Method of making siloxane-based polymides

Abstract

A method of making siloxane-based polyamides which includes at least one repeating unit represented by the formula wherein X is a linear or branched C 1 -C 30 alkylene chain; Y is a linear or branched C 1 -C 20 alkylene chain; DP is an integer having a value of 10-500; n is an integer having a value 1-500. The method involves heating an intimate reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than 100° C. and forming an organic diamide; and thereafter reacting the organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.

I claim:  
     
       1. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula                    
       wherein X is a linear or branched C 3  to C 10  alkylene chain; Y is a linear or branched C 1 -C 20  alkylene chain; R 1 -R 4  are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500; 
       the method comprising heating a reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than 100° C. and forming an organic diamide; and thereafter reacting the organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.  
     
     
       2. A method according to  claim 1  in which the organic diamine is a compound selected from the group consisting of hexamethylene diamine, ethylene diamine, and decamethylene diamine. 
     
     
       3. A method according to  claim 1  in which the olefinic acid is a compound selected from the group consisting of undecylenic acid, acrylic acid, 3-butenoic acid, and 4-pentenoic acid. 
     
     
       4. A method according to  claim 1  in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard. 
     
     
       5. A method according to  claim 4  in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard. 
     
     
       6. A method according to  claim 1  in which the repeating unit of the siloxane-based polyamide is represented by the formula                    
       wherein X is a linear or branched C 3  to C 10  alkylene chain; Y, Y 1 , and Y 2  are linear or branched C 1 -C 20  alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by                    
       wherein R′, R″, and R″′ are linear or branched C 1 -C 10  alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 1 , or DP1 is not the same as DP2. 
     
     
       7. A method of making a siloxane-based polyamide which includes at least one repeating unit represented by the formula                    
       wherein X is a linear or branched C 3  to C 10  alkylene chain; Y is a linear or branched C 1 -C 20  alkylene chain; R 1 -R 4  are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by 1-3 members which are methyl or ethyl; DP is an integer having a value of 10-500; and n is an integer having a value of 1-500; 
       the method comprising reacting an organic diamide with a hydride-terminated polydimethylsiloxane in the presence of a hydrosilylation catalyst to form the siloxane-based polyamide.  
     
     
       8. A method according to  claim 7  in which the siloxane-based polyamide has a number average molecular weight of from 4,000 to 200,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard. 
     
     
       9. A method according to  claim 8  in which the siloxane-based polyamide has a number average molecular weight of from 5,000 to 65,000 daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard. 
     
     
       10. A method according to  claim 7  in which the repeating unit of the siloxane-based polyamide is represented by the formula                                      
       wherein X is a linear or branched C 3  to C 10  alkylene chain; Y, Y 1 , and Y 2  are linear or branched C 1 -C 20  alkylene chains; DP1, DP2, and DP3 are integers each having values of 10-500; n, m, and p are integers each having values of 1-500; Z is represented by                    
       wherein R′, R″, and R′″ are linear or branched C 1 -C 10  alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by 1-3 members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 1 , or DP1 is not the same as DP2. 
     
     
       11. A method of making a siloxane- based polyamide which includes at least one repeating unit represented by the formula                      
       
         wherein X is a linear or branched C 
         3 
         -C 
         10  
         alkylene chain; Y is a linear or branched C 
         1 
         -C 
         20  
         alkylene chain; R 
         1 
         -R 
         4  
         are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by  1 - 3  members which are methyl or ethyl; DP is an integer having a value of  10 - 500 ; and n is an integer having a value of  1 - 500 ;  
       
         the method comprising heating a reaction mixture containing an olefinic acid and an organic diamine at a temperature greater than  100 ° C. and forming an organic diamide; and thereafter reacting the organic diamide with an ≡SiH containing polysiloxane in the presence of a hydrosilylation catalyst to form the siloxane - based polyamide.   
     
     
       12. A method according to  claim 11  in which the organic diamine is a compound selected from the group consisting of hexamethylene diamine, ethylene diamine, and decamethylene diamine. 
     
     
       13. A method according to  claim 11  in which the olefinic acid is a compound selected from the group consisting of undecylenic acid, acrylic acid,  3 - butenoic acid, and  4   - pentenoic acid.   
     
     
       14. A method according to  claim 11  in which the siloxane- based polyamide has a number average molecular weight of from  4 , 000  to  200 , 000  daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.   
     
     
       15. A method according to  claim 14  in which the siloxane- based polyamide has a number average molecular weight of from  5 , 000  to  65 , 000  daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.   
     
     
       16. A method according to  claim 11  in which the repeating unit of the siloxane- based polyamide is represented by the formula                      
       
         or the formula  
         
           
           
               
               
           
         
       
       
         wherein X is a linear or branched C 
         3 
         -C 
         10  
         alkylene chain; Y, Y 
         1 
         , and Y 
         2  
         are linear or branched C 
         1 
         -C 
         20  
         alkylene chains; DP 1 , DP 2 , and DP 3  are integers each having values of  10 - 500 ; n, m, and p are integers each having values of  1 - 500 ; Z is represented by  
         
           
           
               
               
           
         
       
       
         wherein R′, R″, and R′″ are linear or branched C 
         1 
         -C 
         10  
         alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by  1 - 3  members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 
         1 
         , or DP 1  is not the same as DP 2 . 
       
     
     
       17. A method of making a siloxane- based polyamide which includes at least one repeating unit represented by the formula                      
       
         wherein X is a linear or branched C 
         3 
         -C 
         10  
         alkylene chain; Y is a linear or branched C 
         1 
         -C 
         20  
         alkylene chain; R 
         1 
         -R 
         4  
         are independently methyl, ethyl, propyl, isopropyl, a siloxane chain, phenyl, or phenyl substituted by  1 - 3  members which are methyl or ethyl; DP is an integer having a value of  10 - 500 ; and n is an integer having a value of  1 - 500 ;  
       
         the method comprising reacting an organic diamide with an ≡SiH containing polysiloxane in the presence of a hydrosilylation catalyst to form the siloxane - based polyamide.   
     
     
       18. A method according to  claim 17  in which the siloxane- based polyamide has a number average molecular weight of from  4 , 000  to  200 , 000  daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.   
     
     
       19. A method according to  claim 18  in which the siloxane- based polyamide has a number average molecular weight of from  5 , 000  to  65 , 000  daltons, as determined by gel permeation chromatography using polydimethylsiloxane as a standard.   
     
     
       20. A method according to  claim 17  in which the repeating time of the siloxane- based polyamide is represented by the formula                      
       
         or the formula  
         
           
           
               
               
           
         
       
       
         wherein X is a linear or branched C 
         3 
         -C 
         10  
         alkylene chain; Y, Y 
         1 
         , and Y 
         2  
         are linear or branched C 
         1 
         -C 
         20  
         alkylene chains; DP 1 , DP 2 , and DP 3  are integers each having values of  10 - 500 ; n, m, and p are integers each having values of  1 - 500 ; Z is represented by  
         
           
           
               
               
           
         
       
       
         wherein R′, R″, and R′″ are linear or branched C 
         1 
         -C 
         10  
         alkylene groups; and T is CR in which R is hydrogen, methyl, ethyl, propyl, isopropyl, a siloxane chain, or phenyl, wherein the phenyl may optionally be substituted by  1 - 3  members which are methyl or ethyl, or T is a trivalent atom such as N, P and Al; provided n is not the same as m, or Y is not the same as Y 
         1 
         , or DP 1  is not the same as DP 2 .