Polymerization of Diacetylenes in Orderd Reaction Medium

有序反应介质中丁二炔的聚合

• 批准号: 05640666
• 负责人: SUGAWARA Tadashi
• 金额: $ 1.22万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1994
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05640666/
• 关键词: Liquid Crystal Phase Polymerization; Polydiacetylenes; Nematic Phase; Design of Reaction Environment; ネマチック液晶; 反応性中間体; ビラジカル; リビングオリゴマー

Diacethylene derivative carrying a mesogenic core has been prepared and its kinetic behavior of the nematic phase polymerization has been investigated. The obtained results are as follows.1) Diacethylene trimer carrying cyclopropene rings was isolated. The trimer generates a biradical, which has a thermally accessible tripler state (D=0.00253 cm^<-1>, E=0.00041 cm^<-1>), through the ring cleavage by UV irradiation or by heating at temperatures higher than 90ﾟC.2) The molecular and electronic structure of the biradical was calculated by GVB method in collaboration with Prof.S.Nagase (Yokohoma National Univ.). The calculated result is consistent with the experimental result.3) Template effect of the trimer or the pentamer on the oligomerization process of diacethlenes was discovered.These kinetic features can be well rationalized by the flexibility and orderness of the reaction environment of the nematic phase.

已经制备了二甲基衍生物携带中源核心，并且已经研究了其列中相聚合的动力学行为。所获得的结果如下。1）分离出二甲基三聚体携带环丙烯环。该扳机会产生一个Biradical，其具有易于访问的三重态状态（d = 0.00253 cm^<-1>，E = 0.00041 cm^<-1>），通过紫外线辐照或在温度下进行加热的环裂解，高于90°C.2 C.2 C.2）由Biradical的分子和电子结构与Biradical Conteration contection cartection。 Nagase（Yokohoma National Univ。）。计算出的结果与实验结果一致。3）触发器的模板效应或五聚体对二乙烯的寡聚过程的影响。这些动力学特征可以通过确定相反应环境的灵活性和有序性来很好地理解这些动力学特征。

项目成果

Tadashi Sugawara: "Structure and properties of overcrowed condensed polycyclic aromatic hydrocarbons" Toyota Kenkyu Hokoku. 46. 165-173 (1993)

菅原正：“拥挤的稠合多环芳烃的结构和性质”丰田建久报国。

R.Kumai et al.: "Intramolecular Exchange Interaction in Novel Cross-Conjugated Spin System Composed of π-Ion Radical and Nitronyl Nitroxide" J.Am.Chem.Soc.116. 4523-4524 (1994)

R.Kumai 等人：“由 π 离子自由基和硝基硝基氧化物组成的新型交叉共轭自旋系统中的分子内交换相互作用”J.Am.Chem.Soc.116 (1994)。

T.Sugawara et al.: "An Organic Ferromagnet : alpha-Phase Crystal of 2- (2', 5'-Dihydroxyphenyl) -4,4,5,5-tetramethyl 1-4,5-dihydro-1H-imidazolyl-1-oxy-3-oxide (alpha-HQNN)" J.Chem.Soc., Chem.Commun.1723-1724 (1994)

T.Sukawara 等人：“有机铁磁体：2-（2, 5-二羟基苯基）-4,4,5,5-四甲基 1-4,5-二氢-1H-咪唑基-的 α 相晶体

Tadashi Sugawara: "How can crystalline environment provide outstanding stability and chemistry in molecular crystals" “Chemical Reaction in Molecular Crystals"Kodansha,Tokyo and VCH,Weinheim eds.Y.Ohashi, 12 (1993)

Tadashi Sukawara：“结晶环境如何在分子晶体中提供出色的稳定性和化学性”“分子晶体中的化学反应”讲谈社，东京和 VCH，Weinheim eds.Y.Ohashi，12 (1993)

A.Izuoka et al.: "Magnetically Conpled Molecular System Composed of Organic Radicals with Different Spin Multiplicities" J.Am.Chem.Soc.116. 2609-2610 (1994)

A.Izuoka 等人：“由具有不同自旋多重性的有机自由基组成的磁耦合分子系统”J.Am.Chem.Soc.116。