Polyurethanes and graft mixed polymers based on polyurethane and their use for producing coating materials, adhesives and sealing masses

• US 6,632,915 B1
• Filed: 03/20/2002
• Issued: 10/14/2003
• Est. Priority Date: 10/06/1999
• Status: Expired due to Term

• Current Assignee: BASF Coatings AG (BASF SE)
• Original Assignee: BASF Coatings AG (BASF SE)
• Inventors: Wegner, Egon, Schwarte, Stephan, Angermüller, Harald
• Primary Examiner(s): GORR, RACHEL F
• Application Number:
  US10/088,711
• Time in Patent Office: 573 Days
• Field of Search: 528/75, 526/301, 526/302, 525/63, 525/902, 523/201, 523/501
• US Class Current: 528/75
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 283/006 on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08F 290/06 Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08G 18/0823 containing carboxylate salt groups or groups forming them
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3831 containing urethane groups
• CPC Class Codes: C08G 18/4233 derived from polymerised higher fatty acids or alcohols
• CPC Class Codes: C08G 18/4291 prepared from polyester forming components containing monoepoxy compounds C08G18/4266 takes precedence
• CPC Class Codes: C08G 18/6659 with compounds of group C08G18/34
• CPC Class Codes: C08G 18/71 Monoisocyanates or monoisothiocyanates
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 51/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• CPC Class Codes: C09D 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09D 151/08 grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 175/14 Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: Y10S 525/902 Core-shell

Abstract

A polyurethane comprising lateral and/or terminal ethenylarylene groups produced by reacting a polyurethane prepolymer containing free isocyanate groups with an adduct obtained by reacting an ethenylarylene monoisocyanate with a polyol, polyamine, and/or a compound containing hydroxyl and amino groups in a molar ratio of 1:1. Also, a graft copolymer comprising a hydrophobic core comprising at least one monomer and a hydrophilic shell comprising the polyurethane, or a hydrophobic core comprising the polyurethane and a hydrophilic shell that comprises at least one monomer. Also, a graft copolymer comprising a hydrophobic core comprising at least one monomer and a hydrophilic shell comprising a polyurethane produced by dispersing at least one hydrophilic olefinic unsaturated polyurethane comprising lateral, and optionally terminal, ethenylarylene groups in an aqueous medium and copolymerizing at least one hydrophobic monomer in the polyurethane in emulsion.

Claims

1. A polyurethane comprising hydrophilic functional groups and at least one ethenylarylene group, wherein the ethenylarylene group is at least one of pendant and terminal, and comprising a reaction product of

(1) at least one polyurethane prepolymer containing at least one free isocyanate group, and

(2) at least one adduct comprising a reaction product of, in a molar ratio of 1:

1,

(2.1) at least one ethenylarylene monoisocyanate, and

(2.2) at least one of a polyol, a polyamine, and a compound containing at least one hydroxyl group and at least one amino group.

2. The polyurethane of claim 1, wherein the ethenylarylene monoisocyanate has the general formula I:

3. The polyurethane of claim 2, wherein the arylene radical A is one of phenylene, naphthylene, or biphenylylene, and is one of substituted or unsubstiuted.

4. The polyurethane of claim 2, wherein the arylene radical A is at least one of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene.

5. The polyurethane of claim 2, wherein R is a hydrogen atom.

6. The polyurethane of claim 2, wherein the divalent organic radical X is a branched or unbranched C₁-C₁₀ alkanediyl radical.

9. The polyurethane of claim 1, wherein at least one of the ethenylarylene monoisocyanates is 1-(1-isocyanato-1-methylethyl)-3-(1-methylethenyl)benzene.

30. A process comprising providing the polyurethane of claim 1 in one of a sealing compound, an adhesive compound, and a coating composition.

31. The process of claim 30 further comprising one of

i) forming a seal from the sealing compound on a substrate,

ii) forming an adhesive film from the adhesive compound on a substrate, and

iii) forming a coating from the coating composition on a substrate.

32. An article produced by the process of claim 31, wherein the article is one of a seal, an adhesive film, and a coating.

33. The substrate produced by the process of claim 31.

34. The substrate of claim 33, wherein the substrate is one of a molding, a foil, a fiber, a motor vehicle body, an industrial component, an electrical component, a coil, a package, and furniture.

45. A composition comprising the polyurethane of claim 1, wherein the composition is one of a scaling compound, an adhesive compound, and a coating composition.

7. The polyurethane of clam 6, wherein the divalent organic radical X is a branched or unbranched C₃-C₆ alkanediyl radical.

8. The polyurethane of claim 7, wherein the divalent organic radical X is —

C(CH₃)₂—

.

10. A graft copolymer comprising a hydrophobic core and a hydrophilic shell, wherein one of

i) the hydrophobic core comprises a (co)polymerization product of at least one olefinically unsaturated monomer and the hydrophilic shell comprises at least one polyurathane, or

ii) the hydrophobic core comprises at least one polyurethane, and the hydrophilic shell comprises a (co)polymerization product of at least one olefinically unsaturated monomer

 

wherein the graft copolymer is prepared by a process comprising

1) dispersing at least one polyurethane in an aqueous medium, and

2) subjecting at least one olefinically unsaturated monomer to radical (co)polymerization in emulsion in the presence of the at least one polyurethane,

 

wherein the at least one polyurethane comprises at least one ethenylarylene group, wherein the ethenylarylene group is at least one of pendant and terminal, and comprises a reaction product of

(1) at least one polyurethane prepolymer containing at least one free isocyanate group, and

(2) at least one adduct comprising a reaction product of, in a molar ratio of 1;

1,

(2.1) at least one ethenylarylene monoisocyanate, and

(2.2) at least one of a polyol, a polyamine, and a compound containing at least one hydroxyl group and at least one amino group.

11. The graft copolymer of claim, 10 wherein the ethenylarylene group has the general formula II:

12. The graft copolymer of claim 11, wherein the arylene radical A is one of phenylene, naphthylene, or biphenylylene, and is one of substituted or unsubstituted.

13. The graft copolymer of claim 11, wherein R is a hydrogen atom.

14. The graft copolymer of claim 11, wherein the arylene radical A is at least one of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene.

15. The graft copolymer of claim 10, wherein the ethenyarylene group is joined to the polyurethane main chain by way of a divalent or trivalent linking radical III containing at least one of a urethane group and a urea group.

16. The graft copolymer of claim 15, wherein the linking radical III comprises at least one group of general formula IIIa to IIIc

17. The graft copolymer of claim 10, wherein the hydrophilic shell contains at least one of a carboxylic acid group and a carboxylate group.

18. The graft copolymer of claim 17, wherein the ratio of acid number of the shell to acid number of the core is greater than 1.

35. A process comprising providing the graft copolymer of claim 10 in one of a sealing compound, an adhesive compound, and a coating composition.

36. The process of claim 35 further comprising one of

i) forming a seal from the sealing compound on a substrate,

ii) forming an adhesive film from the adhesive compound on a substrate, and

iii) forming a coating from the coating composition on a substrate.

37. An article produced by the process of claim 36, wherein the article is one of a seal, an adhesive film, and a coating.

38. The substrate produced by the process of claim 36.

39. The substrate of claim 38, wherein the substrate is one of a molding, a foil, a fiber, a motor vehicle body, an industrial component, an electrical component, a coil, a package, and furniture.

46. A composition comprising the graft copolymer of claim 10, wherein the composition is one of a sealing compound, an adhesive compound, and a coating composition.

19. A graft copolymer comprising

A) a hydrophobic core comprising a (co)polymerization product of at least one olefinically unsaturated monomer, and

B) a hydrophilic shell comprising at least one polyurethane,

 

wherein the graft copolymer is prepared by a process comprising

1) dispersing at least one hydrophilic olefinically unsaturated polyurethane in an aqueous medium, wherein the hydrophilic olefinically unsaturated polyurethane contains at least one pendant ethenylarylene group and optionally at least one terminal ethenylarylene group, and

2) subjecting at least one hydrophobic olefinically unsaturated monomer to radical (co)polymerization in emulsion in the presence of the polyurethane.

20. The graft copolymer of claim 19, wherein the hydrophilic polyurethane comprises a reaction product of

a) at least one oligomer or polymer containing

at least one hydrophilic functional group and one of

2.1) at least two hydroxyl groups,

2.2) at least two amino groups, or

2.3) at least one hydroxyl group and at least one amino group; and

b) at least one ethylenearylene monoisocyanate.

21. The graft copolymer of claim 20, wherein the at least one oligomer comprises at least one of a polyester and a polyurethane or the at least one polymer comprises at least one of a polyester and a polyurethane.

22. The graft copolymer of claim 19, wherein the ethenylarylene group has the general formula II:

23. The graft copolymer of claim 22, wherein the arylene radical A is one of phenylene, naphthylene, or biphenylylene, and is one of substituted or unsubstituted.

24. The graft copolymer of claim 22, wherein R is a hydrogen atom.

25. The graft copolymer of claim 22, wherein the arylene radical A is at least one of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene.

26. The graft copolymer of claim 19, wherein the ethenylarlene group is joined to the polyurethane main chain by way of a divalent or trivalent linking radical III containing at least one of a urethane group and a urea group.

27. The graft copolymer of claim 26, wherein the linking radical III comprises at least one group of general formula IIIa to IIIc

28. The graft copolymer of claim 19, wherein the hydrophilic shell contains at least one of a carboxylic acid group and a carboxylate group.

29. The graft copolymer of claim 28, wherein the ratio of acid number of the shell to acid number of the core is greater than 1.

40. A process comprising providing the graft copolymer of claim 19, in one of a sealing compound, an adhesive compound, and a coating composition.

41. The process of claim 40 further comprising one of

i) forming a seal from the sealing compound on a substrate,

ii) forming an adhesive film from the adhesive compound on a substrate, and

iii) forming a coating from the coating composition on a substrate.

42. An article produced by the process of claim 41, wherein the article is one of a seal, an adhesive film, and a coating.

43. The substrate produced by the process of claim 41.

44. The substrate of claim 43, wherein the substrate is one of a molding, a foil, a fiber, a motor vehicle body, an industrial component, an electrical component, a coil, a package, and furniture.

47. A composition comprising the graft copolymer of claim 19, wherein the composition is one of a sealing compound, an adhesive compound, and a coating composition.