Epoxy-capped polythioethers

Abstract

Epoxy-capped polythioethers and curable compositions of epoxy-capped polythioethers are disclosed.

1 . An epoxy-capped polythioether having the following structural formula:  
       
         
           
           
               
               
           
         
       
       wherein 
 R 1  is selected from the group consisting of C 2-6  n-alkylene, C 3-6  branched alkylene, C 6-8  cycloalkylene, C 6-10  alkylcycloalkylene, and —[—(CHR 3 ) p —X—] q —CHR 3 ) r —, 
 wherein 
 each R 3  is independently selected from H, and —CH 3    
 each X is independently selected from O, S, —NH—, and —NR 4 —,  
 R 4  is selected from H, and —CH 3 ,  
 p is an integer from 2 to 6,  
 q is an integer from 1 to 5, and  
 r is an integer from 2 to 10,  
 
 
 and each R 2  is a divalent linking group.  
 
     
     
         2 . The epoxy-capped polythioether of  claim 1 , wherein R 1  is derived from a compound selected from the group consisting of dimercaptodioxaoctane, and dimercaptodiethylsulfide.  
     
     
         3 . The epoxy-capped polythioether of  claim 1 , wherein each R 2  is derived from an olefin.  
     
     
         4 . The epoxy-capped polythioether of  claim 3 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 20 carbon atoms, and an oxyalkylene having from 3 to 20 carbon atoms.  
     
     
         5 . The epoxy-capped polythioether of  claim 3 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 5 carbon atoms, and an oxyalkylene having from 3 to 5 carbon atoms.  
     
     
         6 . The epoxy-capped polythioether of  claim 1 , wherein each R 2  is derived from a compound selected from the group consisting of allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 4-vinyl-1-cyclohexene 1,2-epoxide, butadiene monoepoxide, isoprene monoepoxide, and limonene monoepoxide.  
     
     
         7 . The epoxy-capped polythioether of  claim 1 , which is free of hydrolysable chlorine.  
     
     
         8 . An epoxy-capped polythioether having the following structural formula:  
       
         
           
           
               
               
           
         
         where R 1  and R 2  have the meanings set forth in  claim 1 , B is a multivalent radical, and z is a number corresponding to the valence of B.  
       
     
     
         9 . The epoxy-capped polythioether of  claim 8 , wherein each R 1  is independently derived from a compound selected from the group consisting of dimercaptodioxaoctane, and dimercaptodiethylsulfide.  
     
     
         10 . The epoxy-capped polythioether of  claim 8 , wherein each R 2  is derived from an olefin.  
     
     
         11 . The epoxy-capped polythioether of  claim 10 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 20 carbon atoms, and an oxyalkylene having from 3 to 20 carbon atoms.  
     
     
         12 . The epoxy-capped polythioether of  claim 10 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 5 carbon atoms, and an oxyalkylene having from 3 to 5 carbon atoms.  
     
     
         13 . The epoxy-capped polythioether of  claim 8 , wherein each R 2  is derived from a compound selected from the group consisting of allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 4-vinyl-1-cyclohexene 1,2-epoxide, butadiene monoepoxide, isoprene monoepoxide, and limonene monoepoxide.  
     
     
         14 . The epoxy-capped polythioether of  claim 8 , which is free of hydrolysable chlorine.  
     
     
         15 . The epoxy-capped polythioether of  claim 8 , wherein z is from 3 to 6.  
     
     
         16 . The epoxy-capped polythioether of  claim 8 , having an average functionality between 2.05 and 3.  
     
     
         17 . The epoxy-capped polythioether of  claim 8 , wherein B is derived from a compound selected from the group consisting of a polyacid, a polyamine, a polyanhydride, and a polythiol.  
     
     
         18 . A curable composition comprising: 
 (a) at least one epoxy-capped polythioether of  claim 1;  and    (b) at least one curing agent.    
     
     
         19 . The curable composition of  claim 18 , wherein the at least one curing agent is selected from the group consisting of a polyacid, a polyamine, a polyanhydride, and a polythiol.  
     
     
         20 . The curable composition of  claim 18 , further comprising at least one adjuvant resin different from (a) and (b).  
     
     
         21 . The curable composition of  claim 18 , further comprising at least one filler.  
     
     
         22 . The curable composition of  claim 18 , further comprising at least one additive selected from the following: plasticizers, pigments, cure accelerators, adhesion promoters, thixotropic agents, fire retardants, masking agents, antioxidants, and surfactants.  
     
     
         23 . The curable composition of  claim 18 , which is free of hydrolysable chlorine.  
     
     
         24 . A curable composition comprising: 
 (a) at least one epoxy-capped polythioether of  claim 8;  and    (b) at least one curing agent.    
     
     
         25 . The curable composition of  claim 24 , wherein the at least one curing agent is selected from the group consisting of a polyacid, a polyamine, a polyanhydride, and a polythiol.  
     
     
         26 . The curable composition of  claim 24 , further comprising at least one adjuvant resin different from (a) and (b).  
     
     
         27 . The curable composition of  claim 24 , further comprising at least one filler.  
     
     
         28 . The curable composition of  claim 24 , further comprising at least one additive selected from the following: plasticizers, pigments, cure accelerators, adhesion promoters, thixotropic agents, fire retardants, masking agents, antioxidants, and surfactants.  
     
     
         29 . The curable composition of  claim 24 , which is free of hydrolysable chlorine.  
     
     
         30 . An epoxy-capped polythioether formed by reacting n moles of a compound having the structure of Formula I,  
         HS—R 1 —SH  I  wherein    R 1  is selected from the group consisting of C 2-6  n-alkylene, C 3-6  branched alkylene, C 6-8  cycloalkylene, C 6-10  alkylcycloalkylene, and —[—(CHR 3 ) p —X—] q —(CHR 3 ) r —,    wherein 
 R 3  is selected from H, and —CH 3 ,  
 each X is independently selected from O, S, —NH—, and —NR 4 —,  
 R 4  is selected from H, and —CH 3 ,  
 p is an integer from 2 to 6,  
 q is an integer from 1 to 5, and  
 r is an integer from 2 to 10,  
 or a mixture of at least two different compounds having the structure of Formula I, with n+1 moles of a compound having the structure of Formula II:  
                     
   wherein R 2  forms a divalent linking group,    or a mixture of at least two different compounds having the structure of Formula II.    
     
     
         31 . The epoxy-capped polythioether of  claim 30 , wherein R 1  is derived from a compound selected from the group consisting of dimercaptodioxaoctane, and dimercaptodiethylsulfide.  
     
     
         32 . The epoxy-capped polythioether of  claim 30 , wherein each R 2  comprises an olefin.  
     
     
         33 . The epoxy-capped polythioether of  claim 32 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 20 carbon atoms, and an oxyalkylene having from 3 to 20 carbon atoms.  
     
     
         34 . The epoxy-capped polythioether of  claim 32 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 5 carbon atoms, and an oxyalkylene having from 3 to 5 carbon atoms.  
     
     
         35 . The epoxy-capped polythioether of  claim 30 , wherein each R 2  is derived from a compound selected from the group consisting of allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 4-vinyl-1-cyclohexene 1,2-epoxide, butadiene monoepoxide, isoprene monoepoxide, and limonene monoepoxide.  
     
     
         36 . The epoxy-capped polythioether of  claim 30 , which is free of hydrolysable chlorine.  
     
     
         37 . The epoxy-capped polythioether of  claim 30 , having an epoxy equivalent weight range less than 300.  
     
     
         38 . The epoxy-capped polythioether of  claim 30 , having an epoxy equivalent weight range less than 150.  
     
     
         39 . The epoxy-capped polythioether of  claim 30 , which is formed in the presence of a catalyst selected from the group consisting of a free-radical catalyst, an ionic catalyst, and ultraviolet light.  
     
     
         40 . The epoxy-capped polythioether of  claim 39 , wherein the catalyst does not comprise an acidic or basic compound and does not produce acidic or basic compounds upon decomposition.  
     
     
         41 . The epoxy-capped polythioether of  claim 39 , wherein the catalyst comprises a free-radical catalyst.  
     
     
         42 . The epoxy-capped polythioether of  claim 41 , wherein the free-radical catalyst is selected from the group consisting of azo-type catalysts, and alkylperoxides.  
     
     
         43 . An epoxy-capped polythioether formed by reacting a compound having the structure of Formula I,  
         HS—R 1 —SH  I  wherein    R 1  is selected from the group consisting of C 2-6  n-alkylene, C 3-6  branched alkylene, C 6-8  cycloalkylene, C 6-10  alkylcycloalkylene, and —[—(CHR 3 ) p —X—] q —CHR 3 ) r —,    wherein 
 R 3  is selected from H, and —CH 3 ,  
 each X is independently selected from O, S, —NH—, and —NR 4 —,  
 R 4  is selected from H, and —CH 3 ,  
 p is an integer from 2 to 6,  
 q is an integer from 1 to 5, and  
 r is an integer from 2 to 10,  
 or a mixture of at least two different compounds having the structure of Formula I, with a compound having the structure of Formula II:  
                     
   wherein R 2  forms a divalent linking group,    or a mixture of at least two different compounds having the structure of Formula II, and with a polyfunctionalizing agent, or a mixture of at least two different polyfunctionalizing agents.    
     
     
         44 . The epoxy-capped polythioether of  claim 43 , having an average functionality between 2.05 and 3.  
     
     
         45 . The epoxy-capped polythioether of  claim 43 , wherein the polyfunctionalizing agent has a valence of 3.  
     
     
         46 . The epoxy-capped polythioether of  claim 43 , wherein the functionality of the polyfunctionalizing agent is selected from the group consisting of acid groups, amine groups, anhydride groups, and thiol groups.  
     
     
         47 . The epoxy-capped polythioether of  claim 43 , wherein the polyfunctionalizing agent is selected from the group consisting of a polyacid, a polyamine, a polyanhydride, a polythiol, and mixtures thereof.  
     
     
         48 . The epoxy-capped polythioether of  claim 43 , wherein each R 2  comprises an olefin.  
     
     
         49 . The epoxy-capped polythioether of  claim 48 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 20 carbon atoms, and an oxyalkylene having from 3 to 20 carbon atoms.  
     
     
         50 . The epoxy-capped polythioether of  claim 48 , wherein the olefin is selected from the group consisting of an alkylene having from 3 to 5 carbon atoms, and an oxyalkylene having from 3 to 5 carbon atoms.  
     
     
         51 . The epoxy-capped polythioether of  claim 43 , wherein each R 2  is derived from a compound selected from the group consisting of allyl glycidyl ether, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, 4-vinyl-1-cyclohexene 1,2-epoxide, butadiene monoepoxide, isoprene monoepoxide, and limonene monoepoxide.  
     
     
         52 . The epoxy-capped polythioether of  claim 43 , which is free of hydrolysable chlorine.  
     
     
         53 . The epoxy-capped polythioether of  claim 43 , having an epoxy equivalent weight range less than 300.  
     
     
         54 . The epoxy-capped polythioether of  claim 43 , having an epoxy equivalent weight range less than 150.  
     
     
         55 . The epoxy-capped polythioether of  claim 43 , which is formed in the presence of a catalyst selected from the group consisting of a free-radical catalyst, an ionic catalyst, and ultraviolet light.  
     
     
         56 . The epoxy-capped polythioether of  claim 55 , wherein the catalyst does not comprise an acidic or basic compound and does not produce acidic or basic compounds upon decomposition.  
     
     
         57 . The epoxy-capped polythioether of  claim 55 , wherein the catalyst comprises a free-radical catalyst.  
     
     
         58 . The epoxy-capped polythioether of  claim 57 , wherein the free-radical catalyst is selected from the group consisting of azo-type catalysts, and alkylperoxides.