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Inducing β Phase Crystallinity in Block Copolymers of Vinylidene Fluoride with Methyl Methacrylate or Styrene

机译:偏氟乙烯与甲基丙烯酸甲酯或苯乙烯嵌段共聚物的β相结晶性

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摘要

Block copolymers of poly(vinylidene fluoride) (PVDF) with either styrene or methyl methacrylate (MMA) were synthesized and analyzed with respect to the type of the crystalline phase occurring. PVDF with iodine end groups (PVDF-I) was prepared by iodine transfer polymerization either in solution with supercritical CO2 or in emulsion. To activate all iodine end groups Mn2(CO)10 is employed. Upon UV irradiation Mn(CO)5 radicals are obtained, which abstract iodine from PVDF-I generating PVDF radicals. Subsequent polymerization with styrene or methyl methacrylate (MMA) yields block copolymers. Size exclusion chromatography and NMR results prove that the entire PVDF-I is converted. XRD, FT-IR, and differential scanning calorimetry (DSC) analyses allow for the identification of crystal phase transformation. It is clearly shown that the original α crystalline phase of PVDF-I is changed to the β crystalline phase in case of the block copolymers. For ratios of the VDF block length to the MMA block length ranging from 1.4 to 5 only β phase material was detected.
机译:合成了聚偏二氟乙烯(PVDF)与苯乙烯或甲基丙烯酸甲酯(MMA)的嵌段共聚物,并根据出现的结晶相类型进行了分析。具有碘端基的PVDF(PVDF-1)是通过在超临界CO2溶液中或乳液中进行碘转移聚合制备的。为了活化所有的碘端基,使用Mn 2(CO)10。在紫外线照射下,获得了Mn(CO)5自由基,该自由基从PVDF-1生成PVDF自由基的过程中提取出碘。随后与苯乙烯或甲基丙烯酸甲酯(MMA)聚合,可得到嵌段共聚物。尺寸排阻色谱和NMR结果证明整个PVDF-1被转化。 XRD,FT-IR和差示扫描量热法(DSC)分析可用于鉴定晶体相变。清楚地表明,在嵌段共聚物的情况下,PVDF-1的原始α晶相变为β晶相。对于VDF块长度与MMA块长度的比率,范围为1.4至5,仅检测到β相材料。

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