Inversion of polymer micelles formed from double thermo-sensitive diblock copolymers

双热敏二嵌段共聚物形成的聚合物胶束的反转

• 批准号: 14550845
• 负责人: MAEDA Yasushi
• 金额: $ 2.3万
• 依托单位: University of Fukui
• 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-14550845/
• 关键词: THERMOSENSITIVE POLYMER; POLYMER MICELLE; PHASE TRANSITION; IR SPECTROSCOPY; BLOCK COPOLYMER; AQUEOUS SOLUTION; HYDRATION; LCST; ポリ(N-イソプロピルアクリルアミド); 相分離; 水溶液

We have prepared several double thermosensitive diblock copolymers consisting of poly(sulfobetaine) and poly(N-alkyl acrylamide) blocks, which have a upper critical solution temperature(UCST)and a lower critical solution temperature(LeST), respectively, by RAFT(Reversible Addition Fragmentation chain Transfer)process using 4-cyanopentanoic acid dithiobenzoate as a chain transfer regent.The block copolymers form micelles that exhibit a core-corona inversion simply depending on temperature, that is, poly(sulfobetaine)-core and poly(N-alkyl acrylamide)-core micelles are formed below the UCST and above the LCST, respectively.IR spectroscopic investigation on the micellization of a diblock copolymer consisting of poly(3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate)(PdMMAEAPS) and poly(N, N-diethylacrylamide)s (PdEA) blocks showed that the v(C0) and v(S0_3) bands of the PdMMAEAPS block and the amide I band of PdEA block critically changes at the UCST and LCST, respectively.The result indicates that segmental interaction of each block is altered at each transition.Fluorescence measurements using pyrene and 2-anilinonaphtalene showed that these dyes are incorporated in PdEA-core micelles formed above the LCST.Micellization temperatures can be controlled by adding additives such as salts and alcohols.Dependencies of micellization temperature on solvent composition is varied with properties of each block.For example, the UCST of PdMIN4AEAPS block decreases with increasing concentration of NaCI, but the UCST of poly(4-dimethyl(acrylaminopropyl) ammonium propane sulfonate)block increases.

以4-氰基戊酸二硫代苯甲酸酯为链转移剂，通过RAFT(可逆加成断裂链转移)工艺制备了具有较高临界溶解温度(UCST)和较低临界溶解温度(LEST)的聚(磺基甜菜碱)和聚(N-烷基丙烯酰胺)嵌段组成的双温敏两嵌段共聚物。嵌段共聚物形成的胶束简单地随温度呈现核-晕反转，即在UCST以下和LCST以上形成聚(磺基甜菜碱)核和聚(N-烷基丙烯酰胺)核胶束，红外光谱研究了由聚(3-二甲基甲基丙烯酰氧乙基)丙烷磺酸铵(PdMMAEAPS)和聚(N，N-二乙基丙烯酰胺)S(PdEA)嵌段组成的两嵌段共聚物的胶束化过程。红外光谱表明，PdMMAEAPS嵌段的v(C0)和v(S03)带和PdEA嵌段的酰胺I带在UCST和LCST处发生了严重的变化。结果表明，PdMIN4AEAPS嵌段的链段相互作用在每个嵌段的每个转变过程中都发生了变化。用芘和2-苯基萘甲烯进行的荧光测量表明，这些染料被结合到LcST上方形成的PdEA核胶束中。胶束温度可以通过添加盐和醇等添加剂来控制。胶束温度对溶剂组成的依赖关系因每个嵌段的性质而不同。例如，PdMIN4AEAPS嵌段的UCST随NaCI浓度的增加而降低，但聚(4-二甲基丙烯氨丙基丙烷磺酸铵)嵌段的UCST随NaCI浓度的增加而增加。

项目成果

Maeda, Y., Tsubota, M., Ikeda, I: "Fourier-transform IR Spectroscopic Study on Phase Transitions of Copolymers of N-Isopropylacrylamide and Alkyl Acrylates in Water."Colloid Polym.Sci.. 281. 79-83 (2003)

Maeda, Y.、Tsubota, M.、Ikeda, I：“水中 N-异丙基丙烯酰胺和丙烯酸烷基酯共聚物相变的傅里叶变换红外光谱研究。”胶体高分子科学 281. 79-83 (2003)

Maeda, Yasushi: "Fourier-transform IR Spectroscopic Study on Phase Transitions of Copolymers of N-Isopropylacrylamide and Alkyl Acrylates in Water."Colloid Polym.Sci.. 281. 78-83 (2003)

Maeda, Yasushi：“水中 N-异丙基丙烯酰胺和丙烯酸烷基酯共聚物的相变的傅里叶变换红外光谱研究。”胶体高分子科学. 281. 78-83 (2003)

Maeda, Yasushi: "Fourier-transform IR Spectroscopic Study on Phase Transitions of Copolymers of N-Isopropylacrylamide and Alkyl Acrylates in Water"Colloid Polym.Sci.. 281. 79-83 (2003)

Maeda, Yasushi：“水中 N-异丙基丙烯酰胺和丙烯酸烷基酯共聚物相变的傅立叶变换红外光谱研究”Colloid Polym.Sci.. 281. 79-83 (2003)

Maeda, Yasushi: "Hydration and Phase Behavior of Poly(N-vinylcaprolactam) and Poly(N-vinylpyrrolidone) in Water."Macromolecules. 35. 217-222 (2002)

Maeda，Yasushi：“聚（N-乙烯基己内酰胺）和聚（N-乙烯基吡咯烷酮）在水中的水合和相行为。”大分子。

前田 寧: "ポリ(N-置換アクリルアミド)水溶液の温度応答性と水和"接着. 47. 414-421 (2003)

Yasushi Maeda：“聚（N-取代丙烯酰胺）水溶液的温度响应性和水合”粘附力。