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Investigation of the Structures and Dynamics of Fluoropolymers Using Novel Methods of Solid-state ^<19>F NMR Spectroscopy.

使用固态19 F NMR波谱新方法研究含氟聚合物的结构和动力学。

基本信息

批准号：
13450387
负责人：
ANDO Shinji
金额：
$ 9.86万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

Various spectroscopic techniques using ^<19>F magic angle spinning (MAS) and ^1H【double arrow】^<19>F cross polarization (CP)/MAS nuclear magnetic resonance (NMR) spectroscopy were developed to explore new methodology for the analysis of structure and molecular mobility of functional fluoropolymers in the solid state. Novel ^<19>F NMR methods, such as a selective observation of the crystalline domain of polymers whose mobility does not much differ from the amorphous domain, an estimation of the characteristic local mobility in the amorphous polymers, an appraisal method for estimating interatomic H-F distances, etc. were developed in addition to the analysis of CP dynamics in a multi-spin system consisting of highly abundant nuclei and various methods for measuring magnetic relaxation times. Such ^1H【double arrow】^<19>F CP/MAS techniques were applied for (1)polyvinylidene fluoride (PVDF) exhibiting distinct polymorphism and (2)polyvinylfluoride (PVF) whose phase structure has not been c … More larified yet. I)The degrees of crystallinity and structural isomerism were estimated from the intensity of each signal, II)the conformations of the main chain were determined from ^<19>F chemical shifts (resonant positions), III) the difference in molecular mobility among polymorphs and between crystalline/amorphous domains, and the F-H interatomic distances were investigated from the magnetic relaxation measurements and the analysis of ^1H【double arrow】^<19>F CP dynamics, and IV)the gradual changes in conformation of the crystalline domains at elevated temperatures were clarified by the variable temperature (VT) measurements. Subsequently, derivative NMR techniques were applied for (3)Cytop that is an amorphous perfluoropolymer, a crystalline (4)ethylene/tetrafluoro-ethylene copolymer (ETFE), (5)vinylidene fluoride/trifluoroethylene copolymer (P(VDFITrFE)) that exhibits very high ferroelectricity, (6)miscible blends of PVDF/PMMA, (7)polychlorotrifluoroethylene (PCTFE) having high weatherability, (8)immiscible blends of PCTFE/PVDF, and (9)fluorine-containing aromatic polyimides applicable for optical waveguide circuits. This series of research has shown that ^<19>F MAS and the ^1H【double arrow】^<19>F CP/MAS NMR methods are very useful and promising for the analysis of structures and motility of functional fluoropolymers. Less

为了探索固态功能含氟聚合物结构和分子运动性分析的新方法，发展了各种光谱技术，包括^<19>F魔角自旋（MAS）和^1H [双箭头]^<19>F交叉极化（CP）/MAS核磁共振（NMR）。新的13 <19>F NMR方法，例如选择性观察其迁移率与无定形域相差不大的聚合物的结晶域，估计无定形聚合物中的特征局部迁移率，用于估计原子间H-F距离的评价方法，等，除了在一个多-由高丰度原子核组成的自旋系统和测量磁弛豫时间的各种方法。这种^1H[双箭头]^<19>F CP/MAS技术应用于（1）表现出明显多晶型的聚偏氟乙烯（PVDF）和（2）相结构尚未确定的聚氟乙烯（PVF）。 ...更多信息还没成熟I）根据每个信号的强度估计结晶度和结构异构性，II）根据^<19>F化学位移（共振位置）确定主链的构象，III）通过磁弛豫测量和^1H [双箭头]^ F CP分析研究多晶型物之间以及结晶/非晶域之间的分子迁移率差异和F-H原子间距离<19>动力学，和IV）在升高的温度下的结晶域的构象的逐渐变化被澄清的变温（VT）测量。随后，将衍生NMR技术应用于（3）Cytop，其为无定形全氟聚合物，（4）结晶乙烯/正-乙烯共聚物（ETFE），（5）偏二氟乙烯/三氟乙烯共聚物，（6）聚乙烯/三氟乙烯共聚物，和（7）聚乙烯/三氟乙烯共聚物。（P（VDFITrFE）），表现出非常高的铁电性，（6）PVDF/PMMA的可混溶共混物，（7）具有高耐候性的聚三氟氯乙烯（PCTFE），（8）PCTFE/PVDF的不混溶共混物，和（9）可用于光波导电路的含氟芳族聚酰亚胺。这一系列的研究表明，^<19>F MAS和^1H [双箭头]^<19>F CP/MAS NMR方法对于功能性含氟聚合物的结构和运动性分析是非常有用和有前途的。少