Molecular design of cellulosic thermotropic liquid crystals

纤维素热致液晶的分子设计

• 批准号: 07456080
• 负责人: NAKATSUBO Fumiaki
• 金额: $ 4.22万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07456080/
• 关键词: cellulosic liquid crystal; regiospecific substituted derivatives; ring-opening polymerization; substituent effect; 2-propyl cellulose; 2-allkyl cellulose; 2-acyl cellulose; solubility and themal behavior; 内部可塑剤; 主鎖型液晶ポリマー; 流動複屈折現象; 側鎖型液晶ポリマー

From the results of this former research period, it was found that it is indispensable to establish the synthetic method for cellulose for investigating the relationship between structure and property of cellulosic liquid crystals. At present, the regiospecific introduction of the desired functional groups into the 2-or 3-position of cellulose is impossible, but this may be possible by the chemical synthetic method of cellulose. We established the chemical synthetic method cellulose in last year. In this year, we first of all investigated the substituent effect on the polymerization to clarify the reaction mechanism. It was found that 3-O-benzyl group is indispensable for the stereo-and regioregularity, and 2-O-pivaloyl group for regiospecific polymerization. We also succeeded in the stepwise synthesis of celloeicosaose with DP 20. Thus, the method yielding regiospecific substituted cellulose derivatives was established. Then, 2-propyl cellulose was first synthesized as an example. Consequently, it is indicated that the present synthetic method is useful for getting 2-O-alkyl and, probably, also 2-acylated cellulose derivatives. The solubility and thermal behavior of 2-propyl cellulolse were examined resulting several interesting findings. Thus the method for accumulating basic knowledge about cellulosic liquid crystalline properties was established.

从前期的研究结果可以看出，建立纤维素的合成方法对于研究纤维素液晶的结构与性能之间的关系是必不可少的。目前，不可能在纤维素的2-或3-位上特定区域地引入所需的官能团，但这可能通过纤维素的化学合成方法来实现。我们在去年建立了化学合成法纤维素。在这一年里，我们首先研究了取代基对聚合反应的影响，以阐明反应机理。结果表明，3-O-苄基对立体规整性和区域规整性是必不可少的，2-O-新戊酰基对区域专一性聚合是必不可少的。我们还成功地用DP20进行了纤维二十糖的分步合成，从而建立了区域特异性取代纤维素衍生物的合成方法。然后，以2-丙基纤维素为例进行了首次合成。结果表明，该合成方法可用于合成2-O-烷基，也可能是2-酰化纤维素衍生物。研究了2-丙基纤维素的溶解性和热行为，得到了几个有趣的发现。从而建立了积累纤维素液晶性质基础知识的方法。

项目成果

Michiko Hori: "Substituent effects of orthoester group on ring-opening polymerization of a-D-glucose 1,2,4-orthoester derivatives" Macromolecules accepted.

Michiko Hori：“原酸酯基团对α-D-葡萄糖1,2,4-原酸酯衍生物开环聚合的取代效应”《高分子》接受。

Takeshi Nishimura: "First synthesis of cellooctaose by a convergent synthetic method" Carbohydr. Res.294. 53-64 (1996)

Takeshi Nishimura：“通过聚合合成方法首次合成纤维八糖”碳水化合物。

Hiroshi Kamitakahara: "Substituent Effect on Ring-Opening Plolymerization of Regioselectively Acylated 1,4-Anhydro-α-D-glucopyranose Derivatives" Macromolecules. 29. 1119-1122 (1996)

Hiroshi Kamitakahara：“取代基对区域选择性酰化 1,4-脱水-α-D-吡喃葡萄糖衍生物的开环聚合的影响”29. 1119-1122 (1996)。

Takeshi Nishimura: "First stepwise synthesis of cellulose analoges" Tetrahedron Lett.37(51). 9215-9218 (1996)

Takeshi Nishimura：“纤维素类似物的首次逐步合成”Tetrahedron Lett.37(51)。

Hiroshi Kamitakahara: "Substituent effect on ring-opening polymerization of regioselective acylaed alpha-D-glucose 1,2,4-orthopyvalate derivatives" Macromolecules. 29-19. 6126-6131 (1996)

Hiroshi Kamitakahara：“取代基对区域选择性酰基化 α-D-葡萄糖 1,2,4-原戊酸衍生物开环聚合的影响”大分子。