热塑性甲壳素衍生物N,O-苄基壳聚糖的合成及表征

天然高分子的热塑化一直引起人们的极大关注．由于存在大量的分子内和分子间氢键,一般天然高分子都不能加热塑化,从而限制了其应用．纤维素和淀粉的热塑化改性已有了许多研究．典型的热塑性纤维素衍生物有乙基纤维素、醋酸纤维素和经丙基纤维素等[1,2],有些纤维素衍生物还具有热致液晶性．淀粉的某些衍生物也已有热塑性[3]．在分子结构上,甲壳素／壳聚糖比纤维素或淀粉多了乙酰氨基和氨基,更易形成氢键,分子间作用力更强．迄今,国内外已报道了大量甲壳素／壳聚糖衍生物,但均无热塑性．我们曾合成具有热塑性的氰乙基经丙基壳聚糖,但熔点与分解温度之间只有27℃E4J．热塑性甲壳素的研究不仅为甲壳素的加工利用开辟了新途径,而且也将为热致性甲壳素液晶的研究奠定基础,从而进一步丰富和深化目前以纤维素衍生物为主的热致胆舀液晶研究[5,6]．为此,本文研究了一种新的热塑性甲壳素衍生物,并从结构上讨论了其具有热塑性的原因．

Synthesis and Characterization of Thermoplastic Chitin Derivative N,O-Benzyl Chitosan

Chitin derivatives are difficult to be melten because of their very strong inter-molecular and intra-molecular hydrogen bonds. In this paper, N,O-benzyl chitosan was synthesized by means of phase-transfer method. The total degree of substitution for this derivative was 0.8 as determined with ¹HNMR and the degree of substitution on nitrogen was 0.3 as determined with elemental analysis. This is a thermoplastic chitin derivative. It's melting point was 470 Kas measured with DSC. Aviscous isotropic melt occurred at the temperatures between the melting point and the decomposition temperature(513K) while N,O-benzyl chitosan was heated on a hot stage. DSC results agreed with the results of microscopy observation. The benzyl group can not form hydrogen bonds. It is also non-polar and has larger volume. These factors weaken the interactions between chitosan chains, and therefore decrease the melting point, which was lower than the decomposition temperature. As a result, N,O-benzyl chitosan was able to melt.