Sol-Gel Transition and Interaction between Fluorine-Contained Polymer/Organic Solvents

溶胶-凝胶转变和含氟聚合物/有机溶剂之间的相互作用

• 批准号: 14550852
• 负责人: OKABE Masaru
• 金额: $ 1.66万
• 依托单位: Kanagawa Institute of Technology
• 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-14550852/
• 关键词: thermoreversible gel; poly(vinylidene fluoride); sol-gel transition Flory-Huggins interaction parameter; inverse gas chromatography; time-resolved FT-IR; gelation mechanism; PVdF conformation; ゲル化過程; ゲル形成能; in situ IR法; ゲル構造

The Flory-Huggins interaction parameter (χ_12) of poly(vinylidene fluoride)(PVdF)/organic solvent system was measured over wide range of temperature by an inverse gas chromatography (IGC) using many kinds of solvents such as alkane, alkene, ketone, lactone, and nitrogen-containing solvent. The thermoreversible gelation of PVdF solution was discussed from the magnitude of interaction parameter χ_12 between PVdF and solvent. The parameter χ_12 was measured for a concentrated PVdF solution by the usual IGC technique.The parameter χ_12 obtained for each PVdF/solvent system increased slowly with decreasing temperature. The present systems were divided into three groups according to the magnitude of χ_12 in the vicinity of room temperature, i.e., group (a) with χ_12>> 0.5, group (b) with χ_12 ≒ 0.5, and group (c) with χ_12 << 0.5. The group (b), to which ketone and lactone belong, converted to thermoreversible gels accompanying with crystallization of polymer.The gelation process of PVdF/organic solvent system was investigated through measurement of in situ Fourier transform infrared (FT-IR) spectroscopy. The time-resolved FT-IR spectra suggested that the sol-gel transition took place taking the conformation T_3GT_3G' for the system where the parameter χ_12 was nearly equal to 0.5 such as PVdF in γ-butyrolactone. For the system where the parameter χ_12 became larger than 0.5 such as PVdF in cyclohexanone, 3-pentanone, 3-hexanone, 3-heptanone, or 3-octanone, the sol-gel transition occurred taking the conformation TGTG'.

用反相色谱方法测定了聚偏氟乙烯/有机溶剂体系在较宽温度范围内的Flory-Huggins相互作用参数(χ_12)。从聚偏氟乙烯与溶剂相互作用参数χ_12的大小讨论了聚偏氟乙烯溶液的热可逆凝胶化过程。用气相色谱技术测定了聚偏氟乙烯浓溶液的χ_(12)参数，测得各体系的χ_(12)随温度的降低而缓慢增加。根据χ_12在室温附近的大小将本体系分为三组，即(A)组χ_12和χ_12≒为0.5，组(B)χ_12和≒为0.5，以及(C)χ_12和Lt；通过原位傅里叶变换红外光谱研究了聚偏氟乙烯/有机溶剂体系的凝胶过程。时间分辨红外光谱表明，当χ_12参数接近等于0.5时，体系发生了T_3GT_3g‘构象的溶胶-凝胶转变，如γ-丁内酯中的聚偏氟乙烯。对于参数χ_12大于0.5时的体系，如在环己酮、3-戊酮、3-己酮、3-庚酮或3-辛酮中的聚偏氟乙烯，发生了构象为TGTg‘的溶胶-凝胶转变。

项目成果

有岡 由夏: "ポリ(フッ化ビニリデン)/有機溶媒系ゲルのゲル化とモルホロジー"神奈川工科大学研究報告. B-28. 66-67 (2004)

Yuka Arioka：“聚偏二氟乙烯/有机溶剂凝胶的凝胶化和形态”神奈川技术研究所研究报告 B-28（2004）。

瀧川 裕貴: "ポリブチレンサクシネートの有機溶媒中でのゾル-ゲル転移"高分子論文集. 61. 186-191 (2004)

Yuki Takikawa：“有机溶剂中聚丁二酸丁二醇酯的溶胶-凝胶转变”《高分子科学与技术杂志》，61. 186-191 (2004)。

有岡 由夏: "ゲル電解質としてのポリ(フッ化ビニリデン)/有機溶媒系ゲルのゲル化過程とモルホロジー"神奈川工科大学研究報告. B-27. 90-91 (2003)

Yuka Arioka：“聚偏二氟乙烯/有机溶剂凝胶作为凝胶电解质的凝胶化过程和形态”神奈川技术研究所研究报告 B-90-91 (2003)。

Masaru Okabe: "The Flory-Huggins Interaction Parameter and Thermoreversible Gelation of Poly(vinylidene fluoride) in Organic Solvents"Polym. J.. Vol.35. 798-803 (2003)

Masaru Okabe：“有机溶剂中聚偏二氟乙烯的弗洛里-哈金斯相互作用参数和热可逆凝胶化”Polym。

Masaru Okabe: "The Flory-Huggins Interaction Parameter and Thermoreversible Gelation of Poly(vinylidene fluoride) in Organic Solvents"Polymer Journal. 35. 798-803 (2003)

Masaru Okabe：“有机溶剂中聚偏二氟乙烯的弗洛里-哈金斯相互作用参数和热可逆凝胶化”聚合物杂志。