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

• US 9,951,173 B2
• Filed: 02/26/2016
• Issued: 04/24/2018
• 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., Harris, Caroline S., Hunia, Robert M., Frain, Veronica L.
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US15/054,317
• Publication Number:
  US 20160215087A1
• Time in Patent Office: 788 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 vehicle transparency comprising at least one layer of a polyurethane, wherein the polyurethane consists of a reaction product of components consisting of:

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

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

(ii) about 0.3 to about 0.4 equivalents of pentanediol; and

(b) about 0.3 to about 0.6 equivalents of trimethylolpropane based upon the about 1 equivalent of at least one polyisocyanate (i); and

(c) about 0.1 to about 0.4 equivalents of butanediol or pentanediol based upon the about 1 equivalent of at least one polyisocyanate (i),

wherein the prepolymer (a), trimethylolpropane (b), and butanediol or pentanediol (c) 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 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 vehicle transparency of claim 1, wherein the vehicle transparency is an automotive transparency, a nautical transparency, or an aircraft or airplane transparency.

3. The vehicle transparency of claim 2, wherein the vehicle transparency is an automotive transparency.

4. The vehicle transparency of claim 2, wherein the vehicle transparency is an aircraft or airplane transparency.

5. The vehicle transparency of claim 1, wherein the vehicle transparency is ballistic resistant.

6. The vehicle transparency of claim 1, wherein the polyisocyanate is selected from the group consisting of diisocyanates, triisocyanates, dimers, trimers and mixtures thereof.

7. The vehicle transparency of claim 1, wherein the polyisocyanate is 4,4′

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

-methylene-bis-(cyclohexyl isocyanate).

8. The vehicle transparency of claim 1, wherein the polyurethane has a urethane content of about 20 to about 40 weight percent.

9. The vehicle transparency of claim 1, wherein the polyurethane has a cyclic content of about 10 to about 80 weight percent.

10. The vehicle transparency of claim 1, wherein the polyurethane has a molecular weight per crosslink of at least about 500 grams per mole.

11. A laminated transparency comprising:

(1) at least one layer of a polyurethane consisting of a reaction product of components consisting of;

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

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

(ii) about 0.3 to about 0.4 equivalents of pentanediol; and

(b) about 0.3 to about 0.6 equivalents of trimethylolpropane based upon the about 1 equivalent of at least one polyisocyanate (i); and

(c) about 0.1 to about 0.4 equivalents of butanediol or pentanediol based upon the about 1 equivalent of at least one polyisocyanate (i),

wherein the prepolymer (a), trimethylolpropane (b), and butanediol or pentanediol (c) 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 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; and

(2) at least one layer of a substrate selected from the group consisting of glass, organic polymeric materials, and combinations thereof.

12. The laminated transparency of claim 11, wherein the substrate is selected from the group consisting of polycarbonates, polyesters, polyether thermoplastic elastomers, poly(methyl methacrylates), polyhexylene-polycarbonate-based polyurethanes, polyol(allyl carbonate)polymerizates, polyol (allyl carbonate)polymerizates, polymers of aliphatic urethane copolymers, poly(vinyl acetate), polyvinylbutyral, polyurethanes, polymers of diethylene glycol dimethacrylate monomers, polymers of diisopropenyl benzene monomers, polymers of ethoxylated trimethylol propane triacrylate monomers, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, polystyrene, and copolymers of styrene with methyl methacrylate, vinyl acetate and acrylonitrile, and mixtures thereof.

13. The laminated transparency of claim 12, wherein the substrate is selected from the group consisting of polycarbonates, polyesters, polyether thermoplastic elastomers, and mixtures thereof.

14. The laminated transparency of claim 11, wherein the overall thickness of the layer(s) of the polyurethane ranges from about 2 mm to about 15 cm.

15. The laminated transparency of claim 11, wherein the overall thickness of the polyurethane layer ranges from about 2 mm to about 5 cm.

16. The laminated transparency of claim 11, wherein the layer(s) of the polyurethane is positioned on the outside of the laminated transparency.

17. The laminated transparency of claim 11, wherein the layer(s) of the polyurethane is positioned on the inside of the laminated transparency.

18. A laminated transparency comprising:

(1) at least one layer of a polyurethane consisting of a reaction product of components consisting of;

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

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

(ii) about 0.3 to about 0.4 equivalents of pentanediol; and

(b) about 0.3 to about 0.6 equivalents of trimethylolpropane based upon the about 1 equivalent of at least one polyisocyanate (i); and

(c) about 0.1 to about 0.4 equivalents of butanediol or pentanediol based upon the about 1 equivalent of at least one polyisocyanate (i),

(2) at least one layer comprising polycarbonate.

19. The laminated transparency of claim 18, wherein the overall thickness of the layer(s) of the polyurethane ranges from about 2 mm to about 15 cm.

20. The laminated transparency of claim 18, wherein the overall thickness of the polyurethane layer ranges from about 2 mm to about 5 cm.

21. The laminated transparency of claim 18, wherein the layer(s) of the polyurethane is positioned on the outside of the laminated transparency.

22. The laminated transparency of claim 18, wherein the layer(s) of the polyurethane is positioned on the inside of the laminated transparency.

23. An article comprising at least one layer of a polyurethane, wherein the polyurethane consists of a reaction product of components consisting of:

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

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

(ii) about 0.3 to about 0.4 equivalents of pentanediol; and

(b) about 0.3 to about 0.6 equivalents of trimethylolpropane based upon the about 1 equivalent of at least one polyisocyanate (i); and

(c) about 0.1 to about 0.4 equivalents of butanediol or pentanediol based upon the about 1 equivalent of at least one polyisocyanate (i),

wherein the prepolymer (a), trimethylolpropane (b), and butanediol or pentanediol (c) 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 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; and

wherein the article is selected from the group consisting of transparencies, optical articles, photochromic articles, ballistic resistant articles, and glazings.

24. The article of claim 23, further comprising at least one layer of a polycarbonate, polyester, or polyether thermoplastic elastomer.

25. The article of claim 23, wherein the article is an automotive transparency.

26. The article of claim 23, wherein the article has a Young'"'"'s modulus of at least about 350,000 lb/in² (about 2413 MPa), according to ASTM-D 638-03.

27. The article of claim 23, wherein the polyurethane has a K-Factor crack propagation resistance of at least about 1000 lb/in^3/2 (1,098,800 N/m^3/2).

28. A method of inhibiting the penetration of a ballistic projectile trough a transparency comprising:

(a) forming an article according to claim 23;

(b) allowing the ballistic projectile to impact a surface of the article, wherein the ballistic projectile comprises a bullet shot from a handgun, shotgun, rifle, or AK-47; and

(c) deflecting the ballistic projectile off the surface of the article.

29. A method of inhibiting the penetration of a ballistic projectile trough a transparency comprising:

(a) forming an article according to claim 23;

(b) allowing the ballistic projectile to impact a surface of the article, wherein the ballistic projectile comprises a bullet shot from a handgun, shotgun, rifle, or AK-47; and

(c) embedding the ballistic projectile in the surface of the article.