Crystallization behavior of oxyethylene/oxybutylene diblock and triblock copolymers

The crystallization behavior of poly(oxyethylene)-b-poly(oxybutylene) block copolymers with different compositions, morphologies and architectures (EmBn diblock copolymers and EmBnEm, BnEmBn triblock copolymers) were investigated and the effect of volume fraction and architecture on the crystallization temperature (Tc) in non-isothermal crystallization was determined. It is found that the EmBn diblock copolymers having long E blocks exhibit similar crystallization temperatures, irrespective of volume fraction and morphology, but for the block copolymers with shorter E blocks the crystallization temperature increases with both the volume fraction, φE, and the length, m, of the E block. Some block copolymers with extremely low Tc, which fall into the temperature range normally associated with homogenous nucleation, were chosen for time-resolved small-angle X-ray scattering (SAXS) and isothermal crystallization kinetics experiments. The results show that breakout crystallization occurs in all these block copolymers. Therefore, unlike EmBn/Bh blends, there is no obvious relationship between Tc and crystallization behavior in neat block copolymers and homogeneous nucleation does not definitely lead to confined crystallization. The values of χc/χODT for all the block copolymers with hex and bcc morphology were also calculated. It is found that all the block copolymers have χc/χODT<3, in agreement with the previously reported critical value and consistent with their breakout crystallization behavior.