End-capped polymer chains and products thereof

Abstract

According to an aspect of the present invention, a method is provided in which a double diphenylethylene compound is reacted with a polymer that contains a carbocationically terminated chain thereby providing a 1,1-diphenylene end-functionalized chain. Subsequently, an alkylating agent is reacted with the 1,1-diphenylene end-functionalized chain, thereby providing an alkylated 1,1-diphenylene end-functionalized chain. In some embodiments, the method further comprises (a) optionally combining a 1,1-diphenylorganolithium compound with the alkylated 1,1-diphenylene end-functionalized polymer followed by (b) reacting an organolithium compound with the alkylated 1,1-diphenylene end-functionalized polymer. This provides an anionically terminated polymer, which can be used, for example, in subsequent anionic polymerization and coupling reactions. According to another aspect of the present invention, a novel polymer is provided that comprises a polymer chain, which chain further comprises the following: (a) a plurality of constitutional units that correspond to cationically polymerizable monomer species and (b) an end-cap comprising a group or a group, where R is a branched or unbranched alkyl group containing from 1 to 20 carbons and R 1 is a branched, unbranched, or cyclic alkyl group or an aryl group, containing from 1 to 20 carbons. Other aspects of the present invention relate to novel copolymers that comprise: (a) a first polymer block that comprises a plurality of constitutional units that correspond to isobutylene; and (b) a second polymer block that comprises a plurality of constitutional units that correspond to hydroxyethyl methacrylate.

1 . A method comprising:
 (a) contacting under reaction conditions a double diphenylethylene compound with a polymer that comprises a carbocationically terminated chain, said chain further comprising a plurality of constitutional units that correspond to cationically polymerizable monomer species, thereby providing a 1,1-diphenylene end-functionalized chain; and   (b) contacting under reaction conditions said 1,1-diphenylene end-functionalized chain with an alkylating agent, thereby providing an alkylated 1,1-diphenylene end-functionalized chain.   
     
     
         2 . The method of  claim 1 , wherein said alkylating agent is an alkylaluminum compound or an alkylzinc compound. 
     
     
         3 . The method of  claim 1 , wherein said alkylating agent is dimethylzinc. 
     
     
         4 . The method of  claim 1 , wherein said double diphenylethylene compound is 1,4-bis(1-phenylethenyl)benzene. 
     
     
         5 . The method of  claim 1 , further comprising contacting, under reaction conditions, an organolithium compound with said alkylated 1,1-diphenylene end-functionalized polymer, thereby providing an anionically terminated polymer. 
     
     
         6 . The method of  claim 5 , wherein said organolithium compound is of the formula RLi in which R is a hydrocarbon group containing from 1 to 20 carbon atoms per molecule selected from alkyl groups, aryl groups, and alkyl-aryl groups. 
     
     
         7 . The method of  claim 5 , wherein said organolithium compound is selected from methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, p-tolyllithium, cyclohexyllithium, and 4-cyclohexylbutyllithium. 
     
     
         8 . The method of  claim 5 , further comprising combining a 1,1-diphenylorganolithium compound with said alkylated 1,1-diphenylene end-functionalized polymer prior to contact with said organolithium compound. 
     
     
         9 . The method of  claim 8 , wherein the 1,1-diphenylorganolithium compound is of the formula RC(Ø) 2 Li in which R is a hydrocarbon group containing 1 to 20 carbon atoms per molecule and Ø is an unsubstituted or substituted aryl group. 
     
     
         10 . The method of  claim 5 , wherein the 1,1-diphenylorganolithium compound is 1,1-diphenylhexyllithium or 1,1-diphenyl-4-methylpentyllithium. 
     
     
         11 . The method of  claim 5 , further comprising contacting under reaction conditions said anionically terminated polymer with anionically polymerizable monomer species. 
     
     
         12 . The method of  claim 11 , wherein said cationically polymerizable monomer species are isoolefin monomer species and wherein said anionically polymerizable monomer species are methacrylate monomer species. 
     
     
         13 . A copolymer comprising:
 (a) a first polymer block that comprises a plurality of constitutional units that correspond to isobutylene; and   (b) a second polymer block that comprises a plurality of constitutional units that correspond to hydroxyethyl methacrylate.   
     
     
         14 . The copolymer of  claim 13 , wherein said second polymer block comprises a plurality of constitutional units that correspond to hydroxyethyl methacrylate and a plurality of constitutional units that correspond to methyl methacrylate. 
     
     
         15 . The copolymer of  claim 13 , wherein said first polymer block is a polyisobutylene block and said second polymer block is a poly(hydroxyethyl methacrylate) polymer block. 
     
     
         16 . The copolymer of  claim 13 , wherein said first polymer block is a polyisobutylene block and wherein said second polymer block contains, arranged within said second block in a random fashion, a plurality of constitutional units that correspond to hydroxyethyl methacrylate and a plurality of constitutional units that correspond to methyl methacrylate.