Synthesis and Crystallization Behavior of Equisequential ADMET Polyethylene Containing Arylene Ether Defects: Remarkable Effects of Substitution Position and Arylene Size

A new series of polyethylene (PE) containing arylene ether units as defects in the main chain, which were precisely separated by 20 CH2 units, were synthesized via acyclic diene metathesis (ADMET) polymerization. The thermal stability, crystallization, and melting behaviors, crystal structure, and chain stacking were investigated with TGA, DSC, WAXD, and SAXS. It is found that the substitution position in the arylene units has a remarkable influence on the chain stacking and their location in the solid phase. The ortho-substituted phenylene units are excluded from the crystal phase, leading to a low melting temperature (Tm). In contrast, the para-substituted phenylene units can be included into the crystal, leading to a high Tm. The meta-substituted phenylene units can be partially included into the crystal, resulting in mixed crystal structures and an intermediate Tm. Such an effect of substitution position in precision PEs is different from that in poly(ethylene oxide) reported in the literature, which ...