Synthesis, kinetic study, and application of Ti[O(CH₂)₄OCHCH₂]₄ in ring‐opening polymerization of ε‐caprolactone and radical polymerization

Abstract

Abstract Ti[O(CH 2 ) 4 OCHCH 2 ] 4 , used for the ring‐opening polymerization (ROP) of ε‐caprolactone, was synthesized through the ester‐exchange reaction of titanium n ‐propoxide and 1,4‐butanediol vinyl ether, and its chemical structure was confirmed by nuclear magnetic resonance ( 1 H NMR) and thermogravimetric analysis (TGA). The mechanism and kinetics of Ti[O(CH 2 ) 4 OCHCH 2 ] 4 ‐initiated bulk polymerization of ε‐caprolactone were investigated. The results demonstrate that Ti[O (CH 2 ) 4 OCHCH 2 ] 4 ‐initiated polymerization of ε‐caprolactone proceeds through the coordination‐insertion mechanism, and all the four alkoxide arms in Ti[O (CH 2 ) 4 OCHCH 2 ] 4 share a similar activity in initiating ROP of ε‐caprolactone. The polymerization process can be well predicted by the obtained kinetic parameters, and the activation energy is 106 KJ/mol. Then, the rheological method was employed to investigate the feasibility of producing the crosslinked poly(ε‐caprolactone)‐poly ( n ‐butyl acrylate) network by using Ti[O(CH 2 ) 4 OCHCH 2 ] 4 as the ROP initiator. The tensile test demonstrates that the in situ generated crosslinked PCL‐PBA network in PMMA matrix provides the possibility of ameliorating the tensile properties of PMMA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7773–7784, 2008