Novel methods for forming copolymers comprising olefin and protected or unprotected hydroxystyrene units

Abstract

Novel methods for forming copolymers, including block copolymers, which comprise one or more olefin units and one or more protected or unprotected hydroxystyrene units are provided.

1 - 16 . (canceled) 
     
     
         17 . A copolymer comprising a plurality of constitutional units that correspond to one or more olefin monomer species; a plurality of constitutional units that correspond to one or more protected hydroxystyrene monomer species; and a capping species, wherein the capping species is located between at least one of the olefin monomer species and at least one of the protected hydroxystyrene monomer species, wherein the hydroxystyrene monomer species is selected from hydroxystyrenes protected with one or more groups selected from: 
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2  and R 3  are each independently selected from unbranched or branched alkyl, cycloalkyl or alkylaryl. 
     
     
         18 . The copolymer of  claim 17 , wherein the copolymer has at least one mechanical property that differs less than about 50% between any two points of the copolymer and wherein the property is at least one property selected from hardness, recoil, collapse pressure, longitudinal flexibility, crimp profile, tensile strength, flexural strength, impact resistance, elasticity and compressibility. 
     
     
         19 . The copolymer of  claim 17 , wherein said one or more olefin monomer species are selected from isobutylene, 2-methylbutene, isoprene, 3-methyl-1-butene, 4-methyl-1-pentene and beta-pinene. 
     
     
         20 . The copolymer of  claim 17 , wherein said one or more olefin monomer species comprise isobutylene. 
     
     
         21 . The copolymer of  claim 17 , wherein said protected hydroxystyrene monomer species comprise at least one tert-butyldimethylsilyl protected hydroxystyrene. 
     
     
         22 . The copolymer of  claim 17 , wherein said copolymer is a block copolymer comprising: (a) an olefin block that comprises a plurality of constitutional units corresponding to said one or more olefin monomer species and (b) a styrenic block that comprise a plurality of constitutional units corresponding to said one or more protected hydroxystyrene monomer species. 
     
     
         23 . The copolymer of  claim 22 , wherein said one or more olefin monomer species comprise isobutylene, and wherein said protected hydroxystyrene monomer species are tert-butyldimethylsilyl protected hydroxystyrene. 
     
     
         24 . A composition made by a method of making a block copolymer comprising:
 (a) providing a carbocationically terminated polymer comprising one or more olefin blocks;   (b) contacting under a first reaction condition the carbocationically terminated polymer with a capping species that does not homopolymerize under the first reaction condition, thereby forming an end-capped carbocationically terminated polymer;   (c) altering the first reaction condition to substantially prevent polymerization of protected hydroxystyrene monomer species; and   (d) contacting the end-capped carbocationically terminated polymer with the protected hydroxystyrene monomer species and a Lewis acid that is weaker than TiCl 4  under a second reaction condition, thereby providing a block copolymer.   
     
     
         25 . A composition made by the method of making a block copolymer comprising:
 (a) providing a capped carbocationically terminated polymer;   (b) neutralizing an initiator associated with the capped polymer; and   (c) forming a block copolymer by contacting the capped polymer with a monomer in the presence of a second initiator; wherein the second initiator is a Lewis acid selected from Lewis acids that are weaker than TiCl 4 .