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

• US 9,464,169 B2
• Filed: 03/14/2014
• Issued: 10/11/2016
• 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.
• Primary Examiner(s): NILAND, PATRICK DENNIS
• Application Number:
  US14/212,192
• Publication Number:
  US 20140199524A1
• Time in Patent Office: 942 Days
• US Class Current: 1/1
• CPC Class Codes: B32B 17/10 of synthetic resin
• CPC Class Codes: B32B 17/10614 comprising particles for purposes other than dyeing
• CPC Class Codes: B32B 17/10752 containing polycarbonate
• CPC Class Codes: B32B 17/1077 containing polyurethane
• CPC Class Codes: B32B 2250/02 2 layers
• CPC Class Codes: B32B 2250/24 All layers being polymeric
• CPC Class Codes: B32B 2307/412 Transparent
• CPC Class Codes: B32B 2307/558 Impact strength, toughness
• CPC Class Codes: B32B 2307/704 Crystalline
• CPC Class Codes: B32B 2457/20 Displays, e.g. liquid crystal displays, plasma displays
• CPC Class Codes: B32B 2605/00 Vehicles
• CPC Class Codes: B32B 2605/18 Aircraft blades, propellers B32B2603/00
• CPC Class Codes: B32B 27/08 of synthetic resin
• CPC Class Codes: B32B 27/365 comprising polycarbonates
• CPC Class Codes: B32B 27/40 comprising polyurethanes
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• 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 18/4018 Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• CPC Class Codes: C08G 18/44 : Polycarbonates
• CPC Class Codes: C08G 18/6611 : having at least three hydroxy groups
• CPC Class Codes: C08G 18/664 : with compounds of group C08G18/3203
• CPC Class Codes: C08G 18/6644 : having at least three hydroxy groups
• 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 64/42 : Chemical after-treatment
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: Y10T 428/24628 : Nonplanar uniform thickness material
• 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

Abstract

The present invention provides polyurethanes including a reaction product of components including: (a) at least one isocyanate functional prepolymer including a reaction product of: (1) about 1 equivalent of at least one polyisocyanate; and (2) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol; and (b) about 0.01 to about 1 equivalent of at least one branched polyol having at least 3 hydroxyl groups; compositions, coatings and articles made therefrom and methods of making the same.

Claims

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

(a) at least one isocyanate functional prepolymer comprising a reaction product of;

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

(2) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate; and

(b) about 0.01 to about 1 equivalent of at least one polyol having at least 3 hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate,

wherein the components further comprise about 0.01 to about 0.5 equivalent of water based upon the about 1 equivalent of the at least one polyisocyanate.

2. The polyurethane according to claim 1, wherein the water is reacted with the polyisocyanate and polycarbonate polyol to form an isocyanate functional ureaurethane prepolymer.

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

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

(b) about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate; and

(c) about 0.01 to about 1 equivalent of at least one polyol having at least 3 hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate, and

(d) about 0.01 to about 0.5 equivalent of water based upon the about 1 equivalent of the at least one polyisocyanate.

4. A process for preparing a polyurethane article comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.01 to about 1 equivalent of at least one polyol having at least 3 hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours,

wherein the at least one polyol of step (b) is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolmethane, trimethylolpropane, erythritol, pentaerythritol.

5. The process of claim 4, wherein the polyisocyanate of step (a) is selected from the group consisting of diisocyanates, triisocyanates, dimers, trimers and mixtures thereof.

6. The process of claim 4, wherein the polycarbonate polyol of step (a) is prepared from hexanediol and dialkyl carbonate.

7. The process of claim 4, wherein the at least one polyol of step (b) is trimethylolpropane.

8. The process of claim 4, wherein step (b) further comprises mixing about 0.001 to about 0.5 equivalent of at least one polyol different from the at least one polyol of step (b), based upon the about 1 equivalent of the at least one polyisocyanate, with the reaction product (a) and the at least one polyol of step (b).

9. The process of claim 8, wherein the at least one polyol different from the at least one polyol of step (b) is a diol.

10. The process of claim 8, wherein the at least one polyol different from the at least one polyol of step (b) 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, 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 process of claim 4, wherein the mixture of step (a) and/or step (b) further comprises one or more polyurethane polyols, acrylamides, polyvinyl alcohols, hydroxy functional acrylates, hydroxy functional methacrylates, allyl alcohols, dihydroxy oxamides, dihydroxyamides, dihydroxy piperidines, dihydroxy phthalates, dihydroxyethyl hydroquinones and mixtures thereof.

12. The process of claim 4, comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.5 to about 0.8 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate and about 0.1 to about 0.5 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours.

13. The process of claim 4, comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.2 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.7 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate and about 0.1 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours.

14. A polyurethane article prepared by a process comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.01 to about 1 equivalent of at least one polyol having at least 3 hydroxyl groups based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours,

wherein the at least one polyol of step (b) is selected from the group consisting of glycerol, glycerin, tetramethylolmethane, trimethylolmethane, trimethylolpropane, erythritol, pentaerythritol.

15. The polyurethane article of claim 14 prepared by a process comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.01 to about 0.5 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.5 to about 0.8 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate and about 0.1 to about 0.5 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours.

16. The polyurethane article of claim 14 prepared by a process comprising:

(a) heating a mixture of about 1 equivalent of at least one polyisocyanate and about 0.2 equivalent of at least one polycarbonate polyol based upon the about 1 equivalent of the at least one polyisocyanate, to a temperature of about 110°

C. to about 130°

C. for at least about an hour to form a reaction product;

(b) mixing the reaction product (a) with about 0.7 equivalent of trimethylolpropane based upon the about 1 equivalent of the at least one polyisocyanate and about 0.1 equivalent of butanediol, pentanediol or cyclohexane dimethanol based upon the about 1 equivalent of the at least one polyisocyanate until the mixture reaches a temperature of at least about 110°

C. to about 130°

C., optionally by heating if necessary;

(c) casting the reaction product into a mold preheated to a temperature of at least about 100°

C. to about 130°

C.; and

(d) curing the reaction product at a first predetermined temperature of about 100°

C. to about 120°

C. for at least about 0.5 hours; and

then at a second predetermined temperature of about 140°

C. to about 180°

C. for about 15 to about 30 hours.