Tuning the activity of alternative Ru-based initiators for ring-opening metathesis polymerization of norbornene and norbornadiene by the substituent in 4-CH2R-piperidine

Abstract

The novel [RuCl2(PPh3)(2)(4-CH2R-pip)] complexes, with R=H (complex 1), Ph (2) or OH (3), were synthesized and applied as initiators for ROMP of norbornene (NBE) and norbornadiene (NBD) under different reaction times, temperatures and monomer concentrations. There is a clear difference in the homopolymer yields in the order 1 > 2 > 3 at [monomer]/[Ru] molar ratio of 5000, at 25 degrees C for 5-60 min. Difference in the yields tends to disappear at 50 C, with quantitative yields for 15-30 min with any type of initiator. Results from copolymers obtained at RT for 60min from fixed amounts of NBE with four different amounts of NBD suggest that the type of initiator also affects the reactions, with more insertion of NBD with 1. The occurrence of cross-linking enhanced as the NBD loading increased, evidenced by decrease in the M-c and increase in the T-g values, besides the influence of the type of initiator. (C) 2014 Elsevier B.V. All rights reserved.