Copolymerization of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate by rare earth calixarene complexes

Rare earth (Nd, Y, La) p-tert-butylcalix[n]arene (n=4, 6, and 8) complexes alone have been developed to catalyze random and block copolymerizations of trimethylene carbonate (TMC) and 2,2-dimethyltrimethylene carbonate (DTC). The random or block structure and thermal behavior of the copolymers have been characterized by SEC, NMR, DSC, XRD and PLM. Random copolymer with Mw of 14,100 and Mw/Mn of 1.36 was prepared by neodymium p-tert-butylcalix[6]arene complex under the conditions: [TMC+DTC]0/[Nd]=400, 80 °C, 8 h. The reactivity ratios of TMC and DTC are measured to be rTMC=4.68 and rDTC=0.163, respectively. Random copolymerization could be well designed by the feeding ratio to prepare copolymers with controlled Tm and Tg. Only 8% TMC units in the polymer chain destroyed the crystallization of PDTC showing no Tm of the copolymer in the DSC analysis.