Synthesis and crystallization-induced microphase separation of cellulose triacetate-block-poly(γ-benzyl-l-glutamate)
Synthesis and crystallization-induced microphase separation of cellulose triacetate-block-poly(γ-benzyl-l-glutamate)
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DOI：
10.1007/s10570-014-0383-3
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发表时间：
2014-10-01
期刊：
影响因子：
5.7
通讯作者：
Takano, Toshiyuki
中科院分区：
文献类型：
--
作者：
Kamitakahara, Hiroshi;Baba, Akihiro;Takano, Toshiyuki
本文描述了通过还原端叠氮官能化 CTA 和 C 末端炔官能化 PBLG 之间的铜催化叠氮炔环加成 (CuAAC)，首次观察到薄膜和散装纤维素三乙酸酯嵌段聚（γ-苄基-L-谷氨酸）(PBLG) [纤维素三乙酸酯 (CTA)-b-PBLG] 中结晶诱导的微相分离。将还原端葡萄糖残基 C-1 位氨基对 γ-苄基-1-谷氨酸 N-羧酸酐开环聚合 (ROP) 引发反应的反应性与 CuAAC 的 CTA 还原端叠氮基的反应性进行比较，其中 PBLG 在 C 端带有炔基。尽管CTA还原端的氨基没有表现出作为BLG ROP大引发剂的反应性，但CTA还原端的叠氮基与PBLG C端的炔基反应，得到CTA-b-PBLG。通过H-1-和C-13-核磁共振波谱、红外光谱、差示扫描量热法和广角X射线衍射法对CTA-b-PBLG的结构进行了表征。原子力显微镜、场发射扫描电子显微镜和透射电子显微镜清楚地显示了薄膜和 CTA-b-PBLG 本体的微相分离。
This article describes the first observation of crystallization-induced microphase separation in thin film and bulk cellulose triacetate-block-poly(gamma-benzyl-l-glutamate) (PBLG) [cellulose triacetate (CTA)-b-PBLG] via copper-catalyzed azide-alkyne cycloaddition (CuAAC) between azido-functionalized CTA at the reducing end and alkyne-functionalized PBLG at the C-terminus. The reactivity of the amino group at the C-1 position of the glucosyl residue at the reducing end for the initiation reaction of the ring-opening polymerization (ROP) of gamma-benzyl-l-glutamate N-carboxyanhydride was compared to that of the azido group at the reducing end of CTA for CuAAC, with PBLG bearing an alkyne group at the C-terminus. Although the amino group at the reducing end of CTA exhibited no reactivity as a macroinitiator for ROP of BLG, the azido group at the reducing end of CTA reacted with the alkyne group at the C-terminus of PBLG to afford CTA-b-PBLG. The structure of CTA-b-PBLG was characterized by H-1- and C-13-nuclear magnetic resonance spectroscopies, infrared spectroscopy, differential scanning calorimetry, and wide angle X-ray diffractometry. Microphase separation of the film and bulk of CTA-b-PBLG was clearly shown by atomic force microscopy, field-emission scanning electron microscopy, and transmission electron microscopy.