Synthesis and Post-polymerization Modification of Polystyrene Containing Indole Side Group

Su-tao Zhang; Hai Xu; Jiang-hua He; Yue-tao Zhang

doi:10.11777/j.issn1000-3304.2020.20127

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Synthesis and Post-polymerization Modification of Polystyrene Containing Indole Side Group

更新时间：2021-01-26

- Synthesis and Post-polymerization Modification of Polystyrene Containing Indole Side Group
- Acta Polymerica Sinica Vol. 51, Issue 10, Pages: 1147-1152(2020)
- 作者机构：
  
  超分子结构与材料国家重点实验室吉林大学化学学院　长春 130012
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20127
  CLC：
- Published：1 September 2020，
  
  Published Online：27 July 2020，
  
  Received：19 May 2020，
  
  Revised：4 June 2020，
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Su-tao Zhang, Hai Xu, Jiang-hua He, Yue-tao Zhang. Synthesis and Post-polymerization Modification of Polystyrene Containing Indole Side Group. [J]. Acta Polymerica Sinica 51(10):1147-1152(2020)
DOI：

Su-tao Zhang, Hai Xu, Jiang-hua He, Yue-tao Zhang. Synthesis and Post-polymerization Modification of Polystyrene Containing Indole Side Group. [J]. Acta Polymerica Sinica 51(10):1147-1152(2020) DOI： 10.11777/j.issn1000-3304.2020.20127.

摘要

通过可逆加成-断裂链转移(RAFT)聚合合成了一种含吲哚侧基的聚苯乙烯. 在B(C

)

的催化下，硅烷与吲哚C3位的选择性硅烷化反应实现了所得聚苯乙烯的后修饰. 聚合物通过GPC和

H-NMR表征，证明在不破坏聚苯乙烯主链的情况下，聚合物侧链引入了C3硅烷化吲哚侧基. 在选用位阻较小的苯基二甲基硅烷(PhMe

SiH)进行修饰时，所得聚苯乙烯的硅烷化吲哚侧基的嵌入率可达50%. 在选用含四苯乙烯的硅烷进行修饰时，所得聚苯乙烯的硅烷化吲哚侧基嵌入率可达38%，且具有聚集诱导发光(AIE)性质.

Abstract

A vinyl monomer 1-(4-vinylbenzyl)-indole was prepared in 90% yield through one-step synthesis by using commercially available starting material. The reversible addition-fragmentation chain transfer (RAFT) polymerization of 1-(4-vinylbenzyl)-indole was performed with 2

2-azobisisobutyronitrile (AIBN) as initiator and 2-phenyl-2-propylbenzodithiolate as chain transfer agent (CTA)

furnishing a series of polystyrenes containing indole side groups with adjustable molecular weight (

= 5200 – 18500 g/mol). With the catalysis of B(C

)

post-polymerization modification of the produced polymers could be achieved through the regioselective silylation of their indole side groups with different hydrosilanes. Analysis of the polymers by GPC and

H-NMR spectroscopy revealed that the C3-position of indole group at the polystyrene side chain was selectively silylated while the polymer backbone was maintained. The employment of the less sterically crowded PhMe

SiH or silanes containing tetraphenylethene (TPE)-moiety as silane sources led to the production of polymers with 50% or 38% grafting ratio of silylated indole

respectively. Moreover

silanes containing tetraphenylethene (TPE)-moiety would endow the resultant polymer with the aggregation-induced emission feature. Under UV irradiation

almost no fluorescence was observed for polymer containing TPE-moiety dissolved in THF. The addition of large amounts of hexane to THF led to the observation of a relatively strong blue fluorescence. With an increase in the hexane fractions (fw) of mixed solvents

the corresponding fluorescence intensity gradually increased until reaching the maximum value at fw of 90%

which is approximately 57-fold higher than that in pure THF solution.

关键词

聚合物后修饰吲哚侧基C―H硅烷化B(C6F5)3聚集诱导发光

Keywords

Post-polymerization modificationIndole side groupC―H silylationB(C6F5)3Aggregation-induced emission

references

Guenay K A, Theato P, Klok H A. J Polym Sci, Part A: Polym Chem , 2013 . 51 ( 1 ): 1 - 28 . DOI:10.1002/pola.26333http://doi.org/10.1002/pola.26333 .

Theato P, Klok H A. Functional Polymers by Post-Polymerization Modification: Concepts, Guidelines, and Applications. Weinheim: Wiley-VCH , 2013 .

Kakuchi R, Theato P. ACS Macro Lett , 2013 . 2 ( 5 ): 419 - 422 . DOI:10.1021/mz400144qhttp://doi.org/10.1021/mz400144q .

Arz M I, Knights A W, Manners I. Macromol Rapid Commun , 2020 . 41 ( 4 ): 1900468 DOI:10.1002/marc.201900468http://doi.org/10.1002/marc.201900468 .

Dallerba E, Massi M, Lowe A B. Eur Polym J , 2020 . 126 109559 DOI:10.1016/j.eurpolymj.2020.109559http://doi.org/10.1016/j.eurpolymj.2020.109559 .

Li Z L, Sun L H, Ma J M, Zeng Z, Jiang H. Polymer , 2016 . 84 336 - 342 . DOI:10.1016/j.polymer.2016.01.020http://doi.org/10.1016/j.polymer.2016.01.020 .

Sessions L B, Cohen B R, Grubbs R B. Macromolecules , 2007 . 40 ( 6 ): 1926 - 1933 . DOI:10.1021/ma0625915http://doi.org/10.1021/ma0625915 .

Kuhtz H, Cheng F, Schwedler S, Böhling L, Brockhinke A, Weber L, Parab K, Jäkle F. ACS Macro Lett , 2012 . 1 ( 5 ): 555 - 559 . DOI:10.1021/mz300071fhttp://doi.org/10.1021/mz300071f .

Welch G C, Juan R S, Masuda J D, Stephan D W. Science , 2006 . 314 ( 5802 ): 1124 - 1126 . DOI:10.1126/science.1134230http://doi.org/10.1126/science.1134230 .

Welch G C, Stephan D W. J Am Chem Soc , 2007 . 129 ( 7 ): 1880 - 1881 . DOI:10.1021/ja067961jhttp://doi.org/10.1021/ja067961j .

Stephan D W. Science , 2016 . 354 ( 6317 ): aaf7229 DOI:10.1126/science.aaf7229http://doi.org/10.1126/science.aaf7229 .

Stephan D W, Erker G. Angew Chem Int Ed , 2015 . 54 ( 22 ): 6400 - 6441 . DOI:10.1002/anie.201409800http://doi.org/10.1002/anie.201409800 .

Stephan D W. J Am Chem Soc , 2015 . 137 ( 32 ): 10018 - 10032 . DOI:10.1021/jacs.5b06794http://doi.org/10.1021/jacs.5b06794 .

Scott D J, Fuchter M J, Ashley A E. Chem Soc Rev , 2017 . 46 ( 19 ): 5689 - 5700 . DOI:10.1039/C7CS00154Ahttp://doi.org/10.1039/C7CS00154A .

Zhang Y T, Miyake G M, Chen E Y X. Angew Chem Int Ed , 2010 . 49 ( 52 ): 10158 - 10162 . DOI:10.1002/anie.201005534http://doi.org/10.1002/anie.201005534 .

Zhang Y T, Miyake G M, John M G, Falivene L, Caporaso L, Cavallo L, Chen E Y X. Dalton Trans , 2012 . 41 ( 30 ): 9119 - 9134 . DOI:10.1039/c2dt30427ahttp://doi.org/10.1039/c2dt30427a .

Wang Q Y, Zhao W C, He J H, Zhang Y T, Chen E Y X. Macromolecules , 2017 . 50 ( 1 ): 123 - 136 . DOI:10.1021/acs.macromol.6b02398http://doi.org/10.1021/acs.macromol.6b02398 .

Bai Y, He J H, Zhang Y T. Angew Chem Int Ed , 2018 . 57 ( 52 ): 17230 - 17234 . DOI:10.1002/anie.201811946http://doi.org/10.1002/anie.201811946 .

Wang Q Y, Zhao W C, Zhang S T, He J H, Zhang Y T, Chen E Y X. ACS Catal , 2018 . 8 ( 4 ): 3571 - 3578 . DOI:10.1021/acscatal.8b00333http://doi.org/10.1021/acscatal.8b00333 .

Hu L, He J H, Zhang Y T, Chen E Y X. Macromolecules , 2018 . 51 ( 4 ): 1296 - 1307 . DOI:10.1021/acs.macromol.7b02647http://doi.org/10.1021/acs.macromol.7b02647 .

Hu L, Zhao W C, He J H, Zhang Y T. Molecules , 2018 . 23 ( 3 ): 665 DOI:10.3390/molecules23030665http://doi.org/10.3390/molecules23030665 .

Wang H Y, Wang Q Y, He J H, Zhang Y T. Polym Chem , 2019 . 10 ( 26 ): 3597 - 3603 . DOI:10.1039/C9PY00427Khttp://doi.org/10.1039/C9PY00427K .

Zhao W C, Wang Q Y, He J H, Zhang Y T. Polym Chem , 2019 . 10 ( 31 ): 4328 - 4335 . DOI:10.1039/C9PY00626Ehttp://doi.org/10.1039/C9PY00626E .

Zhao W C, He J H, Zhang Y T. Sci Bull , 2019 . 64 ( 24 ): 1830 - 1840 . DOI:10.1016/j.scib.2019.08.025http://doi.org/10.1016/j.scib.2019.08.025 .

Bai Yun(白云), Zhang Yuetao(张越涛). Acta Polymerica Sinica(高分子学报) , 2019 . 50 ( 3 ): 233 - 246 . DOI:10.11777/j.issn1000-3304.2019.18269http://doi.org/10.11777/j.issn1000-3304.2019.18269 .

Bai Y, Wang H Y, He J H, Zhang Y T. Angew Chem Int Ed , 2020 . 59 ( 28 ): 11613 - 11619 . DOI:10.1002/anie.202004013http://doi.org/10.1002/anie.202004013 .

Han Y X, Zhang S T, He J H, Zhang Y T. J Am Chem Soc , 2017 . 139 ( 21 ): 7399 - 7407 . DOI:10.1021/jacs.7b03534http://doi.org/10.1021/jacs.7b03534 .

Han Y X, Zhang S T, He J H, Zhang Y T. ACS Catal , 2018 . 8 ( 9 ): 8765 - 8773 . DOI:10.1021/acscatal.8b01847http://doi.org/10.1021/acscatal.8b01847 .

Zhang S T, Han Y X, He J H, Zhang Y T. J Org Chem , 2018 . 83 ( 3 ): 1377 - 1386 . DOI:10.1021/acs.joc.7b02886http://doi.org/10.1021/acs.joc.7b02886 .

Bandini M, Eichholzer A. Angew Chem Int Ed , 2009 . 48 ( 51 ): 9608 - 9644 . DOI:10.1002/anie.200901843http://doi.org/10.1002/anie.200901843 .

Joucla L, Djakovitch L. Adv Synth Catal , 2009 . 351 ( 5 ): 673 - 714 . DOI:10.1002/adsc.200900059http://doi.org/10.1002/adsc.200900059 .

Festa A A, Voskressensky L G, van der Eycken E V. Chem Soc Rev , 2019 . 48 ( 16 ): 4401 - 4423 . DOI:10.1039/C8CS00790Jhttp://doi.org/10.1039/C8CS00790J .

Bariwal J, Voskressensky L G, van der Eycken E V. Chem Soc Rev , 2018 . 47 ( 11 ): 3831 - 3848 . DOI:10.1039/C7CS00508Chttp://doi.org/10.1039/C7CS00508C .

Bartoli G, Bencivennia G, Dalpozzo R. Chem Soc Rev , 2010 . 39 ( 11 ): 4449 - 4465 . DOI:10.1039/b923063ghttp://doi.org/10.1039/b923063g .

Liang Y C, Dvornikov A S, Rentzepis P M. Macromolecules , 2002 . 35 ( 25 ): 9377 - 9382 . DOI:10.1021/ma020750ohttp://doi.org/10.1021/ma020750o .

Lehmann M, Schulz A, Villinger A. Angew Chem Int Ed , 2009 . 48 ( 40 ): 7444 - 7447 . DOI:10.1002/anie.200902992http://doi.org/10.1002/anie.200902992 .

Xiang K, He L, Li Y, Xu C, Li S. RSC Adv , 2015 . 5 ( 118 ): 97224 - 97230 . DOI:10.1039/C5RA18152Fhttp://doi.org/10.1039/C5RA18152F .

Hu Rong(胡蓉), Xin Dehua(辛德华), Qin Anjun(秦安军), Tang Benzhong(唐本忠). Acta Polymerica Sinica(高分子学报) , 2018 . ( 2 ): 132 - 144 . DOI:10.11777/j.issn1000-3304.2018.17280http://doi.org/10.11777/j.issn1000-3304.2018.17280 .

Hu R, Kang Y, Tang B Z. Polym J , 2016 . 48 359 - 370 . DOI:10.1038/pj.2016.1http://doi.org/10.1038/pj.2016.1 .

Qin A, Lam J W Y, Tang B Z. Prog Polym Sci , 2012 . 37 ( 1 ): 182 - 209 . DOI:10.1016/j.progpolymsci.2011.08.002http://doi.org/10.1016/j.progpolymsci.2011.08.002 .

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