Bonding compositions

Abstract

Polymer bonding compositions having greater than about 1 milliequivalent primary amine/100 grams of the polymer, more preferably greater than about 3 milliequivalent non-tertiary amine/100 grams of the polymer. Preferably the polymer is not significantly crosslinked. These bonding compositions may be especially useful for bonding fluropolymers. Processes for making the novel polymers and the resulting multilayer bonded articles are described. The polymers include polymer-bonded ZNHLSi(OP) a (X) 3-a-b (Y) b units. The bonding composition may be used for making multi-layer polymer laminates such as tubes and films and containers.

1 . A polymer comprising greater than about 3 milliequivalent internalized non-tertiary amine per 100 grams of the polymer; 
 wherein the polymer comprises a plurality of internalized polymer-bonded ZNHLSi(OP) a (X) 3-a-b (Y) b  units;    wherein Z is selected from hydrogen or alkyls;    wherein L is selected from divalent alkylenes and L may be interrupted by one or more divalent aromatic groups or heteroatomic groups;    wherein P represents one or more polymer chains;    wherein a is 1 to 3;    wherein a+b=1 to 3;    wherein each X is a hydrolytically stable group;    wherein each Y is a labile group; and    wherein X or Y, when multiple, may be independently chosen.    
     
     
         2 . The polymer of  claim 1  wherein each X is independently selected from alkyl, cycloalkyl, substituted alkyl, substituted cycloalkyl, aryl and substituted aryl groups with the proviso that when 3-a-b=2, X includes divalent alkylene groups thereby cyclized.  
     
     
         3 . The polymer of  claim 1  wherein each Y is independently selected from the groups consisting of unsubstituted or substituted ester, alkoxy, aryloxy, alkyl carbonyloxy, arylcarbonyloxy, hydroxyl, alkylcarboxamino, halo, arylcarboxamido, amino, and ester equivalent groups.  
     
     
         4 . A polymer comprising greater than about 1 milliequivalent internalized primary amine per 100 grams of the polymer; 
 wherein the polymer comprises a plurality of internalized polymer-bonded ZNHLSi(OP) a (X) 3-a-b (Y) b  units;    wherein Z is hydrogen, alkyl, or substituted alkyl including amino-substituted alkyl;    wherein L is a divalent alkylene or substituted alkylene linking group and L may be interrupted by one or more divalent aromatic groups or heteroatomic groups;    wherein P represents one or more polymer chains;    wherein a is 1 to 3;    wherein a+b=1 to 3;    wherein each X is a hydrolytically stable group;    wherein each Y is a labile group; and    wherein X or Y, when multiple, may be independently chosen.    
     
     
         5 . The polymer of  claim 4  wherein the polymer has a gel content or is less than about 10% by weight of the polymer.  
     
     
         6 . The polymer of  claim 1  wherein the polymer comprises a T-type siloxy structure, a D-type siloxy structure, or an M-type siloxy structure.  
     
     
         7 . A bonding composition comprising the polymer of  claim 1  and a phase active agent.  
     
     
         8 . The bonding composition of  claim 7  wherein the phase active agent is selected from the group consisting of a phosphonium salt, an ammonium salt, a fluoroaliphatic sulfonyl compound, and an arylcarboxylic acid.  
     
     
         9 . A bonding composition comprising the reaction product of an amino substituted organosilane ester or ester equivalent and a polymer that has a plurality of polar functionalities combinatively reactive with the silane ester or ester equivalent to displace the ester or ester equivalent groups and wherein the polymer is covalently bonded to the silane via the silicon atom.  
     
     
         10 . The composition of  claim 9  wherein the polymer is selected from the group consisting of ethylenevinyl alcohol copolymer, ethylenevinyl acetate copolymer, polyesters, polycarbonates, polyamides and polyimides.  
     
     
         11 . The composition of  claim 9  wherein the amino substituted organosilane ester or ester equivalent is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane,  
       
         
           
           
               
               
           
         
       
     
     
         12 . A bonding composition comprising the reaction product of an amino substituted organosilane ester or ester equivalent and a polyamide or a thermoplastic polyurethane wherein the reaction product has internalized Si—O—Si and NHR groups.  
     
     
         13 . A bonding composition comprising the reaction product of an amino substituted organosilane ester or ester equivalent and a polymer with anhydride functionality wherein the amount of aminosilane is sufficient to prevent significant crosslinking; wherein the reaction product has internalized Si—O—Si and NHR groups.  
     
     
         14 . A process for making the composition of  claim 1  comprising extruding a mixture of an amino substituted organosilane ester or ester equivalent and a polymer that has a plurality of polar functionalities combinatively reactive with the silane ester or ester equivalent and wherein the polymer is covalently bonded to the silane via the silicon atom.  
     
     
         15 . A process for making a multilayer bonded article comprising co-extruding or laminating the composition of  claim 1  to a fluoropolymer.  
     
     
         16 . A multilayer bonded article comprising the polymer of  claim 1  bonded to a second polymer, which the second polymer may be fluorinated or not.  
     
     
         17 . The multilayer bonded article of  claim 16  wherein the fluoropolymer layer is selected from the group consisting of THV, HTE, PVDF, ETFE and combinations thereof.  
     
     
         18 . The multilayer bonded article of  claim 16  wherein the second polymer is selected from the group consisting of polyamides, polyurethanes, polyesters, polyimides, polycarbonates, polyureas, polyacrylates and polymethylmethacrylate.