Rubber compositions including siliceous fillers

Abstract

Vulcanizates with desirable properties can be obtained from compositions incorporating polymers that include hydroxyl group-containing aryl functionalities, silica or other particulate filler(s) that contain or include oxides of silicon and a group or compound that can act to covalently bond the filler particles and the polymer. The group can be provided as a substituent of the filler particle, or a discreet compound can be provided in the composition.

1 . A rubber composition comprising
 (a) a polymer comprising ethylenic unsaturation and pendent or terminal functionality that comprises an aryl group comprising at least two OR substituents, wherein R is H or a hydrolyzable group, and   (b) either
 (1) filler particles that comprise oxides of silicon and bound residues of one or more compounds having the general formula YR 1 L, or 
 (2) one or more compounds defined by the general formula YR 1 L and filler particles that comprise oxides of silicon, 
    where Y is a group capable of reacting with said polymer functionality or an oxidation product thereof, R 1  is a hydrocarbylene group, and L is a group that contains at least one Si—O bond.   
     
     
         2 . The rubber composition of  claim 1  wherein said polymer comprises terminal functionality that comprises an aryl group comprising at least two OR substituents. 
     
     
         3 . The rubber composition of  claim 2  wherein said terminal functionality has the general formula 
       
         
           
           
               
               
           
         
       
       where
 Z′ is a single bond or an alkylene group; 
 R 5  is an aryl group comprising two or more OR substituent groups; 
 R 6  is H, a substituted or unsubstituted aryl group which optionally can include one or more hydrolyzable protecting groups, R′, or JR′ where J is O, S, or —NR′ in which each R′ independently is a substituted or unsubstituted alkyl group; and 
 Q″ is the residue of a functionality that is reactive with at least one type of reactive polymer but which itself is non-reactive toward such polymers. 
 
     
     
         4 . The rubber composition of  claim 1  wherein said polymer comprises terminal functionality that comprises an aryl group comprising at least two OH substituents. 
     
     
         5 . The rubber composition of  claim 1  wherein Y comprises an —OH, —SH, —NHR 2 , —CN, —C(O)R 2  or —NCO group where R 2  is H or a substituted or unsubstituted hydrocarbyl group. 
     
     
         6 . The rubber composition of  claim 5  wherein Y is a primary amino group. 
     
     
         7 . The rubber composition of  claim 1  wherein L is defined by —SiR 11   m (OR 11 ) 3-m  where m is 1 or 2 and R 11  is a substituted or unsubstituted hydrocarbyl group, or 
       
         
           
           
               
               
           
         
       
       where n is an integer of from 2 to 5 inclusive, R 2  is H or a substituted or unsubstituted hydrocarbyl group, and is a substituted or unsubstituted hydrocarbyl group. 
     
     
         8 . A vulcanizate prepared from the rubber composition of  claim 1 . 
     
     
         9 . A method of making a rubber composition, said method comprising blending a polymer comprising ethylenic unsaturation and pendent or terminal functionality that comprises an aryl group comprising at least two OR substituents, wherein R is H or a hydrolyzable group, with either
 (1) filler particles that comprise oxides of silicon and bound residues of one or more compounds having the general formula YR 1 L, or   (2) one or more compounds defined by the general formula YR 1 L and filler particles that comprise oxides of silicon,   
       where
 Y is a group reactive with said polymer functionality or an oxidation product thereof, 
 R 1  is a hydrocarbylene group, and 
 L is a group that contains at least one Si—O bond, 
 
       said method optionally further comprising allowing said polymer to covalently bond to said filler particles. 
     
     
         10 . The method of  claim 9  wherein said polymer comprises terminal functionality that comprises an aryl group comprising at least two OR substituents. 
     
     
         11 . The method of  claim 10  wherein said terminal functionality has the general formula 
       
         
           
           
               
               
           
         
       
       where
 Z′ is a single bond or an alkylene group; 
 R 5  is an aryl group comprising two or more OR substituent groups; 
 R 6  is H, a substituted or unsubstituted aryl group which optionally can include one or more hydrolyzable protecting groups, R′, or JR′ where J is O, S, or —NR′ in which each R′ independently is a substituted or unsubstituted alkyl group; and 
 Q″ is the residue of a functionality that is reactive with at least one type of reactive polymers but which itself is non-reactive toward such polymers. 
 
     
     
         12 . The method of  claim 10  wherein said terminal functionality comprises a phenyl group that comprises at least two OR substituents. 
     
     
         13 . The method of  claim 9  wherein said composition comprises one or more compounds defined by the general formula YR 1 L and at least one type of silica. 
     
     
         14 . The method of  claim 9  wherein Y comprises an —OH, —SH, —NHR 2 , —CN, —C(O)R 2  or —NCO group with R 2  being H or a substituted or unsubstituted hydrocarbyl group. 
     
     
         15 . The method of  claim 9  wherein said composition comprises silica particles comprising bound residues of one or more compounds having the general formula YR 1 L. 
     
     
         16 . The method of  claim 9  wherein said polymer comprises terminal functionality that comprises an aryl group comprising at least two OH substituents. 
     
     
         17 . The method of  claim 9  wherein Y is a primary amino group. 
     
     
         18 . The method of  claim 9  wherein L is defined by —SiR 11   m (OR 11 ) 3-m  where m is 1 or 2 and R 11  is a substituted or unsubstituted hydrocarbyl group, or 
       
         
           
           
               
               
           
         
       
       where n is an integer of from 2 to 5 inclusive, R 2  is H or a substituted or unsubstituted hydrocarbyl group, and R 11  is a substituted or unsubstituted hydrocarbyl group. 
     
     
         19 . The method of  claim 9  further comprising blending at least one vulcanizing agent into said rubber composition. 
     
     
         20 . The method of  claim 19  further comprising vulcanizing said rubber composition.