Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom

• US 8,889,815 B2
• Filed: 12/14/2006
• Issued: 11/18/2014
• 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, Lin, Chia-Cheng, Ragunathan, Kaliappa G., Nagpal, Vidhu J.
• Primary Examiner(s): Leonard, Michael L
• Application Number:
  US11/639,057
• Publication Number:
  US 20070173582A1
• Time in Patent Office: 2,896 Days
• Field of Search: 428/423.1, 428/422.8, 528/44, 528/65, 528/72, 528/85, 528/60, 524/589, 524/590, 524/839
• US Class Current: 528/85
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2262/02 Synthetic macromolecular fibres
• CPC Class Codes: B32B 2262/062 Cellulose fibres, e.g. cotton
• CPC Class Codes: B32B 2262/08 Animal fibres, e.g. hair, wool, silk
• CPC Class Codes: B32B 2262/10 Inorganic fibres layered products comprising a layer of natural mineral fibres B32B19/00
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2264/102 Oxide or hydroxide
• CPC Class Codes: B32B 2264/104 Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
• CPC Class Codes: B32B 2270/00 Resin or rubber layer containing a blend of at least two different polymers
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2307/54 Yield strength; Tensile strength
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/584 Scratch resistance
• CPC Class Codes: B32B 2307/71 Resistive to light or to UV
• CPC Class Codes: B32B 2457/20 Displays, e.g. liquid crystal displays, plasma displays
• CPC Class Codes: B32B 2551/00 Optical elements
• CPC Class Codes: B32B 2571/02 defensive, e.g. armour plates, anti-ballistic clothing camouflage nets B32B2459/00
• CPC Class Codes: B32B 2605/006 Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
• CPC Class Codes: B32B 2605/18 Aircraft blades, propellers B32B2603/00
• 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: C08J 3/205 : in the presence of a continuous liquid phase
• CPC Class Codes: Y10T 428/31547 : Of polyisocyanurate
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

The present invention provides polyurethane composition including: (a) at least one polyurethane including a reaction product of components comprising: (i) at least one polyisocyanate; (ii) at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and (iii) at least one diol having 2 to 18 carbon atoms; and (b) at least one reinforcement material selected from the group consisting of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric organic materials, nonpolymeric organic materials, composites thereof, and combinations thereof; coatings and articles made therefrom and methods of making the same.

Claims

1. A polyurethane composition comprising:

(a) at least one polyurethane comprising a reaction product of components comprising;

(1) a polyurethane prepolymer prepared from components comprising;

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

(ii) about 0.1 to about 0.9 equivalent of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, glycerol, or glycerin; and

(iii) about 0.3 to about 0.9 equivalent of at least one polyol having one or more bromine atoms, one or more phosphorus atoms or combinations thereof; and

(2) about 0.1 to about 0.9 equivalents of one or more diols free of bromine atoms and phosphorus atoms and having 2 to 18 carbon atoms; and

(b) at least one reinforcement material selected from the group consisting of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric organic materials, nonpolymeric organic materials, composites thereof, and mixtures thereof.

4. The polyurethane composition according to claim 1, wherein the at least one 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-isocyanatomethyl-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, trimmers, and mixtures thereof.

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

-methylene-bis-(cyclohexyl isocyanate).

6. The polyurethane composition according to claim 1, wherein the at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups is selected from the group consisting of tetramethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.

7. The polyurethane composition according to claim 6, wherein the at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups is trimethylolpropane.

8. The polyurethane composition according to claim 1, wherein the diol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-ethanediol, propanediol, butanediol, 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.

9. The polyurethane composition according to claim 8, wherein the diol is pentanediol or decanediol.

10. The polyurethane composition according to claim 1, wherein the reinforcement material is a polymeric inorganic material selected from the group consisting of polyphosphazenes, polysilanes, polysiloxanes, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures thereof.

11. The polyurethane composition according to claim 1, wherein the reinforcement material is a nonpolymeric inorganic material selected from the group consisting of graphite, metals, metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates, glass, basalt, mineral wool, silicon carbide, carbon, quartz, mullite, aluminum oxide, piezoelectric ceramic materials, and combinations thereof.

12. The polyurethane composition according to claim 1, wherein the reinforcement material is a polymeric organic material selected from the group consisting of thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes, polyimides, polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides, polyphenylene sulfides and polyacetals, polyamides, thermoplastic polyesters, acrylics, polyolefins, polyurethanes and vinyl polymers, (meth)acrylic polymers, copolymers comprising at least one functional group selected from the group consisting of silane groups, carboxyl groups, hydroxyl groups and amide groups, and mixtures thereof.

2. A polyurethane composition comprising:

(a) at least one polyurethane comprising a reaction product of components comprising;

(1) a polyurethane prepolymer prepared from components comprising;

(i) at least one polyisocyanate; and

(ii) at least one branched triol having 4 to 18 carbon atoms and at least 3 hydroxyl groups; and

(2) at least one diol having 2 to 18 carbon atoms; and

(b) at least one reinforcement material selected from the group consisting of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric organic materials, nonpolymeric organic materials, composites thereof, and combinations thereof,

wherein the at least one polyisocyanate is selected from the group consisting of (1) polyisocyanate trimers and (2) branched polyisocyanates selected from the group consisting of 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,5,7-trimethyl-1,8-diisocyanato-5-(isocyanatomethyl)octane, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, 2,4,6-trioxo-1,3,5-tris(6-isocyanatohexyl)hexahydro-1,3,5-triazine, 2,4,6-trioxo-1,3,5-tris(5-isocyanato-1,3,3-trimethyl-cyclohexylmethyl)hexahydro-1,3,5-triazine, tris(4-isocyanatophenyl)methane, 1,3,5-tris(3-isocyanato-4-methylphenyl)-2,3,6-trioxohexahydro-1,3,5 triazine, N-isocyanatohexylamino-carbonyl-N,N′

-bis(isocyanatohexyl)urea and 4-(isocyanatomethyl)-1,8-octane diisocyanate;

the at least one diol is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, 1,2-ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecane diol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, 1,4-bis(hydroxyethyl)piperazine, N,N′

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

the at least one triol is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol and mixtures thereof,

wherein the equivalent ratio of NCO;

OH is about 1.0;

1.0, and wherein the reaction product components comprise less than about 5 weight percent of polyester polyol, polycarbonate polyol, or polyether polyol, and include less than about 0.1 equivalent of amine curing agent for about 1 equivalent of polyisocyanate and, upon mixing, the reaction components are maintained at a reaction temperature of at least about 100°

C. for at least about 10 minutes.

13. The polyurethane composition according to claim 2, wherein the at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups is trimethylolpropane.

14. The polyurethane composition according to claim 2, wherein the at least one diol is pentanediol, or decanediol.

15. The polyurethane composition according to claim 2, wherein the reinforcement material is a polymeric inorganic material selected from the group consisting of polyphosphazenes, polysilanes, polysiloxanes, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures thereof.

16. The polyurethane composition according to claim 2, wherein the reinforcement material is a nonpolymeric inorganic material selected from the group consisting of graphite, metals, metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates, glass, basalt, mineral wool, silicon carbide, carbon, quartz, mullite, aluminum oxide, piezoelectric ceramic materials, and combinations thereof.

17. The polyurethane composition according to claim 2, wherein the reinforcement material is a polymeric organic material selected from the group consisting of thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes, polyimides, polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides, polyphenylene sulfides and polyacetals, polyamides, thermoplastic polyesters, acrylics, polyolefins, polyurethanes and vinyl polymers, (meth)acrylic polymers, copolymers comprising at least one functional group selected from the group consisting of silane groups, carboxyl groups, hydroxyl groups and amide groups, and mixtures thereof.

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

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

(b) about 0.1 to about 0.9 equivalents of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, glycerol or glycerin;

(c) about 0.3 to about 0.9 equivalents of at least one polyol having one or more bromine atoms, one or more phosphorus atoms or combinations thereof;

(d) about 0.1 to about 0.9 equivalents of one or more diols free of bromine atoms and phosphorus atoms and having 2 to 18 carbon atoms; and

(e) at least one reinforcement material selected from the group consisting of polymeric inorganic materials, nonpolymeric inorganic materials, polymeric organic materials, nonpolymeric organic materials, composites thereof, and mixtures thereof.

18. The polyurethane according to claim 3, wherein the at least one 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-isocyanatomethyl-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, trimmers, and mixtures thereof.

19. The polyurethane composition according to claim 3, wherein the at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups is selected from the group consisting of tetramethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.

20. The polyurethane composition according to claim 3, wherein the diol free of bromine atoms and phosphorus atoms and having 2 to 18 carbon atoms is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-ethanediol, propanediol, butanediol, 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.

21. The polyurethane according to claim 3, wherein the reinforcement material is a polymeric inorganic material selected from the group consisting of polyphosphazenes, polysilanes, polysiloxanes, polygeremanes, polymeric sulfur, polymeric selenium, silicones, and mixtures thereof.

22. The polyurethane according to claim 3, wherein the reinforcement material is a nonpolymeric inorganic material selected from the group consisting of graphite, metals, metal oxides, metal nitrides, metal carbides, metal sulfides, metal silicates, metal borides, metal carbonates, and combinations thereof.

23. The polyurethane composition according to claim 3, wherein the reinforcement material is a polymeric organic material selected from the group consisting of thermoset polyesters, vinyl esters, epoxy materials, phenolics, aminoplasts, thermoset polyurethanes, polyimides, polyether sulfones, polyphenyl sulfones, polyetherketones, polyphenylene oxides, polyphenylene sulfides and polyacetals, polyamides, thermoplastic polyesters, acrylics, polyolefins, polyurethanes and vinyl polymers, (meth)acrylic polymers, copolymers comprising at least one functional group selected from the group consisting of silane groups, carboxyl groups, hydroxyl groups and amide groups, and mixtures thereof.