Functional Polyisobutylene-Containing Oligomers and Polymers

Abstract

A method of making functional polyisobutylene (PIB)-containing oligomers and polymers. By the disclosed method, the synthesis of functional PIB-containing polymers can be achieved directly under cationic polymerization conditions and does not include any post-polymerization reactions. The desired functionality is introduced by direct Electrophilic Aromatic Substitution (EAS) reaction using substituted phenyl ring carrying desirable functionalities that do not react with Lewis acid but have weak association with Lewis acid, which still allow living polymerization and EAS reaction under living cationic polymerization conditions. In the disclosed method functional polyisobutylene or isobutylene containing oligomers and polymers can be prepared using stoichiometric or near stoichiometric ratios of the capping or functionalization reagent to polymer end-chain.

1 . A method of preparing a PIB oligomer or polymer wherein a ratio of the capping reagent to polymer end-chain calculated as ratio=equivalents of the capping or functionalization reagent/equivalents of polymer end-chain is in the range of 0.7 to 5. 
     
     
         2 . A method of preparing a PIB oligomer or polymer in a one step reaction, comprising reacting components as shown below: 
       
         
           
           
               
               
           
         
       
       where:
 R 1  is an initiator core structure independently selected from alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl and alkoxy; 
 X is an initiating site bonded to the initiator core structure independently selected from halide, alkoxy, ester; 
 m is an integer from about 2 to about 1,000; 
 n is an integer from about 1 to about 20; 
 CAP is a capping reagent selected from one or more of following structures 1 to 3;
 Ar-(EDG-R 2 -Y) q    
 (Ar)p-Ar-(EDG-R 2 -Y) q    
 PAH-(EDG-R 2 -Y) q    
 
 where EDG is an electron donating group selected from O, NR 3 , S, R 4 ; 
 R2 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl; 
 R3 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl; 
 R4 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl; 
 p is an integer from about 1 to about 20; 
 q is an integer from about 1 to about 20; 
 Y can be independently selected from (meth)acrylate, OH, epoxy, oxetane, cyanate, isocyanate, urethane, urea, NR 5 R 6 , SR 7 , Si(OR 5 ) i R 9   3-l , where R 5 , R 6 , R 7 , R 8 , R 9  can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, heteroaryl; and 
 a ratio of the capping reagent to polymer end-chain calculated as ratio=equivalents of the capping or functionalization reagent/equivalents of polymer end-chain is in the range of 0.7 to 5. 
 
     
     
         3 . The method of  claim 2  wherein a ratio of the capping reagent to polymer end-chain calculated is in the range of 0.8 to 2. 
     
     
         4 . The method of  claim 2  wherein a ratio of the capping reagent to polymer end-chain calculated is in the range of 0.9 to 1.1. 
     
     
         5 . The method of  claim 2  wherein a ratio of the capping reagent to polymer end-chain calculated is substantially stoichiometric. 
     
     
         6 . The method of  claim 2  wherein EDG for capping reagent 1) is selected from NR 3 , S, R 4 . 
     
     
         7 . A PIB oligomer or polymer prepared by the method of  claim 1 . 
     
     
         8 . A curable composition comprising the PIB containing oligomer or polymer of  claim 1  and optionally further comprising one or more of a co-monomer, catalyst, filler, antioxidant, reaction modifier, adhesion promoter, rheology modifier. 
     
     
         9 . Cured reaction products of the curable composition of  claim 8 .