abrasive media)
First cut	800	800	183	321	53
						50% cut	1280	1200	400	427	118
Adhesion, CRS, 1 day, dry/wet	5B/5B	5B/5B	5B/5B	5B/5B	4B/1B
						Adhesion, CRS, 7 days, dry/wet	5B/5B	5B/5B	5B/5B	5B/5B	5B/1B

Table 5: dry paint performance characteristics of 50 PVC paints

50PVC	Example 1	Example 2	Example 3	Example 4	Comparative example 3
						Glossiness 60 degree	2.6	2.9	2.6	2.9	2.7
Opacity	96.67	96.27	96.61	96.5	96.56
						Adhesion (Room temperature)	10	10	10	10	10
Adhesion (baking oven)	10	10	10	10	10
						Scrubbing, first scoring	2058	1911	Run out of paint	2225	377
Scrub, 50% cut	2509	2421	Run out of paint	2591	468
						Adhesion, CRS, 1 day, dry/wet	5B/5B	5B/5B	5B/5B	5B/5B	4B/0B
Adhesion, CRS, 7 days, dry/wet	5B/5B	5B/5B	5B/5B	5B/5B	4B/0B

This clearly shows that the PISA latex prepared by this innovative process has significantly improved scrub resistance and adhesion, especially wet adhesion on metal substrates, compared to traditional surfactant based latexes.

It should be apparent that embodiments and equivalents other than those explicitly discussed above are also within the spirit and scope of the invention. Accordingly, the invention is not limited by the foregoing description, but is defined by the following claims.

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