Study on Synthesis of Tailor-Made Block Copolymers Having Side Chains of Liquid Crystal and its Application to Recording Materials.

具有液晶侧链的特制嵌段共聚物的合成及其在记录材料中的应用研究。

• 批准号: 01850201
• 负责人: ISONO Yoshinobu
• 金额: $ 4.42万
• 依托单位: Nagaoka University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B).
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01850201/
• 关键词: Block Copolyemr; Poly (Aminostyrene; N, N-Dimethyl-4-Vinylphenetylamine; Poly (N, N-Dimethyl-4-Vinylphenethylamine); Molecular Memory; Photocromism; Anionic Polymerization; Cross-Linking by Quarternization; 側鎖型ブロック共重合体液晶; 4ービニルーNーイソプロペニルーNートリメチルシ

To obtain a molecular memory, one needs not only the conditions, easy isomerization of dye to metastable state in recording, suppression of thermal backward isomerization in keeping, and easy backward isomerization in deleting, but also high mechanical strength. For the purpose, it is desirable to use bifunctional die as cross-linker onto block copolymer having a component of high glass transition temperature. It was found that N, N-dimethyl-4-vinylphenethylamine (PTA) is an appropriate monomer for the present purpose. Preparation and purification of PTA monomer is not so difficult. PTA can be polymerized anionically in THF at 195K with cumyl potassium or cumyl cesium as an initiator. The obtained poly (PTA) has a narrow molecular weight distribution. A well defined diblock copolymer, poly (PTA-b-styrene) can be obtained, if PTA is polymerized prior to styrene. The glass transition temperature of poly (PTA) is 315K. A quarternization of the block copolymer with p, p'-bis (chloromethyl) azo-benzene (CAB) can be easily carried out in a membrane form. An isomerization of such incorporated CAB from trans to cis form can be made by irradiation of UV light. Thermal backward isomerization is negligible at room temperature but easy at a temperature higher than the glass transition temperature of poly (PTA). These facts allow us to make a molecular memory by the use of poly (PTA) and CAB.

为了获得分子存储器，不仅需要在记录时染料容易异构化到亚稳态、在保持时抑制热反向异构化和在删除时容易反向异构化的条件，而且需要高机械强度。为此目的，期望使用双官能模具作为具有高玻璃化转变温度的组分的嵌段共聚物上的交联剂。发现N，N-二甲基-4-乙烯基苯乙胺（PTA）是用于本目的的合适单体。PTA单体的制备和提纯并不困难。PTA可以在THF中，以枯基钾或枯基铯为引发剂，在195 K下进行阴离子聚合。所得聚（PTA）具有窄的分子量分布。如果PTA在苯乙烯之前聚合，则可以获得定义明确的二嵌段共聚物，聚（PTA-b-苯乙烯）。聚（PTA）的玻璃化转变温度为315 K。嵌段共聚物与p，p '-双（氯甲基）偶氮苯（CAB）的季铵化可以容易地以膜形式进行。这种掺入的CAB从反式到顺式的异构化可以通过UV光照射进行。热反向异构化在室温下可以忽略不计，但在高于聚（PTA）的玻璃化转变温度的温度下容易发生。这些事实使我们能够通过使用聚（PTA）和CAB来制造分子存储器。

项目成果

Masato Kijima, Kazunori Se, Yoshinobu Isono, and Teruo Fujimoto: "Temperature Dependence of photochemical Isomerization of p, p'-Bis (chloromethyl) azo-benzene Incorporated in Diblock Copolymer by Cross Linkage."

Masato Kijima、Kazunori Se、Yoshinobu Isono 和 Teruo Fujimoto：“通过交联结合到二嵌段共聚物中的对，对-双（氯甲基）偶氮苯的光化学异构化的温度依赖性”。

Masato Kijima,Kazunori Se,and Teruo Fujimoto: "Photochemical Isomerization of p,p'ーBis(chloromethyl)azobenzene Incorporated in Poly(tertiary aminostyrenes) by Cross Linkage." Polymer.

Masato Kijima、Kazunori Se 和 Teruo Fujimoto：“通过交联将对，对-双（氯甲基）偶氮苯光化学异构化到聚（叔氨基苯乙烯）中。”

Masato Kijima,Kazunori Se,Yoshinobu Isono,and Teruo Fujimoto: "Temperature Dependence of Photochemical Isomerization of p,p'ーBis(chloromethyl)azobenzene Incorporated in Diblock Copolymer by Cross Linkage."

Masato Kijima、Kazunori Se、Yoshinobu Isono 和 Teruo Fujimoto：“通过交联结合到二嵌段共聚物中的对，对-双（氯甲基）偶氮苯光化学异构化的温度依赖性”。

Masato Kijima, Reiko Ootomo, Kazunori Se, and Teruo Fujimoto: "Quarternization of Poly (tertiary aminostyrenes) and Characterization of Quarternized Polymers." J. Polym. Sci., Polym. Chem. Ed.

Masato Kijima、Reiko Ootomo、Kazunori Se 和 Teruo Fujimoto：“聚（叔氨基苯乙烯）的季铵化和季铵化聚合物的表征”。

Masato Kijima,Reiko Ootomo,Kazunori Se,and Teruo Fujimoto: "Quarternization of Poly(tertiary aminostyrenes) and Characterization of Quarternized Polymers." J.Polym.Sci.,Polym.Chem.Ed.

Masato Kijima、Reiko Ootomo、Kazunori Se 和 Teruo Fujimoto：“聚（叔氨基苯乙烯）的季铵化和季铵化聚合物的表征”。