Preparation of Polymer Standards with Uniform Molecular Weights and Their Application to the Studies of Polymer Structure and Properties

均一分子量聚合物标准品的制备及其在聚合物结构与性能研究中的应用

• 批准号: 07555293
• 负责人: HATADA Koichi
• 金额: $ 9.28万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555293/
• 关键词: Supercritical Fluid Chromatography; Uniform Polymer; Monodisperse Polymer; Molecular Weight Distribution; Stereoregularity; Poly (methyl methacrylate); Size Exclusion Chromatography; Stereocomplex; 単分散ポリマー; 分子量測定; サイズ排除クロマトグラフィー; ポリアセタール

(1) A Supercritical fluid chromatograph (SFC) equipped with an automatic fractionation system consisting of an automatic injector and six-way valve units was constructed to obtain uniform polymers efficiently. Using this SFC system, the individual homologues (uniform polymers) of isotactic and syndiotactic poly (methyl methacrylate) (PMMA), syndiotactic polystirene, poly (butyl isocyanate), poly(hexyl isocyanate), poly (D-lactide), and poly (L-lactide) were successfully isolated. The structure and purity of uniform polymers were analyzed by NMR and mass spectrometry.(2) The glass transition temperature of uniform isotactic and syndiotactic PMMAs from 13mer to 50mer was determined as a function molecular weight. When the glass transition temperatures were plotted against the reciprocal of molecular weight, the data were well fitted by the linear relationship derived from the free-volume theory. The uniform isotactic PMMAs were highly crystalline, and the degree of crystallinity was foun … More d to exceed 92%.(3) When uniform isotactic PMMAs with definite molecular weights were used as the molecular weight standards in gel permeation chromatography (GPC), the molecular weight distribution of non-uniform isotactic PMMA was able to be determined accurately. A small difference between isotactic and syndiotactic PMMA in hydrodynamic volume was clearly shown by the GPC analysis of uniform polymers.(4) Solutions of uniform poly (hexyl isocyanate) s with numbers of repeating unit (n) from 10 to 30 in (-) -beta-pinene showed induced circular dichroism at the wavelength range where the absorption due to the backbone N-C linkage appears. Solvent-subtracted specific rotation decreased with increasing temperature, and increased monotonously with an increase in n. These chiroptical properties arise from an excess of one-handedness in the helical chain structure. Single crystals were grown from methanol solution of butyl isocyanate 12mer and the crystal structure was determined by X-ray analysis.(5) End-functionalized stereoregular uniform PMMAswere obtained by SFC fractionation and used to construct uniform polymer architectures such as block, comb, and star polymers. Solution properties of the uniform comb nd star PMMs were also investigated. Less

(1) 构建了配备自动分馏系统的超临界流体色谱仪(SFC)，该自动分馏系统由自动进样器和六通阀单元组成，以有效地获得均匀的聚合物。使用该SFC系统，成功分离了等规和间规聚甲基丙烯酸甲酯（PMMA）、间规聚苯乙烯、聚（异氰酸丁酯）、聚（异氰酸己酯）、聚（D-丙交酯）和聚（L-丙交酯）的各个同系物（均匀聚合物）。通过核磁共振和质谱分析了均匀聚合物的结构和纯度。(2)以函数分子量的形式测定了13mer至50mer的均匀全同立构和间同立构PMMA的玻璃化转变温度。当将玻璃化转变温度与分子量的倒数作图时，数据与自由体积理论导出的线性关系很好地拟合。均匀的等规PMMA结晶度较高，结晶度超过92%。(3)以一定分子量的均匀的等规PMMA作为凝胶渗透色谱(GPC)的分子量标准，可以准确测定非均匀的等规PMMA的分子量分布。均匀聚合物的GPC分析清楚地显示了等规和间规PMMA在流体力学体积上的微小差异。(4)(-)-β-蒎烯中重复单元数(n)为10至30的均匀聚(异氰酸己酯)溶液在由于主链N-C键而出现吸收的波长范围内表现出诱发的圆二色性。扣除溶剂的比旋光度随着温度的升高而降低，并随着n的增加而单调增加。这些手性光学特性源于螺旋链结构中过度的单手性。以异氰酸丁酯12聚体的甲醇溶液为原料生长单晶，并通过X射线分析确定晶体结构。(5)通过SFC分级获得末端功能化的有规立构均匀PMMA，并用于构建嵌段、梳状和星形聚合物等均匀聚合物结构。还研究了均匀梳状和星形 PMM 的溶液特性。较少的

项目成果

畑田 耕一: "立体規則性均一構造高分子の構築" 高分子論文集. 54. 661-673 (1997)

Koichi Hatada：“有规立构均质结构聚合物的构建”Kobunshi Proceedings 5​​4. 661-673 (1997)。

Koichi Hatada, Takafumi Nishiura, Tatsuki, Kitayama, Koichi Ute: "Toward Uniform Polymer Architecture Through Stereospecific Living Polymerization and Chromatographic Separation Technique" Macromol.Symp.118. 135-141 (1997)

Koichi Hatada、Takafumi Nishiura、Tatsuki、Kitayama、Koichi Ute：“通过立体定向活性聚合和色谱分离技术实现均匀聚合物结构” Macromol.Symp.118。

Koichi Hatada, Tatsuki Kitayama, Koichi Ute, Takufumi Nishiura: "Preparation of Uniform Stereoregular Polymer, stereoblock Polymer and Copolymer of Methacrylate, and Their Stereocomplex Formation" Macromol.Symp.in press).

Koichi Hatada、Tatsuki Kitayama、Koichi Ute、Takufumi Nishiura：“均匀立构规整聚合物、甲基丙烯酸酯立构嵌段聚合物和共聚物的制备及其立体复合物形成”Macromol.Symp.in press）。

Koichi Ute: "Supercritical Fluid Chromatography with Packed Columus" Marcel Dekker, 472 (1997)

Koichi Ute：“采用填充柱的超临界流体色谱法”Marcel Dekker，472 (1997)

Koichi Hatada: "Uniform Poly(methyl methacrylate)s with Controlled Architecture" Trends in Polymer Science. 5. 223-229 (1997)

Koichi Hatada：“具有受控结构的均匀聚（甲基丙烯酸甲酯）”聚合物科学趋势。