MOLECULAR DESIGN FOR NOVEL STIMULI-SENSITIVE GELS

新型刺激敏感凝胶的分子设计

• 批准号: 09450365
• 负责人: KATO Masao
• 金额: $ 5.25万
• 依托单位: Tokyo University of Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450365/
• 关键词: POLY(SILAMINE); POLY(SILOXYETHYLENE GLYCOL); HYDROGEL; RUBBER ELASTICITY TRANSITION; STIMULI-SENSITIVE GEL; ACTUATOR; DDS; SPINODAL SEPARATION; ボリサイラミン; 相転移; 刺激答性ゲル; テレケリックス; 弾性率

Poly(siloxyethylene glycol) (PSEG), which consists of alternating oligo(dimethylsiloxane) and oligo(ethylene glycol) (OEG) units in the main chain was synthesized through polycondensation reactions between oligosiloxane having two diethylamino groups and OEG. The molecular weight of the polymer was in the range of 3,500 to 17,700 g/mol with monomodal molecular weight distribution. The glass transition temperature of the polymer thus obtained was controlled by changing the silicon content in the polymer. Actually, with increasing Si content, the Tg of the polymer decreased from -53℃(PEG) to -100℃. PSEG having a silicon content of less than 15 wt% was soluble in aqueous media. With increasing solution temperature, phase separation occurred and the solution become turbid. The temperature at the phase separation is known as a lower critical solution temperature(LCST). The LCST was controlled by the silicon content in the polymer. The hydrolytic stabilities of the PSEG in aqueous solution were also examined.Poly(silamine), which consists of alternating ethylene diamine and 3-silapentane, was also prepared via anionic polyaddition reaction of ethylenediamine with divinylsilane in the presence of lithium alkylamide. Poly(silamine) hydrogel exhibits a discontinuous volume phase transition and rubber elasticity transition in respond to pH change for the protonation of amine units in the main chain. It also has been revealed that the rubber elasticity transition is controlled by the anion for the strong interaction between poly(silamine) and anions. The results suggest that the stiffness of poly(silamine) hydrogel decreases with its swelling.

通过双二乙氨基低聚硅氧烷与低聚乙二醇（OEG）的缩聚反应，合成了主链上由低聚二甲基硅氧烷和低聚乙二醇（OEG）交替排列的聚乙二醇（PSEG）。聚合物的分子量在3，500至17，700 g/mol的范围内，具有单峰分子量分布。通过改变聚合物中的硅含量来控制由此获得的聚合物的玻璃化转变温度。实际上，随着Si含量的增加，聚合物的Tg从-53℃（PEG）降低到-100℃。硅含量小于15重量%的PSEG可溶于水性介质。随着溶液温度的升高，溶液发生相分离，溶液变得浑浊。相分离时的温度称为低临界溶解温度（LCST）。LCST由聚合物中的硅含量控制。研究了PSEG在水溶液中的水解稳定性，并通过乙二胺与二乙烯基硅烷在烷基氨基锂存在下的阴离子加聚反应制备了乙二胺与3-硅戊烷交替的聚硅胺。聚硅胺水凝胶由于主链上胺单元的质子化而呈现不连续的体积相变和橡胶弹性转变。由于聚硅胺与阴离子间的强相互作用，橡胶弹性转变受阴离子控制。结果表明，聚硅胺水凝胶的刚度随着其溶胀而降低。

项目成果

加藤政雄: "Water Soluble EB-Resisit Based on Amino-Containing Polymer,Soluble EB-Resist Based on Amino-Containning Polymer"Journal of Photopolymr Science and Technology. 12. 369-372 (1999)

加藤正夫：“基于含氨基聚合物的水溶性EB抗蚀剂，基于含氨基聚合物的可溶性EB抗蚀剂”光聚合物科学技术杂志12. 369-372 (1999)。

Hotaka Ito, Yukio Nagasaki, Masao Kato, Kazunori Kataoka, Teiji Tsuruta, Ken Suzuki, Teruo Okano, Yasuhisa Sakurai: "Properties of Novel Silicon-Containing Blockcopolymer Membrane Consisting of Hydrophilic and Hydrophobic Segments for Artificial Lung"Arti

Hotaka Ito、Yukio Nagasaki、Masao Kato、Kazunori Kataoka、Teiji Tsuruta、Ken Suzuki、Teruo Okano、Yasuhisa Sakurai：“用于人工肺的由亲水和疏水片段组成的新型含硅嵌段共聚物膜的特性”Arti

Yukio Nagasaki, Yoshikazu Nakashima, Ryutaro Ogawa, Masao Kato, Hidenori Ohtsuka, Kazunori Kataoka: "Surface Plasma Polymerization of Poly(ethylene glycol) Heterotelechelic Macromonomers for Construction of Cell Specific Surface"Journal of Photopolymer Sc

Yukio Nagasaki、Yoshikazu Nakashima、Ryutaro Okawa、Masao Kato、Hidenori Ohtsuka、Kazunori Kataoka：“用于构建细胞特定表面的聚乙二醇杂远爪大单体的表面等离子体聚合”Journal of Photopolymer Sc

M.Kato: "Synthesis of NLO diacrylate monomers and their photocopolymerizations with LC diacrylate monomers in mixed liquid crystaline state" Macromol.Chem.Phys.199. 881-888 (1998)

M.Kato：“NLO 二丙烯酸酯单体的合成及其与混合液晶态 LC 二丙烯酸酯单体的光共聚合”Macromol.Chem.Phys.199。

Y.Nagasaki: "Poly(silamine)as Intelligent Materials" CHEMTECH. 23-29 (1997)

Y.Nagasaki：“聚（硅胺）作为智能材料”CHEMTECH。