负离子聚合制备环氧化八臂星形聚异戊二烯及其表征

徐俊; 钱强雨; 何金林; 张明祖; 戴礼兴; 倪沛红

doi:10.11777/j.issn1000-3304.2017.17087

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负离子聚合制备环氧化八臂星形聚异戊二烯及其表征

研究论文 | 更新时间：2021-01-26

- 负离子聚合制备环氧化八臂星形聚异戊二烯及其表征
- Anionic Synthesis and Characterization of Epoxidized Eight-arm Star-shaped Polyisoprene
- 高分子学报 2018年49卷第3期页码：356-365
- 作者机构：
  
  苏州大学材料与化学化工学部新型功能高分子材料国家地方联合工程实验室苏州市大分子设计与精密合成重点实验室江苏省先进功能高分子材料设计及应用重点实验室苏州 215123
- 作者简介：
  
  何金林, E-mail:jlhe@suda.edu.cn Jin-lin He, E-mail:jlhe@suda.edu.cn
- 基金信息：
  
  国家自然科学基金(21774081);国家自然科学基金(21304061);江苏省自然科学基金(BK20171212);北京分子科学国家实验室开放课题基金(20140152);江苏高校优势学科建设工程(PAPD);江苏高校优势学科建设工程(YX10900112)
- DOI：10.11777/j.issn1000-3304.2017.17087
  中图分类号：
- 纸质出版日期：2018-3-20，
  
  收稿日期：2017-4-14，
  
  修回日期：2017-4-27，
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徐俊, 钱强雨, 何金林, 张明祖, 戴礼兴, 倪沛红. 负离子聚合制备环氧化八臂星形聚异戊二烯及其表征[J]. 高分子学报, 2018,49(3):356-365.

Jun Xu, Qiang-yu Qian, Jin-lin He, Ming-zu Zhang, Li-xing Dai, Pei-hong Ni. Anionic Synthesis and Characterization of Epoxidized Eight-arm Star-shaped Polyisoprene[J]. Acta Polymerica Sinica, 2018,49(3):356-365.
徐俊, 钱强雨, 何金林, 张明祖, 戴礼兴, 倪沛红. 负离子聚合制备环氧化八臂星形聚异戊二烯及其表征[J]. 高分子学报, 2018,49(3):356-365. DOI： 10.11777/j.issn1000-3304.2017.17087.

Jun Xu, Qiang-yu Qian, Jin-lin He, Ming-zu Zhang, Li-xing Dai, Pei-hong Ni. Anionic Synthesis and Characterization of Epoxidized Eight-arm Star-shaped Polyisoprene[J]. Acta Polymerica Sinica, 2018,49(3):356-365. DOI： 10.11777/j.issn1000-3304.2017.17087.

摘要

利用仲丁基锂引发异戊二烯进行高真空负离子聚合制备聚异戊二烯基锂活性链(PI-Li)

再与八乙烯基多面体齐聚倍半硅氧烷(OVPOSS)在环己烷中发生加成反应

一步法制得八臂星形聚合物.利用分级沉淀去除稍过量的的线型聚异戊二烯以及低加成产物

即可得到纯的八臂星形聚异戊二烯(8PI-POSS).最后

通过甲酸/过氧化氢对8PI-POSS中的聚异戊二烯链进行部分氧化反应

获得环氧化八臂星形聚异戊二烯(8EPI-POSS).利用核磁共振波谱(

H-

C-NMR)、凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FTIR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)对聚合物的化学结构、分子量及分子量分布进行表征.实验结果表明

通过调节单体与引发剂的摩尔比

成功合成了不同聚合度的8PI-POSS和8EPI-POSS; 并且通过改变氧化反应的温度和时间以及氧化试剂的用量

可以简易改变8EPI-POSS的环氧度.最后

通过热失重分析(TGA)测试了几种聚合物的热分解温度

结果显示

PI均聚物在200℃左右开始分解

而由于POSS的引入

8PI-POSS和8EPI-POSS在340℃左右才开始分解

并且与PI均聚物相比

在800℃还有大概3%的残留组分.

Abstract

The synthesis of epoxidized star-shaped polymers by incorporation of living anionic polymerization with polyhedral oligomericsilsesquioxane (POSS) is seldom reported.In this study

the living (polyisopryl)lithium (PI-Li) is first synthesized in cyclohexane

via

high-vacuum living anionic polymerization using sec-butyllithium as the initiator and isoprene as the monomer.Subsequently

PI-Li is used to react with octavinyl polyhedral oligomericsilsesquioxane (OVPOSS) in cyclohexane to prepare an eight-arm star-shaped polyisoprene (8PI-POSS) in one pot.Purified 8PI-POSS is obtained after fractionation precipitation using cyclohexane/ethanol as solvent/nonsolvent

and characterized by nuclear magnetic resonance (

H-and

C-NMR)

gel permeation chromatography (GPC)

matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectroscopy and Fourier transform infrared spectroscopy (FTIR)

respectively.Star-shaped polyisoprenes with different arm lengths are synthesized by changing the feed ratio of the monomer to the initiator.The compositions of the polymers are determined by comparison of integrals of characteristic signals from

H-NMR spectra.GPC tests demonstrate that the eluent curves of the crude star-shaped polyisoprenes show an apparent shift to higher molecular weight compared with that of the base PI.The purified star-shaped polyisoprene (8PI-POSS) by fractionation precipitation possesses symmetric peaks with relatively narrow polydispersity.MALDI-TOF MS analysis indicates that the observed molecular weight of base PI is in good agreement with the calculated value.In addition

there are two minor peaks with an interval of 16 Da in the MALDI-TOF MS spectrum

which may be attributed to the possible oxidation reaction during storage or MALDI-TOF MS test.Unfortunately

the MALDI-TOF MS spectra of 8PI-POSS are not obtained probably due to their high molecular weights.Finally

the epoxidized star-shaped polyisoprene (8EPI-POSS) is obtained by oxidation of 8PI-POSS catalyzed by HCOOH/H

.The 8EPI-POSS polymer is also characterized by

H-and

C-NMR

GPC and FTIR analyses

respectively.The characteristic signals found in

H-and

C-NMR spectra

as well as in FTIR spectra confirm the formation of epoxy group in the 8EPI-POSS.By changing the temperature and time of oxidation reaction

the star-shaped 8EPI-POSS with different percentages of epoxidation (PE) are prepared.It is also found that the GPC eluent curve of 8EPI-POSS change a little after the oxidation reaction.TGA tests show that the thermal decomposition temperature of 8PI-POSS and 8EPI-POSS are higher than that of the base PI.Moreover

it is also found that about 3% residue is left at about 800 ℃

which maybe because of the incorporation of POSS segment in the star-shaped polymers.The epoxidized star-shaped polyisoprenes reported here may serve as an important intermediate in the preparation of highly branched polymers and as the novel tougheners for epoxy resins.

关键词

高真空活性负离子聚合环氧化星形聚合物多面体齐聚倍半硅氧烷(POSS)聚异戊二烯

Keywords

Living anionic polymerizationEpoxidized star-shaped polymerPOSSPolyisoprene

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活性负离子聚合法制备POSS基七臂星形聚合物及其表征