Crystallization kinetics for semicrystalline random copolymers of vinylidene chloride (VDC) with methyl acrylate (MA), and the effects on the internal morphology of the resin particles formed during synthesis

共聚物 结晶 结晶度 材料科学 共单体 高分子化学 化学工程 聚合物 聚合 丙烯酸甲酯 复合材料 工程类
作者
Elisabeth Bernard,P. T. DeLassus,Bob A. Howell,B.D. Dangel
出处
期刊:Journal of Polymer Science Part B [Wiley]
卷期号:33 (14): 2019-2032 被引量:11
标识
DOI:10.1002/polb.1995.090331404
摘要

Abstract Isothermal crystallization kinetics for random copolymers of vinylidene chloride (VDC) with methyl acrylate (MA) is reported. Syntheses of many semicrystalline polymers follow heterogeneous reaction paths in which the macromolecule chains phase separate from the reaction mixtures. The internal particle morphology (the internal structure of the resin bead) from this type of reaction is granular and porous, as a result of the demixing processes accompanying polymer formation. Demixing in these polymers involves either liquid‐liquid (L‐L) phase separation followed by liquid‐solid (L‐S) transformation (crystallization) or L‐S transformation alone. Crystallization (L‐S transformation) must be an indispensable part of the process if a porous granular structure is to be expected. This is because L‐S transformation is the most probable means by which the demixed structure can be stabilized against complete coalescence or agglomeration, which would lead to totally fused bead internal structure. This is particularly true if the glass transition temperature ( T g ) is lower than the polymerization temperatures, as is the case with the VDC‐MA copolymers. Copolymers that crystallize the fastest will have the finest (most porous) resin bead morphology. The result of this work is consistent with expectation. The homopolymer (PVDC) that crystallizes the fastest has the finest resin bead internal morphology. The copolymers show slower crystallization rates with increasing noncrystallizable MA content. Correspondingly, resin morphology measured by specific surface area decreased with increasing amounts of the noncrystallizable (MA) comonomer unit in the copolymer. This is clearly seen in SEM photographs of the internal bead structures of these copolymers. ©1995 John Wiley & Sons, Inc.
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