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

• US 9,296,920 B2
• Filed: 12/03/2012
• Issued: 03/29/2016
• 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., Harris, Caroline S., Hunia, Robert M., Frain, Veronica L.
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US13/692,478
• Publication Number:
  US 20130160920A1
• Time in Patent Office: 1,212 Days
• Field of Search: 524/589, 524/590, 528/44, 528/59, 528/60, 528/65, 528/67, 528/85
• US Class Current: 1/1
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2605/18 Aircraft blades, propellers B32B2603/00
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C08G 18/00 Polymeric products of isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/08 Processes
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/28 characterised by the compounds used containing active hydrogen
• CPC Class Codes: C08G 18/30 Low-molecular-weight compounds C08G18/2805 takes precedence
• CPC Class Codes: C08G 18/305 creating amino end groups
• CPC Class Codes: C08G 18/3203 Polyhydroxy compounds
• 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 18/3284 containing four hydroxy groups
• CPC Class Codes: C08G 18/341 Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
• CPC Class Codes: C08G 18/381 having bromine atoms
• CPC Class Codes: C08G 18/3868 the sulfur atom belonging to a sulfide group
• CPC Class Codes: C08G 18/3872 the sulfur atom belonging to a sulfoxide or sulfone group
• CPC Class Codes: C08G 18/4018 : Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/4277 : Caprolactone and/or substituted caprolactone
• CPC Class Codes: C08G 18/44 : Polycarbonates
• CPC Class Codes: C08G 18/6607 : with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/6644 : having at least three hydroxy groups
• CPC Class Codes: C08G 18/671 : Unsaturated compounds having only one group containing active hydrogen takes precedence on groups C08G18/675 - C08G18/69
• CPC Class Codes: C08G 18/70 : characterised by the isocyanates or isothiocyanates used
• CPC Class Codes: C08G 18/72 : Polyisocyanates or polyisothiocyanates
• CPC Class Codes: C08G 18/724 : Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
• CPC Class Codes: C08G 18/73 : acyclic
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/765 : alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/7657 : containing two or more aromatic rings
• CPC Class Codes: C08G 18/792 : formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/831 : by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides by aldehydes C08G18/84, by peroxides C08G18/86
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: Y10T 156/10 : Methods of surface bonding and/or assembly therefor
• 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
• CPC Class Codes: Y10T 442/183 : Synthetic polymeric fiber
• CPC Class Codes: Y10T 442/20 : Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• CPC Class Codes: Y10T 442/2197 : Nitrogen containing
• CPC Class Codes: Y10T 442/2623 : Ballistic resistant
• CPC Class Codes: Y10T 442/2721 : Nitrogen containing

Abstract

The present invention provides polyurethanes including a reaction product of components including: (a) an isocyanate functional urethane prepolymer comprising a reaction product of components including: (i) about 1 equivalent of at least one polyisocyanate; and (ii) about 0.1 to about 0.5 equivalents of at least one diol having 2 to 18 carbon atoms; and (b) about 0.05 to about 0.9 equivalents of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (c) up to about 0.9 equivalents of at least one polyol different from branched polyol (b) and having 2 to 18 carbon atoms, wherein the reaction product components are essentially free of polyester polyol and polyether polyol; compositions, coatings and articles made therefrom and methods of making the same.

Claims

1. A method of preparing polyurethane from reaction components comprising:

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

about 0.2 to about 0.5 equivalents of at least one polyol (a) having 5 to 18 carbon atoms to form an isocyanate functional urethane prepolymer; and

(2) reacting the isocyanate functional urethane prepolymer, about 0.05 to about 1.0 equivalents of at least one polyol (b) having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

up to about 0.9 equivalents of at least one polyol (c) different from polyol (b), and having 5 to 18 carbon atoms,

wherein the reaction product components are essentially free of polyester polyol and polyether polyol; and

wherein the prepolymer (a), polyol (b) and polyol (c) (if present) are each preheated to and maintained at a temperature of about 120°

C. to about 140°

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 into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time is from about 0.1 seconds to about 5 minutes.

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

3. The method according to claim 1, 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, 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 method according to claim 1, wherein the polyol (a) is selected from the group consisting of pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, octadecanediol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′

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

5. The method according to claim 1, wherein polyol (a) is pentanediol.

6. The method according to claim 1, wherein the equivalent ratio of polyisocyanate to polyol (a) ranges from about 1:

0.3 to about 1;

0.4.

7. The method according to claim 1, wherein the equivalent ratio of polyisocyanate to polyol (a) is about 1:

0.35.

8. The method according to claim 1, wherein polyol (b) has three hydroxyl groups.

9. The method according to claim 1, wherein polyol (b) is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitan, alkoxylated derivatives thereof and mixtures thereof.

10. The method according to claim 1, wherein polyol (b) is selected from the group consisting of tetramethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.

11. The method according to claim 1, wherein polyol (b) is trimethylolpropane.

12. The method according to claim 1, wherein polyol (c) is selected from the group consisting of pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, octadecanediol, sorbitol, mannitol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, dihydroxytoluene, 1,4-bis(hydroxyethyl)piperazine, N,N′

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

13. The method according to claim 1, wherein the polyol (c) is pentanediol.

14. The method according to claim 1, wherein the reaction product components comprise less than about 0.1 equivalents of polyester polyol or polyether polyol.

15. The method according to claim 1, wherein the reaction components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent polyether polyol.

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

17. The method according to claim 1, wherein the reaction product components are essentially free of amine curing agent.

18. The method according to claim 1, wherein the polyurethane has a urethane content of about 20 to about 40 weight percent.

19. The method according to claim 1, wherein the polyurethane has a cyclic content of about 10 to about 80 weight percent.

20. The method according to claim 1, wherein the polyurethane has a molecular weight per crosslink of at least about 500 grams per mole.

21. The method according to claim 1, wherein the prepolymer and polyol (a) are heated prior to mixing.

22. The method according to claim 1, wherein the about 1 equivalent of at least one polyisocyanate and about 0.2 to about 0.5 equivalents of at least one polyol (a) having 5 to 18 carbon atoms are pre-reacted to form the isocyanate functional urethane prepolymer prior to reacting the isocyanate functional urethane prepolymer with about 0.05 to about 1.0 equivalents of at least one polyol (b) having 4 to 18 carbon atoms and at least 3 hydroxyl groups;

and up to about 0.9 equivalents of at least one polyol (c) different from polyol (b) and having 5 to 18 carbon atoms.

23. The method according to claim 1, wherein the isocyanate functional urethane prepolymer is degassed prior to reacting the isocyanate functional urethane prepolymer with about 0.05 to about 1.0 equivalents of at least one polyol (b) having 4 to 18 carbon atoms and at least 3 hydroxyl groups;

and up to about 0.9 equivalents of at least one polyol (c) different from polyol (b) and having 5 to 18 carbon atoms.

24. The method according to claim 1, wherein the isocyanate functional urethane prepolymer, about 0.05 to about 1.0 equivalents of at least one polyol (b) having 4 to 18 carbon atoms and at least 3 hydroxyl groups;

and up to about 0.9 equivalents of at least one polyol (c) different from polyol (b) and having 5 to 18 carbon are mixed in a high-speed shear mixing head.

25. The method according to claim 1, wherein the isocyanate functional urethane prepolymer, about 0.05 to about 1.0 equivalents of at least one polyol (b) having 4 to 18 carbon atoms and at least 3 hydroxyl groups, and up to about 0.9 equivalents of at least one polyol (c) different from polyol (b) and having 5 to 18 carbon atoms are mixed in a dynamic pin mixer.

26. The method according to claim 25, wherein the residence time of the reactants in the dynamic pin mixer is about 4 to about 30 seconds.

27. The method according to claim 25, wherein the residence time of the reactants in the dynamic pin mixer is about 4 to about 15 seconds.

28. The method according to claim 25, wherein the residence time of the reactants in the dynamic pin mixer is about 4 to about 8 seconds.

29. The method according to claim 1, wherein, after mixing, the reaction components are maintained at a temperature of 100°

C. for at least about 10 minutes prior to curing.

30. The method according to claim 1, wherein, after mixing, the reaction components are maintained at a temperature of at least about 110°

C. for at least about 10 minutes prior to curing.

31. The method according to claim 1, wherein, after mixing, the reaction components are maintained at a temperature of at least about 120°

C. for at least about 10 minutes prior to curing.

32. The method according to claim 1, wherein, after mixing, the reaction components are maintained at a pressure of about 2 to about 6 mm Hg (about 266.6 to about 800 Pascal (Pa)) for a time period of about 10 minutes to about 24 hours.

33. The method according to claim 1, wherein, after mixing, the reaction components are maintained at a pressure of about 2 to about 6 mm Hg (about 266.6 to about 800 Pascal (Pa)) for a time period of about 10 minutes to about 4 hours.

34. The method according to claim 1, wherein, after mixing, the reaction components are degassed for a period of at least about 3 minutes during which time the pressure is reduced from atmospheric to about 3 millimeters of mercury before curing.

35. The method according to claim 1, wherein, after mixing, the reaction components are cured at a temperature ranging from about 110°

C. to about 140°

C. until there are substantially no isocyanate groups present.

36. The method according to claim 1, wherein, after mixing, the reaction components are cured at a temperature ranging from about 110°

C. to about 140°

C. for at least about 6 hours.

37. The method according to claim 1, wherein, after mixing, the reaction components are cured at a temperature ranging from about 110°

C. to about 140°

C. for at least about 24 hours.

38. The method according to claim 1, further comprising heat treating, pressure casting, or pouring liquid polyurethane into a mold and curing the product to form a molded article.

39. The method according to claim 1, further comprising curing the polyurethane to form a molded article at a temperature of about 200°

C. over a period of from about 0.5 hour to about 72 hours.

40. The method according to claim 1, further comprising curing the polyurethane to form a molded article at a temperature of about 80°

C. to about 150°

C. for a period of from about 5 hours to about 48 hours.

41. The method according to claim 1, further comprising curing the polyurethane to form a molded article at a temperature of about 250°

F. (121°

C.) to about 320°

F. (160°

C.) and cured for about 24 to about 48 hours.

42. The method according to claim 1, further comprising aging the polyurethane for at least about 2 weeks after formation.

43. The method according to claim 1, further comprising aging the polyurethane for at least about 2 months after formation.

44. The method according to claim 1, further comprising aging the polyurethane for at least about 7 months after formation.

45. The method according to claim 1, further comprising forming an assembly from at least one layer of the polyurethane of claim 1;

and 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. The method according to claim 45, further comprising laminating the at least one layer of the polyurethane of claim 1;

and 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.

47. A method of preparing polyurethane from reaction components comprising:

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

about 0.2 to about 0.4 equivalents of pentanediol to form an isocyanate functional urethane prepolymer; and

(2) reacting the isocyanate functional urethane prepolymer, about 0.3 to about 0.7 equivalents of trimethylolpropane; and

up to about 0.4 equivalents of pentanediol,

wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent of polyether polyol; and

wherein the prepolymer of (1), and the trimethylolpropane and pentanediol (if present) of (2) are each preheated to and maintained at a temperature of about 120°

C. to about 140°

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 into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time is from about 0.1 seconds to about 5 minutes.

48. A method of preparing polyurethane from reaction components comprising:

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

about 0.2 to about 0.4 equivalents of pentanediol to form an isocyanate functional urethane prepolymer; and

(2) reacting the isocyanate functional urethane prepolymer, about 0.3 to about 0.6 equivalents of trimethylolpropane; and

about 0.1 to about 0.4 equivalents of pentanediol,

wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent of polyether polyol; and

wherein the prepolymer of (1), and the trimethylolpropane and pentanediol (if present) of (2) are each preheated to and maintained at a temperature of about 120°

C. to about 140°

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 into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time is from about 0.1 seconds to about 5 minutes.

49. A method of preparing polyurethane from reaction components comprising:

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

about 0.2 to about 0.5 equivalents of at least one diol having 5 to 18 carbon atoms to form an isocyanate functional urethane prepolymer; and

(2) reacting the isocyanate functional urethane prepolymer, about 0.05 to about 0.9 equivalents of at least one polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

up to about 0.45 equivalents of at least one diol having 5 to 18 carbon atoms,

wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, less than about 5 weight percent of polycarbonate polyol and less than about 5 weight percent of polyether polyol; and

wherein the prepolymer of (1), and the trimethylolpropane and pentanediol (if present) of (2) are each preheated to and maintained at a temperature of about 120°

C. to about 140°

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 into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time is from about 0.1 seconds to about 5 minutes.