Studies of Phase Transition in Block Copolymer Solutions by Small-Angle Light Scattering Spectroscopy

小角光散射光谱研究嵌段共聚物溶液中的相变

• 批准号: 07555604
• 负责人: TSUNASHIMA Yoshisuke
• 金额: $ 1.02万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 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-07555604/
• 关键词: Diblock copolymers; Selective solvents; Phase separation; Micellar formation; Intramicelle motions; Core-shell structures; Phase transition; Small-angle light scattering; PS-PMMAジブロック共重合体; ミセル構造; ミセル内部運動; 自己集合体

A high-speed light scattering spectroscopy system which measures molecular motions appearing in the phase separation and/or the phase transition of block copolymers in solution was constructed, in which the molecular motions detectable are ranging from 10^<-8> to 10^3 second in the magnitude of the relaxation times. At the scattering angles rheta in the range of usual 30-150ﾟ and at rheta smaller than 10ﾟ, phase transitions on polystirene (PS)-block-poly (methyl mathacrylate) diblock copolymer of high molecular weight such as M^w=1.53*10^6 (38.5wt%PS) were investigated in selective mixed solvents of benzene (BZ) and p-cymene (PC) as a function of the mixed ratios and the temperature differences in the temperature jump. When measured at rheta=30-150ﾟ, the diblock copolymer were found to form a monodispersed micelle at the mixed ratio more than 60 vol% of PC and to be in apparent closed association equlibrium between the single copolymer (unimer) and the micelle. The micelle dynamics was … More charcterized by its vast internal motions which occur inside the micelle. The intramicellar motions were attributed to active hydrodynamic heterocontacts between PS and PMMA subchain elements, or the composition fluctuation. At smaller angles as 5-10ﾟ, however, the scattering intensity of the solution fluctuated at the time interval as small as mus, the absolute intensity varing in three order of magnitude. Dynamic light scattering (DLS) from these solutions in quiescent state made clear that the intensity fluctuations were originated from structures whose sizes varing quickly in one to five order to magnitude ; the fuge micellar structures observed are considered not of be stable but transient ones, which are created and disappear in very short time intervals. DLS under Couette flow ascertained this picture with the result that only a single copolymer was observed in the shear field. The temperature difference of 20-80ﾟC induced no detectable conformation change in the present diblock copolymer chain. Less

构建了一个高速光散射光谱系统，用于测量嵌段共聚物在溶液中的相分离和/或相转变中出现的分子运动，其中可检测的分子运动的<-8>弛豫时间的大小在10^-10 ^3秒的范围内。当散射角reta在通常的30-150 °范围内且reta小于10 °时，聚苯乙烯（PS）-嵌段-聚的相变高分子量的（甲基丙烯酸甲酯）二嵌段共聚物，例如M^w=1.53*10^6（38.5wt%PS）在苯（BZ）和对伞花烃（PC）的选择性混合溶剂中进行了研究作为混合比和温度跃变中的温差的函数。在reta =30-150 ℃范围内，当PC的混合比大于60vol%时，嵌段共聚物形成单分散胶束，且共聚物单体与胶束之间呈表观封闭缔合平衡。胶束动力学是 ...更多信息 其特征是在胶束内部发生巨大的内部运动。胶束内运动归因于PS和PMMA子链元素之间的活跃流体动力学异质接触，或组成波动。而在5-10 μ m的小角度下，溶液的散射强度在μ s的时间间隔内发生波动，绝对强度变化在三个数量级。动态光散射（DLS）从这些解决方案在静态清楚地表明，强度波动起源于结构的大小迅速变化在1至5个数量级;观察到的离心胶束结构被认为是不稳定的，但短暂的，这是创建和消失在很短的时间间隔。Couette流动下的DLS证实了这一点，结果是在剪切场中只观察到单一的共聚物。20-80 ℃的温差未引起本发明的二嵌段共聚物链中可检测到的构象变化。少

项目成果

Y.Tsunashima: "Dynamics and Structures of Polymers in Solution" Proc.1st Intl.Sympo., ICRIS '96. 1. 14-19 (1996)

Y.Tsunashima：“溶液中聚合物的动力学和结构”Proc.1st Intl.Sympo.，ICRIS 96。

Y. Tsunashima: "Structure and Dynamics of Micelles Formed with a PS-PMMA Diblock Copolymer in Mixed Selective Solvents" Abstract of 1995 International Chemical Congress of Pacific Basin Societies, Hawaii, Dec. 17-22, 1995. MACR603 (1995)

Y. Tsunashima：“Structure and Dynamics of Micelles Formed with a PS-PMMA Diblock Copolymer in Mixed Selective Solvents” 摘要，1995 年太平洋盆地学会国际化学大会，夏威夷，1995 年 12 月 17-22 日。 MACR603 (1995)

Y. Tsunashima: "Block Copolymer Micelles in Solution" High Polymers, JPn.45. 482-486 (1996)

Y. Tsunashima：“溶液中的嵌段共聚物胶束”高聚物，JPn.45。

Y.Tsunashima: "Polymer Chain Dynamics in Dilute Solution under Couette Flow" Proc.1st Intl.Sympo.,ICRIS'96. 1. 128-131 (1996)

Y.Tsunashima：“库埃特流下稀溶液中的聚合物链动力学”Proc.1st Intl.Sympo.，ICRIS96。

Y.Tsunashima: "Polymer Diffusion in Solution observed by DLS under Simple Flow" Polym.Prepr.Jpn.45・12. 3384-3385 (1996)

Y.Tsunashima：“在简单流动下通过 DLS 观察溶液中的聚合物扩散”Polym.Prepr.Jpn.45・12（1996）。