Intramolecular and Intermolecular Interactions of Polymers with Heteroatoms

聚合物与杂原子的分子内和分子间相互作用

• 批准号: 14550842
• 负责人: SASANUMA Yuji
• 金额: $ 1.98万
• 依托单位: Chiba University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14550842/
• 关键词: intramolecular and intermolecular interactions; conformation; polyether; polysulfide; polyimine; polysilane; polymer liquid crystal; lyotropic liquid crystal; 溶融高分子; 液晶; 分子内相互作用; 分子間相互作用

(1)Intramolecular Interactions of PolysulfidesConformational characteristics of poly(ethylene sulfide) and poly(propylene sulfide) in the theta state have been investigated by NMR experiments and ab initio molecular orbital (MO) calculations for the monomeric model compounds and RIS analysis of configuration-dependent properties of the polymers, and compared with those off the corresponding polyethers. The high melting points of the polysulfides have been elucidated in terms of configuration entropy and intermolecular interactions.(2)Conformational Analysis of Poly(ethylene imine) (PEI)Conformational energies of PEI have been evaluated from MO calculations and NMR experiments for its monomeric model compound, N,N'-dimethylethylenediamine. The chain dimension of PEI was calculated as a function of the hydrogen-bond energy. The enthalpy of the intermolecular hydrogen bond formed in the double-stranded helix was also estimated from MO calculations.(3)Conformational Analysis of PolysilanesConformational characteristics of poly(di-n-butylsilane), poly(di-n-hexylsilane), and poly(methyl-n-propylsilane) have been investigated by a rotational isomeric state scheme with molecular dynamics simulations. Characteristic ratios thus calculated were in fairly good agreement with those determined by light scattering. The phase transition, solubility, and UV absorption of the polysilanes were successfully correlated with the conformational characteristics.(4)Conformational Analysis of Model Compounds of Polymer Liquid CrystalsStructure-property correlations of model compounds of oligomer to polymer liquid crystals have been investigated by thermal analysis, X-ray diffraction, deuterium NMR, etc. Conformational characteristics of 1-butanol incorporated, not only in a lyotropic liquid crystal of sodium octanoate, 1-butanol, and water but also in a nematic liquid crystal have been investigated by deuterium NMR.

（1）聚硫醚的分子内相互作用通过NMR实验、从头计算和RIS分析，研究了聚硫乙烯和聚硫丙烯在θ态的构象特征，并与相应的聚醚进行了比较。从构型熵和分子间相互作用的角度对多硫化物的高熔点进行了解释。（2）聚乙烯亚胺（PEI）的构象分析通过分子轨道计算和核磁共振实验，计算了PEI的构象能。PEI的链尺寸被计算为氢键能的函数。分子间氢键形成的双链螺旋的焓也估计从MO计算。（3）聚硅烷的构象分析采用转动异构态方法和分子动力学模拟方法研究了聚二正丁基硅烷、聚二正己基硅烷和聚甲基正丙基硅烷的构象特征。由此计算的特征比与光散射法测定的特征比相当一致。的聚硅烷的相变，溶解性，和紫外吸收成功地与构象特征。（4）高分子液晶模型化合物的构象分析通过热分析、X-射线衍射、氘核磁共振等方法研究了低聚物模型化合物与高分子液晶的结构-性能关系。和水，但也在一个无水液晶已研究了氘NMR。

项目成果

Yuji Sasanuma: "Intramolecular Interactions of Polyethers and Polysulfides, Investigated by NMR, Ab Initio Molecular Orbital Calculations, and Rotational Isomeric State Scheme : An Advanced Analysis of NMR Data", In Annual Reports on NMR Spectroscopy Vol.

Yuji Sasanuma：“聚醚和多硫化物的分子内相互作用，通过 NMR、从头算分子轨道计算和旋转异构态方案进行研究：NMR 数据的高级分析”，载于 NMR 光谱年度报告卷。

Yuji Sasanuma, Hajime Ohta, Ikuko Touma, Hiroki Matoba, Yugo Hayashi, Akira Kaito: "Conformational Characteristics of Poly(ethylene sulfide) and Poly(ethylene oxide): Solvent Dependence of Attractive and Repulsive Gauche Effects"Macromolecules. 35(9). 374

Yuji Sasanuma、Hajime Ohta、Ikuko Touma、Hiroki Matoba、Yugo Hayashi、Akira Kaito：“聚（硫乙烷）和聚（环氧乙烷）的构象特征：吸引力和排斥性高斯效应的溶剂依赖性”大分子。

笹沼裕二: "ポリエーテルが形成する弱い水素結合"高分子加工. 51. 218-223 (2002)

Yuji Sasanuma：“聚醚形成的弱氢键”聚合物加工 51. 218-223 (2002)。

Yuji Sasanuma: "Conformational Peculiarities of Alcohols Incorporated in Lyotropic and Thermotropic Liquid Crystals"Langmuir. 20. 665-672 (2004)

Yuji Sasanuma：“溶致和热致液晶中醇的构象特性”Langmuir。

Yuji Sasanuma: "Structure-Property Correlations in Model Compounds of Oligomer Liquid Crystals"J.Phys.Chem.B. 108(発表予定). (2004)

Yuji Sasanuma：“低聚物液晶模型化合物的结构-性质相关性”J.Phys.Chem.B. 108（待提交）。