Z型全氟聚醚的结构表征

doi:10.11949/0438-1157.20221490

摘要/Abstract

摘要：

具有功能性端基的全氟聚醚具有优异的化学稳定性及较强的加工可塑性，被广泛用于航天航空、电子、化工等领域。在其制备及应用过程中，基于核磁共振技术的结构表征和解析至关重要。然而由于全氟聚醚及其活性化合物的结构复杂、分子量大且分布较宽，因此在核磁测试中存在制样难、主链骨架结构和端基难以分辨和归属等问题，进而影响对全氟聚醚的定性定量分析。针对Z型惰性及活性全氟聚醚的结构解析，系统考察了不同种类氘代试剂和含氟助溶剂的复配、样品浓度、测试条件等因素的影响，探索得到较优的核磁样品制备条件；进一步分析了Z型全氟聚醚混合物的氟谱，确定了全氟聚醚的主链结构和端基的归属；利用端基分析法计算得到分子量及聚合度、两组分全氟聚醚混合物组成。

关键词: 全氟聚醚, 官能端基的活性全氟聚醚, 结构解析, 化学分析, 聚合物, 混合物

Abstract:

Perfluoropolyether (PFPE) with functional end groups possesses excellent chemical stability and strong processing plasticity, thus being widely applied in high-end fields such as aerospace, electronics, chemical engineering. During production and application, it’s significant to characterize and analyze PFPE structure based on nuclear magnetic resonance technology (NMR). However, due to structure complexity, high molecular weight and wide distribution of PFPE, there have been difficulties in preparing samples for NMR test, distinguishing and attributing the main chain structure and end groups in NMR spectra, which further affects qualitative and quantitative analysis of PFPE. In view of the structural analysis of Z-type PFPE, this study investigated combination of kinds of deuterated solvents and fluorinated cosolvent, sample concentration and test conditions,obtaining a better method of NMR sample preparation. The attribution of main chain structure and end groups of PFPE were determined. Also, the molecular weight, the degree of polymerization, and the composition of two-component PFPE mixture were calculated by analyzing the end groups of PFPE.

Key words: perfluoropolyether, reactive perfluoropolyether with functional end groups, structure elucidation, chemical analysis, polymers, mixtures

中图分类号:

TQ 317.2

唐茹意, 潘罕骞, 郑侠俊, 张广欣, 汪星平, 崔希利, 邢华斌. Z型全氟聚醚的结构表征[J]. 化工学报, 2023, 74(1): 479-486.

Ruyi TANG, Hanqian PAN, Xiajun ZHENG, Guangxin ZHANG, Xingping WANG, Xili CUI, Huabin XING. Structural characterization of Z-type perfluoropolyether[J]. CIESC Journal, 2023, 74(1): 479-486.

图/表 11

参考文献 26

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样品	组成
Ⅰ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃
Ⅱ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOK KOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOK
Ⅲ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃ F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH HOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH
Ⅳ^①	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃ F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH HOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH

样品	组成
Ⅰ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃
Ⅱ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOK KOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOK
Ⅲ	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃ F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH HOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH
Ⅳ^①	F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₃ F₃CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH HOOCF₂CO—(CF₂CF₂O) _p —(CF₂O) _q —CF₂COOH

样品	核磁溶剂	溶解情况
Ⅰ	F113∶CDCl₃=4∶1	良好
	HFX∶CDCl₃=4∶1	良好
	5FP∶CDCl₃=4∶1	微溶
Ⅱ	F113∶CDCl₃=4∶1	微溶
	HFX∶CDCl₃=4∶1	微溶
	5FP∶CDCl₃=4∶1	良好
Ⅲ	F113∶CDCl₃=4∶1	良好
	HFX∶CDCl₃=4∶1	微溶
	5FP∶CDCl₃=4∶1	微溶
Ⅳ	F113∶CDCl₃=4∶1	微溶

样品	核磁溶剂	溶解情况
Ⅰ	F113∶CDCl₃=4∶1	良好
	HFX∶CDCl₃=4∶1	良好
	5FP∶CDCl₃=4∶1	微溶
Ⅱ	F113∶CDCl₃=4∶1	微溶
	HFX∶CDCl₃=4∶1	微溶
	5FP∶CDCl₃=4∶1	良好
Ⅲ	F113∶CDCl₃=4∶1	良好
	HFX∶CDCl₃=4∶1	微溶
	5FP∶CDCl₃=4∶1	微溶
Ⅳ	F113∶CDCl₃=4∶1	微溶

核磁溶剂	溶解情况	氟谱质量
5FP∶CDCl₃=4∶1	微溶	峰形不光滑
5FP∶ methanol-D4=4∶1	微溶	峰形不光滑
5FP∶DMSO=4∶1	微溶	峰形不光滑
5FP∶ acetone-D6=4∶1	微溶	峰形不光滑
F113∶CDCl₃=4∶1	微溶	溶剂峰与端基峰部分重叠
F113∶CDCl₃=5∶1	溶解一般	溶剂峰与端基峰部分重叠
F113∶CDCl₃=6∶1	溶解较好	不能锁场
F113∶CDCl₃=7∶1	溶解良好	不能锁场
CF₃COOD	溶解良好	清晰