Polyurethanes, articles and coatings prepared therefrom and methods of making the same

• US 9,994,670 B2
• Filed: 07/26/2016
• Issued: 06/12/2018
• Est. Priority Date: 09/01/2004
• Status: Active Grant

• Current Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Original Assignee: PPG Industries Ohio Incorporated (Nouryon BV)
• Inventors: Rukavina, Thomas G
• Primary Examiner(s): Niland, Patrick D
• Application Number:
  US15/219,371
• Publication Number:
  US 20160333133A1
• Time in Patent Office: 686 Days
• CPC Class Codes: B32B 17/10 of synthetic resin
• CPC Class Codes: B32B 17/10614 comprising particles for purposes other than dyeing
• CPC Class Codes: B32B 17/10752 containing polycarbonate
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2250/02 2 layers
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/704 Crystalline
• CPC Class Codes: B32B 2457/20 Displays, e.g. liquid crystal displays, plasma displays
• CPC Class Codes: B32B 2605/00 Vehicles
• CPC Class Codes: B32B 2605/18 Aircraft blades, propellers B32B2603/00
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/365 comprising polycarbonates
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/3212 containing cycloaliphatic groups
• CPC Class Codes: C08G 18/3215 containing aromatic groups or benzoquinone groups
• CPC Class Codes: C08G 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/44 : Polycarbonates
• CPC Class Codes: C08G 18/6611 : having at least three hydroxy groups
• CPC Class Codes: C08G 18/664 : with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/6644 : having at least three hydroxy groups
• CPC Class Codes: C08G 18/724 : Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 64/42 : Chemical after-treatment
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: Y10T 428/24628 : Nonplanar uniform thickness material
• CPC Class Codes: Y10T 428/249921 : Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31591 : Next to cellulosic
• CPC Class Codes: Y10T 428/31598 : Next to silicon-containing [silicone, cement, etc.] layer
• CPC Class Codes: Y10T 428/31601 : Quartz or glass
• CPC Class Codes: Y10T 428/31605 : Next to free metal

Abstract

The present invention provides polyurethanes including a reaction product of components including: (a) at least one isocyanate functional prepolymer including a reaction product of: (1) about 1 equivalent of at least one polyisocyanate; and (2) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol; and (b) about 0.01 to about 1 equivalent of at least one branched polyol having at least 3 hydroxyl groups; compositions, coatings and articles made therefrom and methods of making the same.

Claims

1. A polyurethane comprising a reaction product of components comprising:

(a) at least one isocyanate functional prepolymer comprising a reaction product of;

(1) about 1 equivalent of at least one polyisocyanate; and

(2) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate; and

(b) about 0.01 to about 1 equivalent of at least one polyol having at least 3hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate, wherein the at least one polyol (b) is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolmethane, trimethylolpropane, erythritol, pentaerythritol, and wherein the prepolymer (a) and polyol (b) are each preheated to and maintained at a temperature of at least about 100°

C. for at least about 10 minutes immediately prior to mixing together within a mixing chamber of a dynamic pin mixer, wherein the mixing chamber has a volume of about 62cc to about 250 cc, the total flow rate components in the mixing chamber is about 499 to about 4807 grams per minute and the residence time of the components in the mixing chamber is from about 0.1 seconds to about 15 minutes.

2. The polyurethane according to claim 1, wherein the polyisocyanate is selected from the group consisting of diisocyanates, triisocyanates, dimers, trimers and mixtures thereof.

3. The polyurethane according to claim 2, wherein the polyisocyanate is selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, isophorone diisocyanate, 1,6,11-undecane-triisocyanate, 1,3,6-hexamethylene triisocyanate, bis(isocyanatoethyl)-carbonate, bis(isocyanatoethyl)ether, trimethylhexane diisocyanate, trimethylhexamethylene diisocyanate, 2,2′

-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, lysinediisocyanate methyl ester, 4,4′

-methylene-bis-(cyclohexyl isocyanate), 4,4′

-isopropylidene-bis-(cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate, 4,4′

-dicyclohexylmethane diisocyanate, 3-isocyanato methyl-3,5,5-trimethylcyclohexyl isocyanate, meta-tetramethylxylylene diisocyanate, diphenyl methane diisocyanates, diphenyl isopropylidene diisocyanate, diphenylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, bis(isocyanatomethyl) cyclohexane, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)-2,2-propane, bis(isocyanatocyclohexyl)-1,2-ethane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo [2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo [2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo [2.2.1]-heptane, 2-isocyanato-methyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo [2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo [2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo- [2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo [2.2.1]-heptane, α

,α

′

-xylene diisocyanate, bis(isocyanatoethyl)benzene, α

,α

,α

′

,α

′

-tetramethylxylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl) benzene, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl) phthalate, mesitylene triisocyanate, 2,5-di(isocyanatomethyl)furan, α

,α

′

-xylene diisocyanate, bis(isocyanatoethyl)benzene, α

,α

,α

′

,α

′

-tetramethylxylene diisocyanate, 1,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl) benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl) phthalate, 2,5-di(isocyanatomethyl)furan, diphenylether diisocyanate, bis(isocyanatophenylether)ethyleneglycol, bis(isocyanatophenylether)-1,3-propyleneglycol, benzophenone diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, and dimers, trimers and mixtures thereof.

4. The polyurethane according to claim 3, wherein the polyisocyanate is 4,4′

-methylene-bis-(cyclohexyl isocyanate).

5. The polyurethane according to claim 2, wherein the polyisocyanate is a trimer of a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, and mixtures thereof.

6. The polyurethane according to claim 1, wherein the polycarbonate polyol is prepared from hexanediol and dialkyl carbonate.

7. The polyurethane according to claim 1, wherein the polyol (b) is trimethylolpropane.

8. The polyurethane according to claim 1, wherein the components comprise about 0.4 to about 1 equivalent of the at least one polyol (b) having at least 3 hydroxyl groups.

9. The polyurethane according to claim 1, wherein the components comprise about 0.6 to about 0.7 equivalent of the at least one polyol (b) having at least 3 hydroxyl groups.

10. The polyurethane according to claim 1, wherein the components further comprise about 0.001 to about 0.5 equivalent of at least one polyol (c) different from the polyol (b), based upon the about 1 equivalent of the at least one polyisocyanate.

11. The polyurethane according to claim 1, wherein the components further comprise about 0.01 to about 0.3 equivalent of at least one polyol (c) different from the polyol (b), based upon the about 1 equivalent of the at least one polyisocyanate.

12. The polyurethane according to claim 1, wherein the components further comprise about 0.1 equivalent of at least one polyol (c) different from the polyol (b), based upon the about 1 equivalent of the at least one polyisocyanate.

13. The polyurethane according to claim 10, wherein the polyol (c) is a diol.

14. The polyurethane according to claim 10, wherein the polyol (c) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene bis(2-hydroxyethyl) terephthalate, 1,4-bis(hydroxyethyl)piperazine, N,N′

,bis(2-hydroxyethyl)oxamide and mixtures thereof.

15. The polyurethane according to claim 14, wherein the polyol (c) is pentanediol, butanediol or cyclohexanedimethanol.

16. The polyurethane according to claim 1, wherein the components further comprise one or more polyurethane polyols, acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxy phthalates, dihydroxyethyl hydroquinones and mixtures thereof.

17. The polyurethane according to claim 1, wherein the components are essentially free of polyether polyol.

18. The polyurethane according to claim 1, wherein the components are essentially free of polyester polyol other than the polycarbonate polyol.

19. The polyurethane according to claim 1, wherein the components are essentially free of amine curing agent.

20. The polyurethane according to claim 1, wherein, upon mixing, the components are maintained at a temperature of at least about 100°

C. for at least about 10 minutes prior to degassing, and reacted at a temperature of at least about 110°

C. for at least about 6 hours.

21. The polyurethane according to claim 20, wherein, upon mixing, the components are maintained at a temperature of at least about 110°

C. for at least about 10 minutes prior to degassing, and reacted at a temperature of at least about 120°

C. for at least about 6 hours.

22. The polyurethane according to claim 1, comprising a reaction product of components comprising:

(a) an isocyanate functional urethane prepolymer comprising a reaction product of components comprising;

(i) about 1 equivalent of at least one polyisocyanate; and

(ii) about 0.1 to about 0.4 equivalent of polycarbonate diol based upon the about 1 equivalent of the at least one polyisocyanate;

(b) about 0.5 to about 0.8 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate; and

(c) about 0.1 to about 0.5 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate.

23. The polyurethane according to claim 1, comprising a reaction product of components comprising:

(a) an isocyanate functional urethane prepolymer comprising a reaction product of components comprising;

(i) about 1 equivalent of at least one polyisocyanate; and

(ii) about 0.2 equivalent of polycarbonate diol based upon the about 1 equivalent of the at least one polyisocyanate;

(b) about 0.7 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate; and

(c) about 0.1 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate.

24. An article comprising the polyurethane of claim 1.

25. The article according to claim 24, wherein the article is a molded article.

26. The article according to claim 24, wherein the article is selected from the group consisting of optical articles, optical lenses, photochromic articles, photochromic lenses, windows, transparencies, windshields, sidelights, backlights, aircraft transparencies, ballistic resistant articles, windmill components, glazings, exterior viewing surfaces of liquid crystal displays, cathode ray tubes, films, sheeting, conductive films, microwave absorbing films, low resistance films, blast resistant panels, bullet resistant panels, and radomes.

27. An article comprising the polyurethane of claim 1, wherein the article is an aircraft transparency.

28. The article according to claim 24, wherein the article is a curved article.

29. The article according to claim 24, wherein the article is a flat article.

30. An article comprising at least one layer of the polyurethane of claim 1 and at least one layer of polycarbonate.

31. A laminate comprising:

(a) at least one layer of the polyurethane of claim 1; and

(b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

32. A coating composition comprising the polyurethane of claim 1.

33. A polyurethane comprising a reaction product of components comprising:

(a) about 1 equivalent of at least one polyisocyanate;

(b) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate; and

(c) about 0.01 to about 0.1 equivalent of at least one polyol having at least 3 hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate, wherein the at least one polyol (c) is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolmethane, trimethylolpropane, erythritol, pentaerythritol, and wherein the prepolymer (a), polyol (b) and polyol (c) are each preheated to and maintained at a temperature of at least about 100°

C. for at least about 10 minutes immediately prior to mixing together within a mixing chamber of a dynamic pin mixer, wherein the mixing chamber has a volume of about 62 cc to about 250 cc, the total flow rate components in the mixing chamber is about 499 to about 4807 grams per minute and the residence time of the components in the mixing chamber is from about 0.1 seconds to about 15 minutes.

34. The polyurethane according to claim 33, wherein the components further comprise about 0.001 to about 0.5 equivalent of at least one polyol (d) different from the polycarbonate polyol (b) or the polyol (c), based upon the about 1 equivalent of the at least one polyisocyanate.

35. The polyurethane according to claim 33, wherein the components further comprise one or more polyurethane polyols, acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxy phthalates, dihydroxyethyl hydroquinones and mixtures thereof.

36. The polyurethane according to claim 33, wherein the components further comprise about 0.01 to about 0.5 equivalent of water based upon the about 1 equivalent of the at least one polyisocyanate.

37. The polyurethane according to claim 33, wherein the components are essentially free of polyether polyol.

38. The polyurethane according to claim 33, wherein the components are essentially free of polyester polyol other than the polycarbonate polyol.

39. The polyurethane according to claim 33, wherein the components are essentially free of amine curing agent.

40. An article comprising the polyurethane of claim 33.

41. The article according to claim 40, wherein the article is selected from the group consisting of optical articles, optical lenses, photochromic articles, photochromic lenses, windows, transparencies, windshields, sidelights, backlights, aircraft transparencies, ballistic resistant articles, windmill components, glazings, exterior viewing surfaces of liquid crystal displays, cathode ray tubes, films, sheeting, conductive films, microwave absorbing films, low resistance films, blast resistant panels, bullet resistant panels, and radomes.

42. The article according to claim 40, wherein the article is a curved article.

43. The article according to claim 40, wherein the article is a flat article.

44. An article comprising at least one layer of the polyurethane of claim 33 and at least one layer of polycarbonate.

45. A laminate comprising:

(a) at least one layer of the polyurethane of claim 33; and

(b) at least one layer of a substrate selected from the group consisting of paper, glass, ceramic, wood, masonry, textile, metal or organic polymeric material and combinations thereof.

46. A coating composition comprising the polyurethane of claim 33.