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

• US 9,822,211 B2
• Filed: 08/21/2014
• Issued: 11/21/2017
• 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., Harris, Caroline S., Hunia, Robert M., Frain, Veronica L., Wang, Yan
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US14/465,436
• Publication Number:
  US 20140364026A1
• Time in Patent Office: 1,188 Days
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2605/18 Aircraft
• 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 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 0.1 to about 0.5 equivalents of at least one polyol having 2 to 18 carbon atoms selected from the group consisting of dodecanediol, octadecanediol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, 1,4-bis(hydroxyethyl)piperazine, N,N′

,bis(2-hydroxyethyl)oxamide, 2-methyl-butanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, polyethylene glycol, cycloalkane diol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, cyclododecanediol, 4,4′

-isopropylidene-biscyclohexanol, hydroxypropylcyclohexanol, cyclohexanediethanol, 1,2-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 4,4′

-isopropylidene-biscyclohexanol, bis(4-hydroxycyclohexanol)methane and mixtures thereof; and

(b) about 0.05 to about 1.0 equivalents of at least one branched polyol having 4 to 18 carbon atoms and at least 3 hydroxyl groups, based upon the about 1 equivalent of at least one polyisocyanate (i), the polyol (b) being selected from the group consisting of tetramethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof; 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, based upon the about 1 equivalent of at least one polyisocyanate (i),

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 polyether polyol, wherein the prepolymer (a), polyol (b), and polyol (c) (if present) are each preheated to and maintained at a temperature of at least 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 of components into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time of the components in the mixing chamber is from about 0.1 seconds to about 5 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 a diisocyanate 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 3, wherein the diisocyanate is 4,4′

-methylene-bis-(cyclohexyl isocyanate) or the trans, trans isomer of 4,4′

-methylene-bis-(cyclohexyl isocyanate).

5. The polyurethane according to claim 1, wherein the polyisocyanate is selected from the group consisting of aliphatic, cycloaliphatic, aromatic and heterocyclic isocyanates, dimers and trimers thereof and mixtures thereof.

6. The polyurethane according to claim 1, wherein the equivalent ratio of polyisocyanate to polyol having 2 to 18 carbon atoms for preparing the isocyanate functional urethane prepolymer ranges from about 1:

0.3 to about 1;

0.4.

7. The polyurethane according to claim 1, wherein the equivalent ratio of polyisocyanate to polyol having 2 to 18 carbon atoms for preparing the isocyanate functional urethane prepolymer is about 1:

0.35.

8. The polyurethane according to claim 1, wherein the branched polyol has three hydroxyl groups.

9. The polyurethane according to claim 1, wherein the branched polyol is trimethylolpropane.

10. The polyurethane according to claim 1, 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, octadecanediol, 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.

11. The polyurethane according to claim 10, wherein the diol (c) is butanediol.

12. The polyurethane according to claim 10, wherein the diol (c) is pentanediol.

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

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

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

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

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

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

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

C. for at least about 10 minutes.

21. An article comprising the polyurethane of claim 1.

22. The article according to claim 21, wherein the article is a molded article.

23. The article according to claim 21, wherein the article is selected from the group consisting of transparencies, optical articles, photochromic articles, ballistic resistant articles, and glazings.

24. The article according to claim 21, wherein the article has a Gardner Impact strength of at least about 400 in-lb (45 Joules) according to ASTM-D 5420-04.

25. An article comprising the polyurethane of claim 21, wherein the article is an airplane transparency.

26. The article according to claim 25, wherein the article comprises at least one layer of the polyurethane of claim 19 and at least one layer of polycarbonate.

27. 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.

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

20. A 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 0.1 to about 0.5 equivalents of at least one diol having 2 to 18 carbon atoms selected from the group consisting of dodecanediol, octadecanediol, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, 1,4-bis(hydroxyethyl)piperazine, N,N′

,bis(2-hydroxyethyl)oxamide, 2-methyl-butanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, polyethylene glycol, cycloalkane diol, cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanol, cyclododecanediol, 4,4′

-isopropylidene-biscyclohexanol, hydroxypropylcyclohexanol, cyclohexanediethanol, 1,2-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 4,4′

-isopropylidenebiscyclohexanol, bis(4-hydroxycyclohexanol)methane and mixtures thereof; 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, based upon the about 1 equivalent of at least one polyisocyanate (i), the polyol (b) being selected from the group consisting of tetramethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof; and

(c) up to about 0.45 equivalents of at least one diol having 2 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 polyether polyol, wherein the prepolymer (a), polyol (b), and polyol (c) (if present) are each preheated to and maintained at a temperature of at least about 120°

C. to about 140°

C. for at least about 10 minutes immediately prior to mixing together using 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 of components into the mixing chamber is about 499 to about 4807 grams per minute, and wherein the residence time of the components in the mixing chamber is from about 0.1 seconds to about 5 minutes.