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Crystallinity in secondary cellulose esters

机译:仲纤维素酯的结晶度

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AbstractCellulose esters which have a high degree of esterification are readily crystallizable by simple heat treatments. Such esters include cellulose triacetate, cellulose tripropionate, and mixed cellulose triesters. X‐ray diffraction analysis shows distinct crystal patterns for these crystalline cellulose esters, and differential thermal analysis shows strong melting peaks. X‐ray diffraction analysis of secondary cellulose esters, that is, esters having a substantially lower degree of esterification, shows very diffuse patterns which are only slightly indicative of crystalline structure. Differential thermal analysis, on the other hand, shows strong endothermic peaks which appear to indicate melting of crystalline material. Once melted, secondary cellulose esters cannot be recrystallized easily by simple heat treatments, but it has been found that treatment with certain solvents will induce crystallization. For instance, precipitation of secondary cellulose acetate from acetic acid gave a material which showed two melting peaks by differential thermal analysis, and precipitation from acetone gave a material which showed a single melting peak. A secondary mixed ester, cellulose acetate butyrate, precipitated from acetone had three melting peaks. The coincidence of two of the peak temperatures of this ester with those of the separate triesters of acetic and butyric acids indicated a block rather than a random substitution into the cellulose ch
机译:摘要 酯化程度高的纤维素酯类,经简单的热处理易结晶。这些酯包括三乙酸纤维素、三丙酸纤维素和混合纤维素三酯。X射线衍射分析显示这些结晶纤维素酯具有不同的晶体图案,差热分析显示强烈的熔融峰。仲纤维素酯(即酯化程度低得多的酯)的X射线衍射分析显示出非常弥漫的图案,仅略微指示晶体结构。另一方面,差热分析显示出强烈的吸热峰,这似乎表明晶体材料熔化。仲次纤维素酯一旦熔化,就不能通过简单的热处理轻易重结晶,但已经发现用某些溶剂处理会诱导结晶。例如,通过差热分析,从乙酸中析出二次醋酸纤维素得到一种材料,该材料显示出两个熔融峰,而丙酮沉淀得到一种材料,该材料显示出一个熔融峰。从丙酮沉淀的仲混合酯,醋酸丁酸纤维素有三个熔点峰。该酯的两个峰值温度与乙酸和丁酸的单独三酯的峰值温度重合,表明纤维素被嵌段而不是随机取代。

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