羧酸端基Y型全氟聚醚的氟谱解析及结构表征

doi:10.11949/0438-1157.20231411

摘要/Abstract

摘要：

全氟聚醚及其衍生物（PFPEs）是一类高附加值的含氟聚合物，特异的理化性质使其具有较好的商业前景。目前国内相关产品严重依赖进口，对PFPEs的研究比较缺乏，尤其对Y型PFPEs的研究非常少，亟需加强对相关领域的开发和研究。核磁共振氟谱（¹⁹F NMR）是解析PFPEs结构的重要技术，但由于技术封锁、制备困难等原因，有关Y型PFPE羧酸（PFPE-CA）的¹⁹F NMR谱图解析尚不完善。本研究采用合适的制样条件，得到了清晰的Y型PFPE-CA的¹⁹F NMR谱图，并对主链和端基中不同化学环境的F原子化学位移进行归属。通过对谱峰进行积分可计算活性混合物的组成以及样品的数均分子量。该分析方法准确、快捷，为之后Y型PFPEs的生产及分离技术的突破提供了研究基础。

关键词: 全氟聚醚羧酸, Y型, 结构解析, 聚合物, 核磁共振, 电子材料

Abstract:

Perfluoropolyether and their derivatives (PFPEs) are a class of fluoropolymers with high added value. Their specific physicochemical properties make them have a good commercial prospect. At present, domestic related products are heavily dependent on imports, and there is a lack of research on PFPEs, especially on Y-type PFPEs, so it is urgent to strengthen the development and research in related fields. Nuclear magnetic resonance fluorine spectroscopy (¹⁹F NMR) is an important technique for the structure analysis of perfluorinated polyether compounds. However, due to technical blockade and difficulties in preparation, the analysis of ¹⁹F NMR spectroscopy of Y-type PFPE carboxylic acid (PFPE-CA) is still not perfect. In this study, ¹⁹F NMR spectra of Y-type PFPE-CA with flat base were obtained under suitable sample preparation conditions, and chemical shifts of F atoms in different chemical environments in the main chain and end group were attributed. The composition of the active mixture and the number average molecular weight of the sample can be calculated by integrating the spectral peaks. This analysis method is accurate and fast, and provides a research basis for the breakthrough of production and separation technology of Y-type PFPEs.

Key words: perfluoropolyether carboxylic acid, Y-type, structural analysis, polymers, NMR, electronic materials

中图分类号:

TQ 317.2

张文惠, 唐茹意, 崔希利, 邢华斌. 羧酸端基Y型全氟聚醚的氟谱解析及结构表征[J]. 化工学报, DOI: 10.11949/0438-1157.20231411.

Wenhui ZHANG, Ruyi TANG, Xili CUI, Huabin XING. Fluorine spectrum analysis and structural characterization of Y-type perfluoropolyether carboxylic acid[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231411.

图/表 6

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基团		化学位移
惰性端基	CF₃—O—CF₂—	-57.64
	CF₃—O—CF(CF₃) —	-55.82
	CF₃—CF₂—CF₂—O—	-83.67
	CF₃—CF₂—CF₂—O—	-132.00
	CF₃—CF₂—O—	-89.23
	CF₃—CF₂—O—	-90.63
	(CF₃)₂CF—	-82.86
	(CF₃)₂CF—	-148.21
活性端基	—CF₂COOH	-76.60 ~-77.87
重复单元	—OCF₂CF(CF₃)O—	-80.81 ~-82.86
	—OCF₂CF(CF₃)O—	-146.78
	—OCF₂—	-51.39

基团		化学位移
惰性端基	CF₃—O—CF₂—	-57.64
	CF₃—O—CF(CF₃) —	-55.82
	CF₃—CF₂—CF₂—O—	-83.67
	CF₃—CF₂—CF₂—O—	-132.00
	CF₃—CF₂—O—	-89.23
	CF₃—CF₂—O—	-90.63
	(CF₃)₂CF—	-82.86
	(CF₃)₂CF—	-148.21
活性端基	—CF₂COOH	-76.60 ~-77.87
重复单元	—OCF₂CF(CF₃)O—	-80.81 ~-82.86
	—OCF₂CF(CF₃)O—	-146.78
	—OCF₂—	-51.39

基团	峰面积a		矫正后峰面积A
—OCF₃	1.24	0.413	0.450
—OCF₂CF₂CF₃	0.37	0.123	0.138
—OCF₂CF₂CF₃	0.26	0.130	0.138
—OCF₂CF₃	0.07	0.035	0.043
—OCF₂CF₃	0.13	0.043	0.043
—CF(CF₃)₂	1.52	0.253	0.280
—CF(CF₃)₂	0.26	0.260	0.280
—CF₂COOH	2.00	1.000	1.089
—OCF₂—	0.34	0.170	0.185
—OCF₂CF(CF₃) —	13.36	2.672	2.861
—OCF₂CF(CF₃) —	2.58	2.580	2.861

基团	峰面积a		矫正后峰面积A
—OCF₃	1.24	0.413	0.450
—OCF₂CF₂CF₃	0.37	0.123	0.138
—OCF₂CF₂CF₃	0.26	0.130	0.138
—OCF₂CF₃	0.07	0.035	0.043
—OCF₂CF₃	0.13	0.043	0.043
—CF(CF₃)₂	1.52	0.253	0.280
—CF(CF₃)₂	0.26	0.260	0.280
—CF₂COOH	2.00	1.000	1.089
—OCF₂—	0.34	0.170	0.185
—OCF₂CF(CF₃) —	13.36	2.672	2.861
—OCF₂CF(CF₃) —	2.58	2.580	2.861

序号	样品质量/g	V/mL	V₀ /mL	酸值/(mg KOH/g)
1	0.9127	9.99	21.49	70.403
2	0.8785	10.73	21.49	68.437
3	0.7634	12.05	21.49	69.094
4	0.8375	11.26	21.49	68.252
5	0.9513	9.77	21.49	68.839
6	0.8513	10.94	21.49	69.246