CIESC Journal ›› 2023, Vol. 74 ›› Issue (1): 479-486.DOI: 10.11949/0438-1157.20221490
• Material science and engineering, nanotechnology • Previous Articles
Ruyi TANG1(), Hanqian PAN1, Xiajun ZHENG2, Guangxin ZHANG2, Xingping WANG2, Xili CUI1,3(
), Huabin XING1,3
Received:
2022-11-15
Revised:
2022-12-20
Online:
2023-03-20
Published:
2023-01-05
Contact:
Xili CUI
唐茹意1(), 潘罕骞1, 郑侠俊2, 张广欣2, 汪星平2, 崔希利1,3(
), 邢华斌1,3
通讯作者:
崔希利
作者简介:
唐茹意(1998—),女,硕士研究生,tangry@zju.edu.cn
基金资助:
CLC Number:
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.
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.
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 |
Ⅳ① | F3CO—(CF2CF2O) p —(CF2O) q —CF3 F3CO—(CF2CF2O) p —(CF2O) q —CF2COOH HOOCF2CO—(CF2CF2O) p —(CF2O) q —CF2COOH |
Table 1 Composition of PFPE samples
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 |
Ⅳ① | 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 |
Table 2 Dissolution of PFPE samples in different NMR solvents
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 |
Table 3 Types of deuterated reagents and their volume ratio with fluorine-containing co-solvents on the dissolution of Z-type PFPE(sample Ⅳ)
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 |
基团 | 序列 | 化学位移δ | 结构 |
---|---|---|---|
A1 | AAA; BAA | -88.31~-90.49 | —OCF2CF2O |
A2 | BAA; BAB | -90.50~-92.01 | —OCF2O |
B1 | ABA | -51.56~-53.21 | —OCF2CF2O |
B2 | ABB | -53.53~-54.55 | —OCF2CF2O |
B3 | BBB | -55.43~-56.18 | —OCF2O |
E | E | -124.95~-127.91 | —OCF2 |
F | F | -128.44~-131.82 | —OCF2 |
G1 | EA | -83.47~-84.91 | —OCF2CF2CF2 |
FA | -83.47~-84.91 | —OCF2CF2 | |
G2 | EB | -85.31~-86.72 | —OCF2CF2CF2 |
FB | -85.31~-86.72 | —OCF2CF2 | |
C1 | AC | -56.20~-56.93 | —OCF2CF2O |
C2 | BC | -57.56~-58.75 | —OCF2O |
D1 | AD | -79.70~-80.26 | —OCF2CF2O |
D2 | BD | -77.95~-78.48 | —OCF2O |
Table 4 Group arrangement and corresponding chemical shifts of Z-type PFPE
基团 | 序列 | 化学位移δ | 结构 |
---|---|---|---|
A1 | AAA; BAA | -88.31~-90.49 | —OCF2CF2O |
A2 | BAA; BAB | -90.50~-92.01 | —OCF2O |
B1 | ABA | -51.56~-53.21 | —OCF2CF2O |
B2 | ABB | -53.53~-54.55 | —OCF2CF2O |
B3 | BBB | -55.43~-56.18 | —OCF2O |
E | E | -124.95~-127.91 | —OCF2 |
F | F | -128.44~-131.82 | —OCF2 |
G1 | EA | -83.47~-84.91 | —OCF2CF2CF2 |
FA | -83.47~-84.91 | —OCF2CF2 | |
G2 | EB | -85.31~-86.72 | —OCF2CF2CF2 |
FB | -85.31~-86.72 | —OCF2CF2 | |
C1 | AC | -56.20~-56.93 | —OCF2CF2O |
C2 | BC | -57.56~-58.75 | —OCF2O |
D1 | AD | -79.70~-80.26 | —OCF2CF2O |
D2 | BD | -77.95~-78.48 | —OCF2O |
基团 | 结构 | 分子量 | F原子个数 | 矫正方法 |
---|---|---|---|---|
D | — | MD=95 | 2 | 以SD=(SD1+SD2)为基准 |
A | — | MA=116 | 4 | SA=(SA1+SA2)/2 |
B | — | MB=66 | 2 | SB=(SB1+SB2+SB3) |
C | —O | MC=85 | 3 | SC=(SC1+SC2)/1.5 |
E | —CF2 | ME=216 | 4 | SE=SE/2 |
F | —CF2 | MF=166 | 2 | SF |
Table 5 Correction method for the peak area of each group in 19F NMR spectrum of Z-type PFPE
基团 | 结构 | 分子量 | F原子个数 | 矫正方法 |
---|---|---|---|---|
D | — | MD=95 | 2 | 以SD=(SD1+SD2)为基准 |
A | — | MA=116 | 4 | SA=(SA1+SA2)/2 |
B | — | MB=66 | 2 | SB=(SB1+SB2+SB3) |
C | —O | MC=85 | 3 | SC=(SC1+SC2)/1.5 |
E | —CF2 | ME=216 | 4 | SE=SE/2 |
F | —CF2 | MF=166 | 2 | SF |
基团 | 峰面积 | 矫正后峰面积 | 聚合度 |
---|---|---|---|
惰性端基C:—OCF3 | 4.13 | 4.13/1.5=2.75 | 端基峰面积均值: |
活性端基D:—CF2COOH | 2.18 | 2.18 | (2.75+2.18)/2=2.47 |
重复单元A:—CF2CF2O— | 103.81 | 103.81/2=51.91 | 聚合度p:51.91/2.47=21.02 |
重复单元B:—CF2O— | 47.62 | 47.62 | 聚合度q:47.62/2.47=19.28 |
重复单元E:—CF2 | 4.78 | 4.78/2=2.39 | 聚合度m:2.39/2.47=0.97 |
重复单元F:—CF2 | 2.56 | 2.56 | 聚合度n:2.56/2.47=1.04 |
Table 6 The results of polymerization degree and molecular weight of Z-type PFPE mixture (sample Ⅲ)
基团 | 峰面积 | 矫正后峰面积 | 聚合度 |
---|---|---|---|
惰性端基C:—OCF3 | 4.13 | 4.13/1.5=2.75 | 端基峰面积均值: |
活性端基D:—CF2COOH | 2.18 | 2.18 | (2.75+2.18)/2=2.47 |
重复单元A:—CF2CF2O— | 103.81 | 103.81/2=51.91 | 聚合度p:51.91/2.47=21.02 |
重复单元B:—CF2O— | 47.62 | 47.62 | 聚合度q:47.62/2.47=19.28 |
重复单元E:—CF2 | 4.78 | 4.78/2=2.39 | 聚合度m:2.39/2.47=0.97 |
重复单元F:—CF2 | 2.56 | 2.56 | 聚合度n:2.56/2.47=1.04 |
Fig. 4 19F NMR spectrum of two-component Z-type functionalized PFPE carboxylate potassium salt (sample Ⅱ) and integration results of its end-group peaks
端基种类 | 化学位移δ | 基团 | 积分面积 | 矫正后 积分面积和 |
---|---|---|---|---|
惰性端基C | -55.80~-56.20 | —OCF2CF2 | 0.61 | 0.58 |
-57.31~-57.84 | —OCF2 | 0.26 | ||
活性端基D | -77.98~-78.27 | —OCF2O | 1.00 | 1.99 |
-79.70~-79.97 | —OCF2CF2O | 0.99 |
Table 7 Integral results of end-group peaks of two-component Z-type active PFPE carboxylate potassium salt (sample Ⅱ)
端基种类 | 化学位移δ | 基团 | 积分面积 | 矫正后 积分面积和 |
---|---|---|---|---|
惰性端基C | -55.80~-56.20 | —OCF2CF2 | 0.61 | 0.58 |
-57.31~-57.84 | —OCF2 | 0.26 | ||
活性端基D | -77.98~-78.27 | —OCF2O | 1.00 | 1.99 |
-79.70~-79.97 | —OCF2CF2O | 0.99 |
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