活性负离子聚合制备八臂星形嵌段共聚物及其氢化反应研究

王彬; 张明祖; 何金林; 倪沛红

doi:10.11777/j.issn1000-3304.2020.20035

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活性负离子聚合制备八臂星形嵌段共聚物及其氢化反应研究

论文 | 更新时间：2021-01-26

- 活性负离子聚合制备八臂星形嵌段共聚物及其氢化反应研究
  增强出版
- Living Anionic Synthesis of Eight-arm Star-shaped Block Copolymer and Study on Its Hydrogenation
- 高分子学报 2020年51卷第9期页码：1010-1020
- 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江苏省先进功能高分子材料设计及应用重点实验室苏州市大分子设计与精密合成重点实验室　苏州 215123
- 作者简介：
  
  E-mail: jlhe@suda.edu.cn
- 基金信息：
  
  国家自然科学基金面上项目(基金号 21774081)和江苏省自然科学基金面上项目(基金号 BK20171212)资助
- DOI：10.11777/j.issn1000-3304.2020.20035
  中图分类号：
- 纸质出版日期：2020-8-15，
  
  网络出版日期：2020-4-15，
  
  收稿日期：2020-2-14，
  
  修回日期：2020-2-17，
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王彬, 张明祖, 何金林, 倪沛红. 活性负离子聚合制备八臂星形嵌段共聚物及其氢化反应研究[J]. 高分子学报, 2020,51(9):1010-1020.

Bin Wang, Ming-zu Zhang, Jin-lin He, Pei-hong Ni. Living Anionic Synthesis of Eight-arm Star-shaped Block Copolymer and Study on Its Hydrogenation[J]. Acta Polymerica Sinica, 2020,51(9):1010-1020.
王彬, 张明祖, 何金林, 倪沛红. 活性负离子聚合制备八臂星形嵌段共聚物及其氢化反应研究[J]. 高分子学报, 2020,51(9):1010-1020. DOI： 10.11777/j.issn1000-3304.2020.20035.

Bin Wang, Ming-zu Zhang, Jin-lin He, Pei-hong Ni. Living Anionic Synthesis of Eight-arm Star-shaped Block Copolymer and Study on Its Hydrogenation[J]. Acta Polymerica Sinica, 2020,51(9):1010-1020. DOI： 10.11777/j.issn1000-3304.2020.20035.

摘要

首先使用活性负离子聚合法合成(聚苯乙烯-

-聚异戊二烯)锂(PS-PI-Li)活性链，再利用其与八乙烯基多面体低聚倍半硅氧烷(OVPOSS)发生偶联反应，通过分级沉淀去除少量低偶联产物，即可得到纯的八臂星形嵌段共聚物(PS-PI)

POSS；最后，采用对甲苯磺酰肼(TSH)对(PS-PI)

POSS中的PI链段进行氢化加成反应，制得另一种含有饱和烃链段的新型八臂星形嵌段共聚物(PS-HPI)

POSS，并初步探究TSH投料量和反应时间对氢化加成反应的影响. 采用凝胶渗透色谱(GPC)、核磁共振氢谱(

H-NMR)和傅里叶变换红外光谱(FTIR)详细表征了聚合物的化学结构、分子量和分子量分布，并利用热失重分析(TGA)测试了(PS-PI)

POSS在氢化加成反应前后的热稳定性.

Abstract

The preparation and characterization of eight-arm star-shaped block copolymer (PS-PI)

POSS and study on its hydrogenation are reported in this paper. Firstly

living polystyrene-

-polyisoprene block copolymer chain (PS-PI-Li) was synthesized in benzene

via

high-vacuum living anionic polymerization with styrene and isoprene as the monomers and

sec

-butyllithium as the initiator. Subsequently

octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) was used to react with slightly excess PS-PI-Li in benzene to prepare an eight-arm star-shaped block copolymer (PS-PI)

POSS. After obtaining purified (PS-PI)

POSS by fractionation precipitation using toluene and methanol as the solvent/nonsolvent pair

the chemical structures and molecular weight information of (PS-PI)

POSS and precursors were characterized by proton nuclear magnetic resonance (

H-NMR)

Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Finally

the hydrogenation of (PS-PI)

POSS was carried out with

-toluenesulfonyl hydrazide (TSH) in xylene under a nitrogen astmosphere. Four kinds of hydrogenated eight-arm star-shaped (PS-HPI)

POSS were synthesized by changing the feeding amount of TSH. The chemical structures of hydrogenated copolymers were characterized by means of FTIR

H-NMR and GPC.

H-NMR analysis indicated that (PS-HPI)

POSS-4 and (PS-HPI)

POSS-8 samples obtained by using 4 and 8 molar equiv. TSH were almost completely hydrogenated

while (PS-HPI)

POSS-2 sample using 2 molar equiv. TSH displayed a few residual double bonds of PI block. GPC analysis demonstrated that (PS-HPI)

POSS-8 showed less degradation and narrower polydispersity compared with other (PS-HPI)

POSS samples. To explore the effect of reaction time on hydrogenation

some samples were taken out at different time during hydrogenation reaction. With the aiding of

H-NMR and GPC analyses

the (PS-HPI)

POSS samples collected at different time points were characterized. The

H-NMR result indicated that hydrogenation of (PS-PI)

POSS was completed after 12 h reaction. In order to compare the thermal stability of (PS-PI)

POSS and (PS-HPI)

POSS

TGA tests were conducted. It was indicated that the 5% initial decomposition temperature of (PS-HPI)

POSS reached 410 − 420 °C

higher than that of (PS-PI)

POSS (~ 360 °C). Besides

the quick decomposition temperature of (PS-HPI)

POSS was above 470 °C

much higher than that of (PS-PI)

POSS (~ 405 °C). Our study provides a fast and efficient method for the preparation of eight-arm star-shaped block copolymer

which could be further hydrogenated to enhance its thermal stability. This kind of novel star-shaped block copolymers containing both hard and soft segments may find potential application in thermoplastic elastomers.

关键词

活性负离子聚合星形聚合物多面体低聚倍半硅氧烷氢化反应

Keywords

Living anionic polymerizationStar-shaped polymerPolyhedral oligomeric silsesquioxaneHydrogenation

references

Hirao A, Goseki R, Ishizone T. Macromolecules , 2014 . 47 ( 6 ): 1883 - 1905 . DOI:10.1021/ma401175mhttp://doi.org/10.1021/ma401175m .

Polymeropoulos G, Zapsas G, Ntetsikas K, Bilalis P, Gnanou Y, Hadjichristidis N. Macromolecules , 2017 . 50 ( 4 ): 1253 - 1290 . DOI:10.1021/acs.macromol.6b02569http://doi.org/10.1021/acs.macromol.6b02569 .

Goseki R, Matsuo Y, Hirao A. Polym Chem , 2018 . 9 ( 7 ): 834 - 844 . DOI:10.1039/C7PY01948Chttp://doi.org/10.1039/C7PY01948C .

Lee S, Chang T. Macromol Chem Phys , 2017 . 218 ( 12 ): 1700087 DOI:10.1002/macp.201700087http://doi.org/10.1002/macp.201700087 .

Goseki R, Ito S, Hirao A. Polymer , 2017 . 124 284 - 292 . DOI:10.1016/j.polymer.2017.07.058http://doi.org/10.1016/j.polymer.2017.07.058 .

Hong L X, Yang S H, He J P. Eur Polym J , 2015 . 65 171 - 190 . DOI:10.1016/j.eurpolymj.2015.02.019http://doi.org/10.1016/j.eurpolymj.2015.02.019 .

Yan Xuesheng(晏雪生), Xu Jun(徐俊), He Jinlin(何金林), Zhang Mingzu(张明祖), Dai Lixing(戴礼兴), Ni Peihong(倪沛红). Acta Polymerica Sinica(高分子学报) , 2017 . ( 3 ): 454 - 463 . DOI:10.11777/j.issn1000-3304.2017.16128http://doi.org/10.11777/j.issn1000-3304.2017.16128 .

Hadjichristidis N, Iatrou H, Pispas S, Pitsikalis M. J Polym Sci, Part A: Polym Chem , 2000 . 38 3211 - 3234 . DOI:10.1002/1099-0518(20000915)38:18<3211::AID-POLA10>3.0.CO;2-Lhttp://doi.org/10.1002/1099-0518(20000915)38:18<3211::AID-POLA10>3.0.CO;2-L .

Uhrig D, Mays J W. J Polym Sci, Part A: Polym Chem , 2005 . 43 ( 24 ): 6179 - 6222 . DOI:10.1002/pola.21016http://doi.org/10.1002/pola.21016 .

Ma Hongwei(马红卫), Zhang Chunqing(张春庆), Li Yang(李杨), Wang Yurong(王玉荣), Hu Yanming(胡雁鸣),Li Zhansheng(李战胜), Zhao Zhongfu(赵忠夫), Shen Kaihua(申凯华). Acta Polymerica Sinica(高分子学报) , 2011 . ( 12 ): 1390 - 1394.

Xu Jun(徐俊), Qian Qiangyu(钱强雨), He Jinlin(何金林), Zhang Mingzu(张明祖), Dai Lixing(戴礼兴), Ni Peihong(倪沛红). Acta Polymerica Sinica(高分子学报) , 2018 . ( 3 ): 356 - 365 . DOI:10.11777/j.issn1000-3304.2017.17087http://doi.org/10.11777/j.issn1000-3304.2017.17087 .

Zhu Liji(朱李继), Li Yang(李杨), Wang Yurong(王玉荣), Zhang Chunqing(张春庆). Polymer Bulletin(高分子通报) , 2009 . ( 8 ): 14 - 23.

Chae C G, Bak I G, Lee J S. Macromolecules , 2018 . 51 ( 17 ): 6771 - 6781 . DOI:10.1021/acs.macromol.8b01458http://doi.org/10.1021/acs.macromol.8b01458 .

Zhang Y, Li J, Li X H, He J P. Macromolecules , 2014 . 47 ( 18 ): 6260 - 6269 . DOI:10.1021/ma501283bhttp://doi.org/10.1021/ma501283b .

An Zesheng(安泽胜), Chen Changle(陈昶乐), He Junpo(何军坡), Hong Chunyan(洪春雁), Li Zhibo(李志波),Li Zichen(李子臣), Liu Chao(刘超), Lv Xiaobing(吕小兵), Qin Anjun(秦安军), Qu Chengke(曲程科),Tang Benzhong(唐本忠), Tao Youhua(陶友华), Wan Xinhua(宛新华), Wang Guowei(王国伟), Wang Jia(王佳),Zheng Ke(郑轲), Zou Wenkai(邹文凯). Acta Polymerica Sinica(高分子学报) , 2019 . 50 ( 10 ): 1083 - 1132.

Liu P B, Ma H W, Han L, Shen H Y, Yang L C, Li C, Hao X Y, Li Y. Angew Chem Int Ed , 2018 . 57 ( 50 ): 16538 - 16543 . DOI:10.1002/anie.201809857http://doi.org/10.1002/anie.201809857 .

Forens A, Roos K, Dire C, Gadenne B, Carlotti S. Chinese J Polym Sci , 2020 . 38 357 - 362 . DOI:10.1007/s10118-020-2355-4http://doi.org/10.1007/s10118-020-2355-4 .

Chae C G, Yu Y G, Seo H B, Kim M J, Wen Z W, Lee J S. Macromolecules , 2019 . 52 ( 13 ): 4828 - 4838 . DOI:10.1021/acs.macromol.9b00559http://doi.org/10.1021/acs.macromol.9b00559 .

Matic A, Hess A, Schanzenbach D, Schlaad H. Polym Chem , 2020 . 11 ( 7 ): 1364 - 1368 . DOI:10.1039/c9py01783fhttp://doi.org/10.1039/c9py01783f .

Bai H Y, Zhang Z, Ma H W, Han L, Mu X C, Huang W, Liu P B, Wu Y B. Polym Chem , 2019 . 10 1140 - 1149 . DOI:10.1039/C8PY01825Ahttp://doi.org/10.1039/C8PY01825A .

Chae C G, Bak I G, Lee J S. Macromolecules , 2019 . 52 ( 9 ): 3530 - 3542 . DOI:10.1021/acs.macromol.9b00397http://doi.org/10.1021/acs.macromol.9b00397 .

Domanskyi S, Gentekos D T, Privman V, Fors B P. Polym Chem , 2020 . 11 326 - 336 . DOI:10.1039/C9PY00074Ghttp://doi.org/10.1039/C9PY00074G .

Zheng K, Ren J, He J P. Macromolecules , 2019 . 52 ( 17 ): 6780 - 6791 . DOI:10.1021/acs.macromol.9b00920http://doi.org/10.1021/acs.macromol.9b00920 .

Polymeropoulos G, Bilalis P, Feng X Y, Thomas E L, Gnanou Y, Hadjichristidis N. Macromolecules , 2019 . 52 ( 15 ): 5583 - 5589 . DOI:10.1021/acs.macromol.9b01013http://doi.org/10.1021/acs.macromol.9b01013 .

Yu Y G, Seo C, Chae C G, Seo H B, Kim M J, Kang Y, Lee J S. Macromolecules , 2019 . 52 ( 11 ): 4349 - 4358 . DOI:10.1021/acs.macromol.9b00678http://doi.org/10.1021/acs.macromol.9b00678 .

Higashihara T, Hayashi M, Hirao A. Prog Polym Sci , 2011 . 36 ( 3 ): 323 - 375 . DOI:10.1016/j.progpolymsci.2010.08.001http://doi.org/10.1016/j.progpolymsci.2010.08.001 .

Bi L K, Fetters L J. Macromolecules , 1976 . 9 ( 5 ): 732 - 742 . DOI:10.1021/ma60053a010http://doi.org/10.1021/ma60053a010 .

Burns A B, Register R A. Macromolecules , 2016 . 49 ( 6 ): 2063 - 2070 . DOI:10.1021/acs.macromol.5b02764http://doi.org/10.1021/acs.macromol.5b02764 .

Avgeropoulos A, Hadjichristidis N. J Polym Sci, Part A: Polym Chem , 1997 . 35 813 - 816 . DOI:10.1002/(SICI)1099-0518(199703)35:4<813::AID-POLA28>3.0.CO;2-Phttp://doi.org/10.1002/(SICI)1099-0518(199703)35:4<813::AID-POLA28>3.0.CO;2-P .

He Q, Mao J, Wesdemiotis C, Quirk R P, Foster M D. Macromolecules , 2017 . 50 ( 15 ): 5779 - 5789 . DOI:10.1021/acs.macromol.7b01121http://doi.org/10.1021/acs.macromol.7b01121 .

Kang X H, Liu S Q, Xu L, Wang N. Macromol Res , 2018 . 26 ( 10 ): 924 - 933 . DOI:10.1007/s13233-018-6122-0http://doi.org/10.1007/s13233-018-6122-0 .

Zhang W B, He J L, Yue K, Liu C, Ni P H, Quirk R P, Cheng S Z D. Macromolecules , 2012 . 45 ( 21 ): 8571 - 8579 . DOI:10.1021/ma301597fhttp://doi.org/10.1021/ma301597f .

Ricci G, Boccia A C, Leone G, Pierro I, Zanchin G, Scoti M, Auriemma F, de Rosa C. Molecules , 2017 . 22 ( 5 ): 755 - 767 . DOI:10.3390/molecules22050755http://doi.org/10.3390/molecules22050755 .

Burns A B, Register R A. Macromolecules , 2016 . 49 ( 24 ): 9521 - 9530 . DOI:10.1021/acs.macromol.6b02175http://doi.org/10.1021/acs.macromol.6b02175 .

Hahn S F. J Polym Sci, Part A: Polym Chem , 1992 . 30 397 - 408 . DOI:10.1002/pola.1992.080300307http://doi.org/10.1002/pola.1992.080300307 .

Kobayashi S, Kataoka H, Ishizone T, Kato T, Ono T, Kobukata S, Arimoto K, Ogi H. React Funct Polym , 2009 . 69 409 - 415 . DOI:10.1016/j.reactfunctpolym.2008.12.010http://doi.org/10.1016/j.reactfunctpolym.2008.12.010 .

Kobayashi S, Kataoka H, Ishizone T. Macromolecules , 2009 . 42 ( 14 ): 5017 - 5026 . DOI:10.1021/ma900742hhttp://doi.org/10.1021/ma900742h .

Kobayashi S, Kataoka H, Ishizone T, Kato T, Ono T, Kobukata S, Ogi H. Macromolecules , 2008 . 41 ( 14 ): 5502 - 5508 . DOI:10.1021/ma7028743http://doi.org/10.1021/ma7028743 .

Higaki Y, Suzuki K, Kiyoshima Y, Toda T, Nishiura M, Ohta N, Masunaga H, Hou Z, Takahara A. Macromolecules , 2017 . 50 ( 16 ): 6184 - 6191 . DOI:10.1021/acs.macromol.7b01193http://doi.org/10.1021/acs.macromol.7b01193 .

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