本實驗利用微分掃描式熱卡計(DSC)、偏光顯微鏡(POM)以探討poly (vinyl methyl ether) (PVME)與一系列聚酯類高分子(CH2/CO=2~7)摻合系統之相容性與其作用力。分析改變聚酯類高分子主鏈上CH2/CO的比值對於摻合系統相行為的影響。當聚酯類高分子主鏈上CH2/CO=3.5~7時與poly (vinyl methyl ether)為相容系統。進一步利用DSC測量玻璃轉移溫度和作用力參數證明相容性。對於相容系統皆存在有單一玻璃轉移溫度，並發現對於高結晶度高分子(如PBA、PHA、PCL、PHS)，其玻璃轉移溫度明顯與低結晶度高分子(如PTA、PEAz)有所不同。在高結晶度的聚酯類高分子含量多時，玻璃轉移溫度存在有明顯正偏差。並利用平衡熔點求出相容系統的作用力參數為-0.17~-0.33，且存在有最大值，因此可知聚酯類高分子(CH2/CO=3.5~7)與poly (vinyl methyl ether)為相容系統，且沒有特殊作用力存在。再進一步探討含有相同碳數比(CH2/CO)的PHA和PCL在加入PVME後，其球晶與regime的關係。

Various phase behavior of blends of poly(vinyl methyl ether) (PVME) with a series of polyesters with different ratios of aliphatic carbons to ester groups were examined using differential scanning calorimetry (DSC) and optical microscopy (OM). Effects of varying the main-chain polarity of the constituent polyesters on the phase behavior of the blends were analyzed. Miscibility in PVME/polyester blends were found only in polyesters with backbone CH2/CO ratio = 3.5 to 7.0. Tg-composition relationships for blends of PVME with highly crystalline polyesters (PBA, PHA, PCL, PHS) were found to differ significantly from those for PVME blends with less-crystalline polyesters (PTA, PEAz). Crystallinity of highly-crystalline polyester constituents in blends caused significant asymmetry in the Tg-composition relationships, and induced positive deviation of blends’ Tg above linearity; on the other hand, blends of PVME with less crystalline polyesters exhibit typical Fox or Gordon-Taylor types of relationships. The interaction parameters for the miscible blends were found to range from -0.17 to -0.33, reflecting generally weak interactions. Phase behavior was analyzed and compared among blends of PVME with rapidly-crystallizing vs. less-crystallizing polyesters, respectively. Effects of polyesters’ crystallinity and structures on phase behavior of PVME/polyester blends are discussed. As analogous polyester to PCL, PHA (with the same CH2/CO ratio) was used for comparison purpose; however, PHA has a stronger tendency for crystallization than PCL. Both PVME/PCL and PVME/PHA blends were proven to be miscible with weak and non-specific interactions, which is typical in blends involving ether-containing and carboxyl-containing polymers. Difference in spherulite ring-band patterns between neat PCL, neat PHA and miscible blends was probed to correlate with growth regimes. Spherulite growth in thin-film forms and transformation of spherulite patterns in different regimes were investigated. For neat PCL, in transition from regime III to regime II, the spherulites are patterned in ring-less to ring-banded types, respectively, in different regimes. For the PVME/PCL (20/80) blend, ring bands in spherulites are easily seen in Regime-III, but ring bands disappear in Regime-II. For neat PHA, in transition from regime II to regime I, the spherulites are patterned in ring-banded to ring-less types. For the PVME/PHA (20/80) blend, ring bands in spherulites are easily seen only in crystallization from Tc=40 ~ 42oC (Regime-II), but ring bands disappear in crystallization from Tc=30 ~ 38oC (Regime-II) and Tc=46 ~ 50oC (Regime-I).

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