Confined crystallization behaviors of cross-linked comb-like copolymers

Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol (PEG) and methoxy polyethylene glycol (MPEG) by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate (TDI) and/or hexamethylene-1,6-diisocyanate homopolymer (HDI trimer). The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG (M_n = 2000 g/mol) can fold and align easilier than those of MC-PEG (M_n = 2000 g/mol), when the content of PEG is the same.