Process for crosslinking of acrylic ester copolymers

Abstract

Disclosed is a process for crosslinking copolymers of acrylic esters by converting some of the ester groups to ester or amide groups which contain unsaturation, and then sulfur or peroxide curing the resulting polymers. The resulting crosslinked polymers often have excellent vulcanizate properties, and are useful especially in elastomeric form as seals and gasket.

1 . A process for crosslinking a polymer, comprising: 
 (a) transesterifying or amidating a first polymer consisting essentially of about 60 or more mole percent of                          and up to about 40 mole percent of one or more comonomers selected from the group consisting of aromatic hydrocarbon olefins, acrylonitrile, olefinic monomers containing one or more functional groups selected from the group consisting of chlorine, epoxy, and carboxylic acid, and cyanoalkyl acrylates wherein alkyl comprises 2-8 carbons, with an alcohol or a primary amine which contains one or more olefinic bonds, to form a second polymer having side chains containing said olefinic bonds; and    (b) crosslinking said second polymer using a sulfur or peroxide cure system;    and wherein:    R 1  is methyl or hydrogen; and    R 2  is hydrocarbyl, substituted hydrocarbyl, or a mixture thereof.    
     
     
         2 . The process as recited in  claim 1  wherein said first polymer is an elastomer.  
     
     
         3 . The process as recited in  claim 2  wherein each R 2  is independently alkyl containing 1-8 carbon atoms optionally substituted by one or more ether oxygens.  
     
     
         4 . The process as recited in  claim 3  wherein R 1  is hydrogen and each R 2  is independently selected from the group consisting of ethyl, butyl, methoxyethyl, ethoxyethyl, and mixtures thereof, with the proviso that at least 50 mol % of the R 2  groups must be ethyl, butyl, or a combination thereof.  
     
     
         5 . The process as recited in  claim 1  wherein said comonomer is acrylonitrile.  
     
     
         6 . The process as recited in claims  1 ,  2 ,  4  or  5  wherein a transesterification is carried out.  
     
     
         7 . The process as recited in  claim 6  wherein a transesterification catalyst is present.  
     
     
         8 . The process as recited in  claim 7  wherein said catalyst is a tetraalkyl titanate or a tin compound.  
     
     
         9 . The process as recited in  claim 6  wherein said alcohol has the formula HR 3 (CR 4 ═CR 5 R 6 ) t CH 2 OH wherein R 3  and each R 5  are each independently a covalent bond, alkylene or alkylidene, and R 4  and R 6  are each independently hydrogen or alkyl, and t is 1, 2 or 3.  
     
     
         10 . The process as recited in  claim 6  wherein said alcohol is one or more of oleyl, linoleyl or linolenyl alcohols.  
     
     
         11 . The process as recited in  claim 1  wherein during (b) said first polymer is also present, provided that said second polymer is at least 20% by weight of the total of said first polymer and said second polymer.  
     
     
         12 . A composition comprising: 
 (a) a second polymer made by transesterifying or amidating a first polymer consisting essentially of about 60 or more mole percent of                          and up to about 40 mole percent of one or more comonomers selected from the group consisting of aromatic hydrocarbon olefins, acrylonitrile, olefinic monomers containing one or more functional groups selected from the group consisting of chlorine, epoxy, and carboxylic acid, and cyanoalkyl acrylates wherein alkyl comprises 2-8 carbons, with an alcohol or a primary amine which contains one or more olefinic bonds; and    (b) a sulfur or peroxide cure system;    and wherein: 
 R 1  is methyl or hydrogen; and  
 R 2  is hydrocarbyl and/or substituted hydrocarbyl.  
   
     
     
         13 . The composition as recited in  claim 12  wherein said first polymer is an elastomer.  
     
     
         14 . The composition as recited in  claim 13  wherein each R 2  is independently alkyl containing 1-8 carbon atoms optionally substituted by one or more ether oxygens.  
     
     
         15 . The composition as recited in  claim 14  wherein R 1  is hydrogen and each R 2  is independently selected from the group consisting of ethyl, butyl, methoxyethyl, ethoxyethyl, and mixtures thereof, with the proviso that at least 50 mol % of the R 2  groups must be ethyl, butyl, or a combination thereof.  
     
     
         16 . The composition as recited in  claim 13  wherein said comonomer is acrylonitrile.  
     
     
         17 . The composition as recited in  claim 12  further comprising up to 80% by weight of a polymer consisting essentially of at least 60 mole percent of  
       
         
           
           
               
               
           
         
       
       and up to about 40 mole percent of one or more comonomers selected from the group consisting of aromatic hydrocarbon olefins, acrylonitrile, olefinic monomers containing one or more functional groups selected from the group consisting of chlorine, epoxy, and carboxylic acid, and cyanoalkyl acrylates wherein alkyl comprises 2-8 carbons, and wherein R 1  is methyl or hydrogen; and R 2  is hydrocarbyl, substituted hydrocarbyl, or a mixture thereof.  
     
     
         18 . A composition comprising: 
 (a) a polymer consisting essentially of at least 60 mole percent of                          and up to about 40 mole percent of one or more comonomers selected from the group consisting of aromatic hydrocarbon olefins, acrylonitrile, olefinic monomers containing one or more functional groups selected from the group consisting of chlorine, epoxy, and carboxylic acid, and cyanoalkyl acrylates wherein alkyl comprises 2-8 carbons; and    (b) a sulfur or peroxide cure system;    wherein:    R 1  is methyl or hydrogen; and R 2  is hydrocarbyl, substituted hydrocarbyl, or a mixture thereof, provided that at least 0.5 mole percent of R 2  contains olefinic unsaturation.    
     
     
         19 . The composition as recited in  claim 18  wherein said polymer is an elastomer.  
     
     
         20 . The composition as recited in  claim 19  wherein each R 2  which does not contain olefinic unsaturation is independently alkyl containing 1-8 carbon atoms optionally substituted by one or more ether oxygens.  
     
     
         21 . The composition as recited in  claim 20  wherein R 1  is hydrogen and R 2  which does not contain unsaturation is selected from the group consisting of ethyl, butyl, methoxyethyl, ethoxyethyl, and mixtures thereof.  
     
     
         22 . The composition as recited in  claim 19  wherein said polymer consists essentially of 100 mol % of (I).  
     
     
         23 . The composition as recited in  claim 18  further comprising up to 80% by weight of a polymer consisting essentially of about 60 or more mole percent of  
       
         
           
           
               
               
           
         
       
       and up to about 40 mole percent of one or more comonomers selected from the group consisting of aromatic hydrocarbon olefins, acrylonitrile, olefinic monomers containing one or more functional groups selected from the group consisting of chlorine, epoxy, and carboxylic acid, and cyanoalkyl acrylates wherein alkyl comprises 2-8 carbons, and wherein R 1  is methyl or hydrogen; and R 2  is hydrocarbyl, substituted hydrocarbyl, or a mixture thereof; provided that none of R 2  contains olefinic unsaturation.  
     
     
         24 . The process as recited in  claim 1  or  6  wherein said first polymer is dried before step (a).  
     
     
         25 . The product of the process of  claim 1 ,  6  or  7 .