本研究以50/50重量百分比，將對排聚苯乙烯(sPS，Mw~200 kg/mol)摻入不同分子量之亂排聚苯乙烯(aPS)中，分子量分別為Mw~3.68 kg/mol (aPS-M)、Mw~300 kg/mol (aPS-H)及Mw~1880 kg/mol (aPS-U)；並以70/30、50/50及30/70重量百分比，將對排聚苯乙烯(sPS，Mw~200 kg/mol)與同排聚苯乙烯(iPS，Mw~400 kg/mol)混摻，得到不同比例雙結晶成分摻合體(sPS/iPS)。利用FTIR結合加熱裝置(hot stage)，再搭配timebase軟體，形成一組time-temperature-resolved FTIR，來探討sPS在不同摻合體中，冷結晶、熔融結晶之結晶行為，以及結晶形態之變化。

冷結晶實驗首先探討neat sPS，經Avrami equation得到n值為~2.9，將k值利用WLF equation分析得到sPS於冷結晶下，分子鏈段運動排列所需的活化能~4.9 kJ/mol；其次，以50/50重量百分比在sPS摻入不同分子量aPS的系統中，sPS/aPS-M的k值會比neat sPS大，sPS/aPS-H及sPS/aPS-U則明顯比neat sPS小，而n值則在2.5附近；對於sPS/iPS的系統，混摻熔融態在OM下可發現有相分離存在，藉由相對結晶度對時間的作圖，可以看出具有二階段的結晶，n值會隨sPS/iPS混摻比例(70/30、50/50及30/70)不同有很大的變化，分別為2.7、2.2及1.1。

由熔融結晶實驗，探討在Tc=250 oC，發現sPS/aPS-M之k值比neat sPS明顯小很多，sPS/aPS-H及sPS/aPS-U則略小neat sPS。其次，sPS/iPS混摻在250 oC等溫結晶結束後，快速降溫至175 oC下等溫結晶，疑似有二階段的結晶，而n值會隨iPS混摻比例的提高明顯下降，分別為3.07、2.86、2.31。此外，高溫狀態下，部分FTIR吸收峰會有往低波數偏移的現象。

In this study, syndiotactic polystyrene (sPS, Mw~200 kg/mol) was blended with different tacticities polystyrene. We used 50/50 weight ratio to blend with three different kinds of molecular weight atactic polystyrene (aPS-M, Mw~3.68 kg/mol; aPS-H, Mw~300 kg/mol; aPS-U, Mw~1880 kg/mol), and blended different ratios (70/30, 50/50 and 30/70) with isotactic polystyrene (iPS, Mw~300 kg/mol). Then, I will discuss the crystallization behavior and morphology of these blends by a new design—time-temperature-resolved FTIR.

The first part is cold crystallization experiment. For neat sPS system, the average n value is about 2.9. Using WLF equation, we can figure out that the activation energy of the sPS chain diffusion is ca. 5.2 kJ/mol. In different molecular weight aPS system, the k values of sPS/aPS-H and sPS/aPS-U blend are bigger than the one of sPS, whereas the k value of sPS/aPS-M blend is smaller than the one of sPS. For all of these sPS/aPS blends, the average n value is about 2.5. In sPS/iPS blend system, we can find the phase separation on melt state. Going a step further to discuss the crystallization behavior, we can observe the two step crystallization obviously by plotting relative crystallinity versus time. And the n values have big difference with different iPS blend ratio (70/30, 50/50 and 30/70)－2.7, 2.2 and 1.1 individually.

In the melt crystallization experiments, we focus on a crystallized temperature－Tc=250 oC to discuss sPS/aPS blend. Unlike the cold crystallization result, the k values of sPS/aPS blend are smaller than the one of sPS. On the other hand, we design the two step crystallization experiment－250 oC to 175 oC to carry out the crystallization behavior of sPS/iPS blend system. The result shows that the higher the iPS blend ratio, the lower the n value－3.1, 2.9 and 2.3 individually. Besides, some FTIR absorbance peak would take place red shift at high temperature state.

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