Golf Balls Including Crosslinked Thermoplastic Polyurethane

Abstract

This disclosure relates to golf balls made from a crosslinked thermoplastic polyurethane elastomer. The crosslinked thermoplastic polyurethane elastomer includes crosslinks located in the hard segments, where the crosslinks being the reaction product of unsaturated bonds located in the hard segments as catalyzed by a free radical initiator. The crosslinks may be formed from an unsaturated diol as a chain extender. The unsaturated diol may be trimethylolpropane monoallylether (TMPME). The golf ball may include the crosslinked thermoplastic polyurethane elastomer in the cover layer, in which case the cover layer may exhibit a high degree of scuff resistance.

1 . A golf ball comprising:
 a crosslinked thermoplastic polyurethane elastomer;   the crosslinked thermoplastic polyurethane elastomer including hard segments and soft segments;   wherein the crosslinked thermoplastic polyurethane elastomer includes crosslinks located in the hard segments, the crosslinks being the reaction product of unsaturated bonds located in an allyl side chain of an unsaturated diol chain extender as catalyzed by a free radical initiator.   
     
     
         2 . The golf ball of  claim 1 , wherein the crosslinked thermoplastic polyurethane elastomer comprises an unsaturated diol, having two primary hydroxyl groups and at least one allyl ether side group, of the formula 
       
         
           
           
               
               
           
         
       
       in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4. 
     
     
         3 . The golf ball of  claim 2 , wherein a weight ratio of the free radical initiator to the unsaturated diol chain extender is about 5:100. 
     
     
         4 . The golf ball of  claim 2 , wherein the crosslinked thermoplastic polyurethane elastomer is the reaction product formed from reacting an organic isocyanate with a mixture of the following reactants:
 (a) the unsaturated diol chain extender of the formula   
       
         
           
           
               
               
           
         
       
       in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4;
 wherein a weight ratio of the crosslinked thermoplastic polyurethane elastomer to the unsaturated diol chain extender is from about 100:0.1 to about 100:25; 
 (b) a secondary chain extender, having at least two reaction sites with isocyantes and having a molecular weight of less than about 450; 
 (c) a long chain polyol having a molecular weight of between about 500 and about 4,000; and 
 (d) a sufficient degree amount of free radical initiator, so as to be capable of generating free radicals that induce crosslinking structures in the hard segments by free radical initiation. 
 
     
     
         5 . The golf ball of  claim 1 , wherein the golf ball comprises a core and a cover layer substantially surrounding the core;
 the cover layer comprises an inner cover layer substantially surrounding the core and an outer cover layer substantially surrounding the inner cover layer; and   the outer cover layer comprises the crosslinked thermoplastic polyurethane elastomer having crosslinks located in the hard segments.   
     
     
         6 . The golf ball of  claim 1 , wherein the golf ball comprises a core and a cover layer substantially surrounding the core; and
 the cover layer comprises the crosslinked thermoplastic polyurethane elastomer having crosslinks located in the hard segments.   
     
     
         7 . A golf ball comprising: an inner core layer, an outer core layer substantially surrounding the inner core layer, an inner cover layer substantially surrounding the outer core layer, and an outer cover layer substantially surrounding the inner cover layer;
 wherein the outer cover layer comprises a crosslinked thermoplastic polyurethane elastomer having crosslinks located in hard segments, the crosslinks being the reaction product of unsaturated bonds located in the hard segments as catalyzed by a free radical initiator; and   the golf ball satisfies the following requirements:   (1) the golf ball has a compression deformation of from about 2 to about 4 millimeters under a load of 10 to 130 kilograms;   (2) the inner core layer has a coefficient of restitution at 40 meters per second from about 0.79 to about 0.92, the coefficient of restitution of the inner core being higher than that of the golf ball.   
     
     
         8 . The golf ball of  claim 7 , wherein the unsaturated bond is located in a trimethylolpropane monoallylether chain extender. 
     
     
         9 . The golf ball of  claim 7 , wherein the outer cover layer has a Shore D hardness of between about 20 and about 75. 
     
     
         10 . The golf ball of  claim 7 , wherein the free radical initiator is selected from the group consisting of peroxides, sulfurs, and sulfides. 
     
     
         11 . The golf ball of  claim 7 , the outer cover layer has a flexural modulus of from about 1 kpsi to about 150 kpsi. 
     
     
         12 . The golf ball of  claim 7 , wherein the crosslinked thermoplastic polyurethane elastomer comprises an unsaturated diol, having two primary hydroxyl groups and at least one allyl ether side group, of the formula 
       
         
           
           
               
               
           
         
         in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4. 
       
     
     
         13 . The golf ball of  claim 7 , wherein:
 the crosslinked thermoplastic polyurethane elastomer is the reaction product formed from reacting an organic isocyanate with a mixture of the following reactants:   (a) an unsaturated diol chain extender of the formula   
       
         
           
           
               
               
           
         
       
       in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4;
 wherein a weight ratio of the crosslinked thermoplastic polyurethane elastomer to the unsaturated diol chain extender is from about 100:0.1 to about 100:25; 
 (b) a secondary chain extender, having at least two reaction sites with isocyantes and having a molecular weight of less than about 450; 
 (c) a long chain polyol having a molecular weight of between about 500 and about 4,000; and 
 (d) a sufficient degree amount of free radical initiator, so as to be capable of generating free radicals that induce crosslinking structures in the hard segments by free radical initiation, wherein the free radical initiator is present in the crosslinked thermoplastic polyurethane elastomer in a weight ratio of free radical initiator to unsaturated diols of from about 0.1:100 to about 100:100. 
 
     
     
         14 . A golf ball comprising: an inner core layer, an outer core layer substantially surrounding the inner core layer, an inner cover layer substantially surrounding the outer core layer, and an outer cover layer substantially surrounding the inner cover layer;
 wherein the outer cover layer comprises a crosslinked thermoplastic polyurethane elastomer having crosslinks located in hard segments, the crosslinks being the reaction product of unsaturated bonds located in the hard segments as catalyzed by a free radical initiator; and   the golf ball satisfies the following requirements:   (1) the outer cover layer has a Shore D hardness from about 20 to about 75; and   (2) the outer cover layer has a flexural modulus of from about 1 kpsi to about 150 kpsi.   
     
     
         15 . The golf ball of  claim 14 , wherein the golf ball has a compression deformation of from about 2 to about 4 millimeters under a load of 10 to 130 kilograms. 
     
     
         16 . The golf ball of  claim 14 , wherein the inner core layer has a coefficient of restitution at 40 meters per second from about 0.79 to about 0.92, the coefficient of restitution of the inner core being higher than that of the golf ball. 
     
     
         17 . The golf ball of  claim 14 , wherein the crosslinked thermoplastic polyurethane elastomer comprises unsaturated diols as chain extenders. 
     
     
         18 . The golf ball of  claim 17 , wherein the weight ratio of the crosslinked thermoplastic polyurethane elastomer to the unsaturated diols is from 100:0.1 to 100:15. 
     
     
         19 . The golf ball of  claim 14 , wherein the crosslinked thermoplastic polyurethane elastomer comprises an unsaturated diol, having two primary hydroxyl groups and at least one allyl ether side group, of the formula 
       
         
           
           
               
               
           
         
       
       in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4. 
     
     
         20 . The golf ball of  claim 14 , wherein the crosslinked thermoplastic polyurethane elastomer includes crosslinks formed from allyl ether side groups, and the crosslinked thermoplastic polyurethane elastomer is the reaction product formed from reacting an organic isocyanate with a mixture of the following reactants:
 (a) an unsaturated diol, having two primary hydroxyl groups and at least one allyl ether side group, of the formula   
       
         
           
           
               
               
           
         
       
       in which R is alkyl group with or without modified functional groups, and x and y are integers of 1 to 4;
 (b) a chain extender, having at least two reaction sites with isocyantes and having a molecular weight of less than about 450; 
 (c) a long chain polyol having a molecular weight of between about 500 and about 4,000; and 
 (d) a sufficient amount of free radical initiator, so as to be capable of generating free radicals that induce crosslinking structures in the hard segments by free radical initiation.