Synthesis and Properties of Amphiphilic Polymers

两亲性聚合物的合成与性能

• 批准号: 06044114
• 负责人: YAMAOKA Hitoshi
• 金额: $ 4.61万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06044114/
• 关键词: Amphiphilic polymer; Block polymer; Living cationic polymerization; Polymer micelle; Surface activity; Small-angle neutron scattering; Small-angle X-ray scattering

This 2-year Japan-U.S.bilateral research project has been directed to "amphiphilic polymers", or macromolecules consisting of both hydrophilic and hydrophobic moieties, for which efforts have been focused on : (a) precision sample syntheses ; (b) their behavior in solution and at surface or interface ; (c) factors affecting their hydrophilic and hydrophobic interactions ; and (d) relations between their spatial shapes and functions. A brief summary follows :1.Synthesis of Amphiphilic PolymersFour series of well-defined amphiphilic polymers have been synthesized by the living cationic polymerization developed by the Japanese members :(A) AB-block copolymers of 2-hydroxyethyl and 2-phenoxyethyl vinyl ethers ;(B) AB-block copolymers of 2-hydroxyethyl and n-butyl vinyl ethers ;(C) Partially deuterated analogs of block copolymers A and B where the phenyl and the n-butyl pendant groups are deuterated, respectively ;(D) Tetraarmed block copolymers of vinyl ether and stirene derivatives.2.Ligh … More t Scattering and X-Ray Scattering AnalyzesSolubilization of hydrophobic dyes into water by these polymers confirmed that they are amphiphilic and thus form micelles, which were further analyzed by scattering methods :(a) Dynamic light scattering (DLS) for the micelle sizes ;(b) Forced Rayleigh scattering for the diffusion constants (by the American members) ;(c) Small-angle X-ray scattering (SAXS) for the shape and number of the micelles.For example, the DLS analysis (a) of the 4-arm polymers D showed their sharp response to solvent polarity, unimers in ethanol and micelles in chloroform. The SAXS data (c) for the linear polymers A and B indicated that increasing polymer concentration increases the number of micelles without changing their shapes.3.Neutron Scattering AnalysisSmall-angle neutron scattering (SANS) was applied to the partially deuterated amphiphiles C in D_2O/H_2O mixtures for the contrast variation method. Dependence of SANS profiles on the solvent composition revealed core-shell architectures of the block polymers, the shapes of which change from spherical to ellipsoidal on increasing length of the hydrophobic segments.4.Surface and Interface AnalysisEffective surface activity of polymers A and B were shown by clear reduction of the surface and interfacial tensions of water in their presence at low concentrations. These amphiphiles also interact with silica surface ; the strength and distance of the interaction was evaluated by evanescent light wave scattering. Less

这一为期两年的日美双边研究项目针对“两亲聚合物”，即由亲水和疏水部分组成的大分子，其工作重点是：（a）精密样品合成;（B）它们在溶液中和表面或界面上的行为;（c）影响它们的亲水和疏水相互作用的因素;（d）它们在水溶液中的行为;（e）它们在水溶液中的行为。以及（d）它们的空间形状和功能之间的关系。1.两亲性聚合物的合成利用活性阳离子聚合法合成了四个系列的两亲性聚合物：（A）2-羟乙基和2-苯氧乙基乙烯基醚的AB-嵌段共聚物，（B）2-羟乙基和正丁基乙烯基醚的AB-嵌段共聚物，（C）苯基和正丁基侧基分别被氘代的嵌段共聚物A和B的部分氘代类似物，（D）2-羟乙基和2-苯氧乙基乙烯基醚的AB-嵌段共聚物。（D）乙烯基醚和苯乙烯衍生物的四臂嵌段共聚物。 ...更多信息 用动态光散射法（DLS）测定胶束的大小;（B）用强迫瑞利散射法测定胶束的扩散常数;（3）用X射线光散射法测定胶束的大小;（4）用X射线光散射法测定胶束的大小;（5）用X射线光散射法测定胶束的大小（美国成员）;（c）胶束形状和数量的小角X射线散射（SAXS）。4-臂聚合物D的DLS分析（a）显示它们对溶剂极性、乙醇中的单聚体和氯仿中的胶束的强烈响应。线性聚合物A和B的SAXS数据（c）表明，增加聚合物浓度会增加胶束的数量，而不会改变它们的形状。3.中子散射分析采用小角中子散射（SANS）方法对部分氘代两亲物C在D_2O/H_2O混合溶液中的散射行为进行了研究。SANS曲线对溶剂组成的依赖性揭示了嵌段聚合物的核-壳结构，其形状随着疏水链段长度的增加而从球形变为椭球形。4.表面和界面分析聚合物A和B的有效表面活性通过在低浓度下它们存在时水的表面和界面张力的明显降低来显示。这些两亲物也与二氧化硅表面相互作用;通过倏逝光波散射评估相互作用的强度和距离。少

项目成果

H.Yamaoka: "Small-angle Neutron Scattering Study of the Micelle Structure of Amphiphilic Block Copolymers" Physica B. 213 & 214. 700-702 (1995)

H.Yamaoka：“两亲嵌段共聚物胶束结构的小角中子散射研究”Physica B.213

H.Yamaoka: "Living Anionic Ring-Opening Polymerization of 1,1-Dimethylsilacyclobutane" Macromolecules. 28. 7029-7031 (1995)

H.Yamaoka：“1,1-二甲基硅环丁烷的活性阴离子开环聚合”大分子。

M.Sawamoto: "Multifunctional Coupling Agents for Living Cationic Polymerization. 3. Synthesis of Tri- and Tetraarmed Poly (vinyl ethers) with Tri- and Tetrafunctional Silyl Enol Ethers" Macromolecules. 27. 1297-1302 (1994)

M.Sawamoto：“用于活性阳离子聚合的多功能偶联剂。3.用三官能和四官能硅烯醇醚合成三臂聚（乙烯基醚）”大分子。

H.Yamaoka,H.Matsuoka,K.Sumaru,H.Hanada,M.Imai: "Small Angle Neutron Scattering Study of the Micelle Structure of Amphiphilic Block Copolymers" Physica B. (印刷中). (1995)

H.Yamaoka、H.Matsuoka、K.Sumaru、H.Hanada、M.Imai：“两亲嵌段共聚物胶束结构的小角中子散射研究”Physica B.（出版中）。

H.Fukui,M.Sawamoto,T.Higashimura: "Synthesis of Amphiphilic Tetraarmed Star Poly(Vinyl Ethers) by Coupling Reactions with Tetrafunctional Silyl Enol Ether" Macromolecules. (印刷中). (1995)

H.Fukui、M.Sawamoto、T.Higashimura：“通过与四官能硅烯醇醚偶联反应合成两亲性四臂星形聚（乙烯基醚）”（出版中）。