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

• US 9,657,134 B2
• Filed: 12/12/2012
• Issued: 05/23/2017
• 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, Hunia, Robert M, Harris, Caroline S, Frain, Veronica L
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US13/712,110
• Publication Number:
  US 20140023866A1
• Time in Patent Office: 1,623 Days
• Field of Search: 524589, 524590, 528 44, 528 65, 528 85
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2605/18 Aircraft
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• 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 18/305 creating amino end groups
• 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 18/381 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 18/44 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 18/724 Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
• CPC Class Codes: C08G 18/758 containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 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 64/42 : Chemical after-treatment
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31554 : Next to second layer of polyamidoester
• CPC Class Codes: Y10T 428/31591 : Next to cellulosic
• CPC Class Codes: Y10T 428/31601 : Quartz or glass
• CPC Class Codes: Y10T 428/31605 : Next to free metal
• CPC Class Codes: Y10T 442/674 : Nonwoven fabric with a preformed polymeric film or sheet

Abstract

The present invention provides polyurethanes including a reaction product of components including: (a) about 1 equivalent of at least one polyisocyanate; (b) about 0.05 to about 1 equivalents of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; (c) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol; and (d) about 0.1 to about 0.9 equivalents of at least one polyol different from the branched polyol and having 2 to 18 carbon atoms, wherein the reaction product components are essentially free of polyether polyol and the reaction components are maintained at a temperature of at least about 100° C. for at least about 10 minutes; compositions, coatings and articles made therefrom and methods of making the same.

Claims

1. The polyurethane 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 0.3 to about 0.4 equivalents of cyclohexane dimethanol; and

(b) about 0.1 to about 0.3 equivalents of trimethylolpropane, based upon the about 1 equivalent of at least one polyisocyanate (i);

(c) about 0.4 to about 0.5 equivalents of cyclohexane dimethanol, based upon the about 1 equivalent of at least one polyisocyanate (i); and

(d) about 0.01 to about 0.3 equivalents of at least one polycarbonate diol, based upon the about 1 equivalent of at least one polyisocyanate (i),

wherein the reaction components comprise less than about 5 weight percent of polyether polyol;

wherein the prepolymer (a), the trimethylolpropane (b), the cyclohexane dimethanol (c), and the polycarbonate diol (d) 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, degassed, and reacted at a temperature of at least about 110°

C. for at least about 6 hours; and

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.

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 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 polyurethane according to claim 1, wherein the polyisocyanate is dicyclohexylmethane diisocyanate.

5. The polyurethane according to claim 1, wherein the polycarbonate diol is polyhexylene carbonate diol.

6. The polyurethane according to claim 1, wherein the reaction components comprise less than about 0.1 equivalents of polyether polyol.

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

8. The polyurethane according to claim 1, wherein the reaction 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.

9. The polyurethane 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.

10. The polyurethane according to claim 1, wherein, after mixing, reaction components are maintained at a temperature of at least about 100°

C. for at least about 20 minutes prior to curing.