Phase separation and polymer crystallization in a poly(4-methyl-1-pentene)- dioctylsebacate-dimethylphthalate system via thermally induced phase separation

The effects of the polymer concentration and quenching temperature on the phase separation, the membrane morphology and polymer crystallization behavior in a poly(4-methyl-1-pentene) (TPX)-dioctylsebacate (DOS)-dimethylphthalate (DMP) system via thermally induced phase separation were studied with a pseudobinary phase diagram, with the weight ratio of DOS:DMP = 1:1. SEM was used to observe the membrane morphology and structure, whereas the TPX crystallization behavior was studied with DSC and WAXD. Liquid-liquid phase separation occurred, although quenching under the crystallization temperature. As the quenching temperature decreased, the pore size decreased, with better connected pore structure formed. The membranes quenched at 333 and 363 K showed good cellular structures, with an average pore size of about 2.3μm, whereas the pores of the membranes quenched at 393 and 423 K were not well formed, with some lamellar crystals on the inner side. The diluent assisted the mobility of the polymer chain, which improved the polymer crystallization. Dual-melting-peak behavior occurred for all the samples studied here. As the quenching temperature increased, the first peak of the melting trace moved to a higher temperature, whereas the second one stayed almost the same. The flexibility of the TPX main chain was restricted by the side groups, which allowed liquid-liquid phase separation to occur first when quenched below the equilibrium crystallization temperature. This allowed primary and secondary crystallization, which was responsible for the dual-melting-peak behavior.