多维核磁共振波谱方法研究含氟高分子结构
结题报告
批准号:
21305098
项目类别:
青年科学基金项目
资助金额:
28.0 万元
负责人:
李晓虹
依托单位:
学科分类:
B0403.谱学方法与理论
结题年份:
2016
批准年份:
2013
项目状态:
已结题
项目参与者:
万瑛博、徐丞龙、徐乔臻
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中文摘要
含氟高分子工业应用广泛,是耐腐蚀涂料,耐高/低温润滑剂和膜交换材料等领域的理想材料。为达到通过控制反应条件提高其性能的目的,需要对其化学结构与性能和合成反应条件的关系进行研究。液体核磁共振波谱信号准确,灵敏,是表征化合物的有力手段。过去,由于含氟高分子溶解性问题,其结构测定通常使用其他分析手段,结果无法满足对其精细结构研究的需要。本项目选择合适溶剂对一系列含氟材料进行液体核磁共振波谱研究。其中包括:Nafion 离聚物,Tedlar PVF 聚氟乙烯,Krytox 全氟聚醚和Viton 含氟橡胶。通过多维核磁方法对选定区域选择性激发和去耦,可以在短时间内得到信号清晰,峰型简单的谱图。便于确定化学结构,了解反应机理。更结合平行检测核磁手段(PANSY)节约采集时间,提高检测效率,增加信噪比。可建立起快速高效液体核磁检测含氟高分子材料的标准流程。推动我国含氟材料结构测定水平的提高。
英文摘要
Fluoropolymers are important commercial materials ideally suited for protective coatings, lubricants and membrane barriers; in applications that expose them to extreme environments, require extreme longevity or require unusual surface properties. Detailed characterization of fluoropolymers is critical as there is a direct relationship between a polymer's structural features and its chemical, physical and mechanical properties. Correlation between polymer properties, synthesis conditions, and amount and type of structures permits polymer scientist to reproduce the preparation of material with optimum performance. Solution NMR produces sharp, accurate and sensitive signals. It is one of the most important methods to characterize polymers. In the past, because of the poor solubilities in most solvents, the characterization of fluoropolymers were often carried with analytical methods other than solution NMR, such as GPC, MS or IR, even solid state NMR etc. The results came from those resources could not provide abundant information for the fine structure analysis of fluoropolymers.The goal of this work is to provide examples of using Modern n-dimensional NMR and PANSY techniques to characterize a series of fluoropolymers including: Nafion, Tedlar, Krytox and Viton. Simple and clear peak patterns will be acquired within short time period by using the special designed modern n-dimensional NMR with PANSY techniques. Fine structures of fluoropolymers will be studied and related reactions mechanism will be understood. Standard procedures for studying fluoropolymers' structures by NMR will be developed. The results will help with the improvements of current fluoropolymers industry and also promote a better usage of the NMR instruments.
本项目通过平行采集核磁 (PANSY),扩散序谱(DOSY)等新型核磁方法结合多维核磁对一系列含氟材料包括:聚偏氟乙烯PVF,全氟聚醚PFPE及聚偏氟乙烯-二氟丙烯酸共聚物PVDF-co-DFAA等含氟橡胶进行液体核磁共振波谱研究。PANSY方法节约采集时间,提高检测效率,增加信噪比。19F DOSY区别于传统1H DOSY,加入adiabatic形状脉冲,在19F谱较大谱窗内均匀激发信号;优化梯度时间,消除19F-19F同核耦合造成的19F谱信号畸变。利用DOSY检测含氟聚合物的扩散速率,对区分链端与主链结构,聚合物长链端基与支化短链端基扩散行为的区别及含量分析,分子量和分子量分布测定有重要意义。本项研究对同样有较宽谱窗,较大同核J耦合常数的元素如31P和195Pt的DOSY研究也具有重大意义。
期刊论文列表
专著列表
科研奖励列表
会议论文列表
专利列表
DOI:10.1021/acs.inorgchem.6b01894
发表时间:2016-10
期刊:Inorganic chemistry
影响因子:4.6
作者:Yajuan Hao;Q. Tang;Xiaohong Li;Meirong Zhang;Yingbo Wan;Lai Feng;N. Chen;Z. Slanina;L. Adamowicz-L.
通讯作者:Yajuan Hao;Q. Tang;Xiaohong Li;Meirong Zhang;Yingbo Wan;Lai Feng;N. Chen;Z. Slanina;L. Adamowicz-L.
From Ring-in-Ring to Sphere-in-Sphere: Self-Assembly of Discrete 2D and 3D Architectures with Increasing Stability
从环中环到球中球:离散 2D 和 3D 架构的自组装,稳定性不断提高
DOI:10.1021/ja511443p
发表时间:2015-02-04
期刊:JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子:15
作者:Sun, Bin;Wang, Ming;Li, Xiaopeng
通讯作者:Li, Xiaopeng
Sc2O@C-3v(8)-C-82: A Missing Isomer of Sc2O@C-82
Sc2O@C-3v(8)-C-82:Sc2O@C-82 的缺失异构体
DOI:10.1021/acs.inorgchem.5b02901
发表时间:2016
期刊:INORGANIC CHEMISTRY
影响因子:4.6
作者:Tang Qiangqiang;Abella Laura;Hao Yajuan;Li Xiaohong;Wang Yingbo;Rodriguez-Fortea Antonio;Poblet Josep M.;Feng Lai;Chen Ning
通讯作者:Chen Ning
DOI:10.1002/chem.201500904
发表时间:2015-07
期刊:Chemistry
影响因子:--
作者:Ting Yang;Yajuan Hao;Laura Abella;Q. Tang;Xiaohong Li;Yingbo Wan;A. Rodríguez‐Fortea;J. Poblet;Lai Feng;N. Chen
通讯作者:Ting Yang;Yajuan Hao;Laura Abella;Q. Tang;Xiaohong Li;Yingbo Wan;A. Rodríguez‐Fortea;J. Poblet;Lai Feng;N. Chen
Incorporating Pendent Fullerenes with High Refractive Index Backbones: A Conjunction Effect Method for High Refractive Index Polymers
将悬垂富勒烯与高折射率主链结合:高折射率聚合物的联合效应方法
DOI:10.1021/acs.macromol.5b01791
发表时间:2015-12-08
期刊:MACROMOLECULES
影响因子:5.5
作者:Chen, Shuang;Chen, Dongxue;Li, Christopher Y.
通讯作者:Li, Christopher Y.
国内基金
海外基金