HIGH PERFORMANCE POLYURETHANE ELASTOMERS FROM MDI PREPOLYMERS WITH REDUCED CONTENT OF FREE MDI MONOMER

• US 20090076239A1
• Filed: 11/21/2008
• Published: 03/19/2009
• Est. Priority Date: 11/30/1999
• Status: Abandoned Application

• Current Assignee: Ajaib Singh, Richard L. Palinkas, Ronald O. Rosenberg, Rui Xie, Thomas H. Peter
• Original Assignee: Ajaib Singh, Richard L. Palinkas, Ronald O. Rosenberg, Rui Xie, Thomas H. Peter
• Inventors: Xie, Rui, Singh, Ajaib, Rosenberg, Ronald O., Palinkas, Richard L., Peter, Thomas H.
• Application Number:
  US12/275,969
• Publication Number:
  US 20090076239A1
• Time in Patent Office: Days
• US Class Current: 528/60
• 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 18/285 Nitrogen containing compounds
• CPC Class Codes: C08G 18/286 Oximes
• CPC Class Codes: C08G 18/3206 aliphatic
• CPC Class Codes: C08G 18/3215 containing aromatic groups or benzoquinone groups
• CPC Class Codes: C08G 18/3814 Polyamines
• CPC Class Codes: C08G 18/3821 Carboxylic acids; Esters thereof with monohydroxyl compounds
• CPC Class Codes: C08G 18/3868 the sulfur atom belonging to a sulfide group
• CPC Class Codes: C08G 18/4841 containing oxyethylene end groups
• CPC Class Codes: C08G 18/4845 containing oxypropylene or higher oxyalkylene end groups
• CPC Class Codes: C08G 18/4854 Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/7671 containing only one alkylene bisphenyl group

Abstract

Polyurethane prepolymers having a reduced amount of unreacted monomeric diisocyanate, particularly diphenylmethane diisocyanate (MDI), prepared by distilling the prepolymer reaction product in the presence of at least one inert solvent whose boiling point is slightly below that of the monomeric diisocyanate; and to high performance cast polyurethane elastomers from the thus obtained prepolymers using diamine and/or diol chain extenders.

Claims

1-13. -13. (canceled)

14. A polyurethane elastomer comprising the reaction product of i) a prepolymer terminated with diphenylmethane diisocyanate, said prepolymer comprising no more than about 0.3% free diphenylmethane diisocyanate and having at least about 80% of theoretical NCO content for pure ABA structure with ii) a chain extender selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

an aliphatic triol;

an aliphatic tetrol;

4,4′

-methylene-bis(2-chloroaniline);

4,4,′

-methylene-bis(3-chloro-2,6-diethylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof;

wherein the equivalent ratio of prepolymer to chain extender is in the range of from about 0.7;

1 to about 1.2;

1.

15. The elastomer of claim 14 wherein at least one chain extender is selected from the group consisting of trimethylene glycol di-p-amino-benzoate;

4,4′

-methylene-bis (3-chloroaniline);

4,4′

-methylene-bis(3-chloro-2,6-diethylaniline);

diethyl toluene diamine; and

dimethylthio-toluene diamine.

16. The elastomer of claim 14 wherein the chain extender is trimethylene glycol di-p-amino-benzoate.

17. The elastomer of claim 14 wherein the chain extender is 4,4′

-methylene-bis(2-chloroaniline).

18. The elastomer of claim 14 wherein the chain extender is diethyl toluene diamine.

19. A polyurethane elastomer comprising the reaction product of:

A) a diphenylmethane diisocyanate-terminated prepolymer comprising the reaction product of;

i) a first polyol comprising at least one component having a low molecular weight in the range of from about 62 to about 400, and selected from the group consisting of ethylene glycol, isomers of propylene glycol, isomers of butane diol, hexanediol, trimethylolpropane, pentaerythritol, poly(tetramethylene ether) glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and mixtures thereof;

ii) a second polyol having a high molecular weight in the range of from about 400 to about 5000; and

iii) a stoichiometric excess of diphenylmethane diisocyanate monomer at an NCO;

OH ratio in the range of from about 2;

1 to about 20;

1;

wherein unreacted diphenylmethane diisocyanate monomer is removed from said reaction product by a process comprising distilling the reaction product in the presence of at least one inert solvent having a boiling point about 1°

C. to about 100°

C. below the boiling point of the diphenylmethane diisocyanate monomer at a pressure of 10 torr, wherein the weight ratio of the inert solvent to the diphenylmethane diisocyanate monomer ranges from about 90;

10 to about 10;

90, and the inert solvent comprises about 5% to about 85% by weight of the total weight of the combination of the prepolymer reaction product mixture plus solvents;

with

B) a chain extender selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

aliphatic triols;

aliphatic tetrols;

4,4′

-methylene-bis(2-chloroaniline);

4,4′

-methylene-bis(3-chloro-2,6-diethylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof;

wherein the equivalent ratio of chain extender to prepolymer is in the range of from about 0.7;

1 to about 1.2;

1.

20. A wheel or roll comprising a core and a polyurethane cover wherein the cover comprises the reaction product of:

A) a prepolymer comprising the reaction product of a polyol and diphenyl methane diisocyanate wherein excess diphenyl methane diisocyanate has been removed to less than 2 wt %, and

B) an amine or diol chain extender.

21. The wheel or roll of claim 20 wherein the amine or diol chain extender is selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

an aliphatic triol;

an aliphatic tetrol;

4,4′

-methylene-bis(2-chloroaniline);

4,4′

-methylene-bis(3-chloro-2,6-diethylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof.

22. A wheel or roll comprising a core and a polyurethane cover wherein the cover comprises a polyurethane elastomer comprising the reaction product of i) a prepolymer terminated with diphenylmethane diisocyanate, said prepolymer comprising no more than about 0.3% free diphenylmethane diisocyanate and having at least about 80% of theoretical NCO content for pure ABA structure with ii) a chain extender selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

an aliphatic triol;

an aliphatic tetrol;

4,4′

-methylene-bis(2-chloroaniline);

4,4′

-methylene-bis(3-chloro-2,6-diet-hylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof;

wherein the equivalent ratio of prepolymer to chain extender is in the range of from about 0.7;

1 to about 1.2;

1.

23. A golf ball comprising a core and a cover, where the cover is a polyurethane elastomer comprising the reaction product of:

A) a prepolymer comprising the reaction product of a polyol and diphenyl methane diisocyanate wherein excess diphenyl methane diisocyanate has been removed to less than 2 wt %, and

B) at least one hydroxy or amine functional chain extender.

24. The golf ball of claim 23 wherein the amine or diol chain extender is selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

an aliphatic triol;

an aliphatic tetrol;

4,4′

-methylene-bis(2-chloroaniline);

4,4′

-methylene-bis (3-chloro-2,6-diethylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenaedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof

25. A golf ball comprising a core and a polyurethane cover wherein the cover comprises a polyurethane elastomer comprising the reaction product of i) a prepolymer terminated with diphenylmethane diisocyanate, said prepolymer comprising no more than about 0.3% free diphenylmethane diisocyanate and having at least about 80% of theoretical NCO content for pure ABA structure with ii) a chain extender selected from the group consisting of 1,4-butanediol;

1,3-propanediol;

ethylene glycol;

1,6-hexanediol;

hydroquinone-bis-hydroxyethyl ether;

resorcinol di(beta-hydroxyethyl) ether;

resorcinol di(beta-hydroxypropyl) ether;

1,4-cyclohexane dimethanol;

an aliphatic triol;

an aliphatic tetrol;

4,4′

-methylene-bis(2-chloroaniline);

4,4′

-methylene-bis(3-chloro-2,6-diet-hylaniline);

diethyl toluene diamine;

t-butyl toluene diamine;

dimethylthio-toluene diamine;

trimethylene glycol di-p-amino-benzoate;

methylenedianiline;

methylenedianiline-sodium chloride complex; and

mixtures thereof;

wherein the equivalent ratio of prepolymer to chain extender is in the range of from about 0.7;

1 to about 1.2;

1.

26. A multicomponent system for producing polyurea-urethane elastomers comprising

A) a prepolymer comprising the reaction product of a polyol and diphenyl methane diisocyanate wherein excess diphenyl methane diisocyanate has been removed to less than 2 wt %, and

B) methylene dianiline or its complex with sodium chloride.

27. (canceled)

28. A thermoplastic urethane elastomer comprising the reaction product of

A) a prepolymer comprising the reaction product of a polyol and diphenyl methane diisocyanate wherein excess diphenyl methane diisocyanate has been removed to less than 2 wt %, and

B) at least one hydroxy or amine functional chain extender.