Synthesis and Characterization of Perfluorocyclobutyl Copoly(aryl ether)s Containing Biphenyl and Sulfonyl Moieties

Qian Liu; Yu-xue Yang; Shou-hai Zhang; Ren-dong Xue; Xi-gao Jian

doi:10.11777/j.issn1000-3004.2017.17211

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Synthesis and Characterization of Perfluorocyclobutyl Copoly(aryl ether)s Containing Biphenyl and Sulfonyl Moieties

Research Article | 更新时间：2021-01-26

- Synthesis and Characterization of Perfluorocyclobutyl Copoly(aryl ether)s Containing Biphenyl and Sulfonyl Moieties
- Acta Polymerica Sinica Vol. 0, Issue 5, Pages: 581-587(2018)
- 作者机构：
  
  大连理工大学化工学院辽宁省高性能树脂工程技术研究中心辽宁省高分子科学与工程重点实验室　大连 116024
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3004.2017.17211
  CLC：
- Published：2018-5，
  
  Received：2 August 2017，
  
  Revised：9 October 2017，
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Qian Liu, Yu-xue Yang, Shou-hai Zhang, Ren-dong Xue, Xi-gao Jian. Synthesis and Characterization of Perfluorocyclobutyl Copoly(aryl ether)s Containing Biphenyl and Sulfonyl Moieties. [J]. Acta Polymerica Sinica 0(5):581-587(2018)
DOI：

Qian Liu, Yu-xue Yang, Shou-hai Zhang, Ren-dong Xue, Xi-gao Jian. Synthesis and Characterization of Perfluorocyclobutyl Copoly(aryl ether)s Containing Biphenyl and Sulfonyl Moieties. [J]. Acta Polymerica Sinica 0(5):581-587(2018) DOI： 10.11777/j.issn1000-3004.2017.17211.

摘要

以二苯醚为溶剂，4

4′-双(三氟乙烯氧基)苯砜(DTS)与4

4′-双(三氟乙烯氧基)联苯(DTB)为单体进行高温溶液共聚合. 通过调控2种单体的加入比例(DTS:DTB为3:7 ~ 7:3)经[2

+ 2

]热环化反应，制备了一系列含联苯和砜基结构全氟环丁基共聚芳醚(PFCB-S-BP). 采用凝胶渗透色谱(GPC)对该系列共聚芳醚的分子量及分子量分布进行了测定，结果表明两单体发生共聚合反应，合成的共聚芳醚数均分子量均大于1.4 × 10

，且分子量分布较窄介于1.4 ~ 1.6之间. 采用红外吸收光谱、核磁共振波谱等对PFCB-S-BP结构进行了表征. PFCB-S-BP的红外光谱中三氟乙烯基醚单体在1824 cm

−1

处的特征吸收峰消失，而在957 cm

−1

出现了强的全氟环丁基特征吸收峰，1315和1100 cm

−1

处砜基的特征吸收峰强度随DTS/DTB比例的增加而变强. PFCB-S-BP的氢核磁谱图中，

= 7.9处为苯环上砜基邻位氢原子的信号峰，其强度随着反应单体DTS/DTB比例的增大而增强. 氟核磁谱图(

F-NMR)中，化学位移在−127 ~ −134的复杂多重峰是由于全氟环丁基环顺式和反式取代不同引起的. 结果表明DTS与DTB单体发生了共聚合反应，成功合成了全氟环丁基聚芳醚PFCB-S-BP，并测试了其耐热性、热稳定性、溶解性等性能. PFCB-S-BP的5%热失重温度均高于470 °C，玻璃化转变温度均高于145 °C，具有较好的热稳定性. PFCB-S-BP可溶解于

-甲基-2-吡咯烷酮、

-二甲基乙酰胺和氯仿等常用有机溶剂，表现出良好的溶解性.

Abstract

High temperature solution copolymerization of 4

4′-sulfonyl-bis(trifluorovinyloxy)biphenyl (DTS) and 4

4 ′-bis(trifluorovinyloxy)biphenyl (DTB) were carried out in diphenyl ether as the solvent. A series of perfluorocyclobutyl copoly(aryl ether)s containing biphenyl and sulfonyl moieties (PFCB-S-BP) were prepared

via

thermal [2

+ 2

] cycloaddition polymerization by controlling the ratio of DTS to DTB. PFCB-S-BP was synthesized when the ratio of DTS to DTB ranged from 3/7 to 7/3. Molecular weight and its distribution of PFCB-S-BP were measured by gel permeation chromatography (GPC). The GPC curves showed a narrow and unimodal elution peak. The number-average molecular weight of PFCB-S-BP was larger than 1.4 × 10

with a narrow molecular weight distribution ranging from 1.4 to 1.6. The chemical structures was characterized by Fourier transform infrared spectroscopy Fourier transform infrared spectroscopy (FTIR)

hydrogen nuclear magnetic resonance (

H-NMR) and fluorine nuclear magnetic resonance (

F-NMR). The characteristic signal of trifluorovinyl ether group of monomers at 1824 cm

−1

disappeared in Fourier transform infrared spectroscopy (FTIR) spectra of PFCB-S-BP and the strong perfluorocyclobutyl group characteristic peak at 957 cm

−1

appeared. The intensities of sulfonyl group characteristic absorption peaks at 1100 and 1315 cm

−1

increased with the increase in the ratio of DTS to DTB. From

H-NMR of PFCB-S-BP

the signal at 7.9 was assigned to the protons of benzene ring adjacent to sulfonyl group. The intensity of the signal increased with an increase in the ratio of DTS to DTB. For

F-NMR of PFCB-S-BP

the multiple peaks ranging from −127 to −134 were ascribed to the

cis

- and

trans

-substituted PFCB rings. These results indicated that DTS copolymerized with DTB

and PFCB-S-BP copolymers were successfully synthesized. The thermal property and solubility of PFCB-S-BP were also tested.

of PFCB-S-BP increased slightly from 146 °C to 153 °C with an increase in the ratio of DTS to DTB from 3/7 to 7/3. The decomposition temperature for 5% weight loss of PFCB-S-BP was above 470 °C. These results showed that PFCB-S-BP exhibited high thermal stability and was soluble in common organic solvents such as

-methyl-2-pyrrolidinone

-dimethylacetamide and chloroform.

关键词

三氟乙烯氧基全氟环丁基聚芳醚共聚

Keywords

TrifluorovinyloxyPerfluorocyclobutylPoly(aryl ether)Copolymerization

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