Control of free-radical polymerization of 2,2,2-trifluoroethyl methacrylate (TEMA) by a substituted fluorinated tetraphenylethane-type INITER

This paper deals with the free radical polymerization of 2,2.2-trifluoroeth yl methacrylate (TEMA) initiated by a substituted fluorinated tetraphenylet hane-type INITER. The synthesis of a new fluorinated substituted tetraphenylethane is describ ed. This initiator, prepared from benzophenone: and 3,3,3(trifluoropropyl)c hlorodimethylsilane behaves as an INITER when used to polymerize TEMA. In t he first period of polymerization. telechelic oligomers are formed. They we re isolated from the mixture and their structure was characterized by H-1-N MR spectroscopy, By thermal cleavage at the bonds between the last monomer unit and the end groups from the: initiates, these telechelic oligomers are effective initiators of further free-radical polymerization of ethylenic m onomers, yielding block copolymers besides the respective homopolymer. Thus , in a second step, styrene was introduced into poly(TEMA) to produce block copolymers with a macroinitiator efficiency dose to 85%. (C) 2001 Elsevier Science B.V. All rights reserved.