Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene

Cheng-wei Dong; Xue-fei Leng; Li Han; Chao Li; Lin-can Yang; He-yu Shen; Hong-wei Ma; Yang Li

doi:10.11777/j.issn1000-3304.2020.20204

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Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene

Research Article | 更新时间：2021-03-05

- Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene
  增强出版
- Acta Polymerica Sinica Vol. 52, Issue 3, Pages: 287-296(2021)
- 作者机构：
  
  大连理工大学化工学院　大连 116024
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20204
  CLC：
- Published：3 March 2021，
  
  Published Online：16 October 2020，
  
  Received：31 August 2020，
  
  Revised：21 September 2020，
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Cheng-wei Dong, Xue-fei Leng, Li Han, Chao Li, Lin-can Yang, He-yu Shen, Hong-wei Ma, Yang Li. Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene. [J]. Acta Polymerica Sinica 52(3):287-296(2021)
DOI：

Cheng-wei Dong, Xue-fei Leng, Li Han, Chao Li, Lin-can Yang, He-yu Shen, Hong-wei Ma, Yang Li. Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene. [J]. Acta Polymerica Sinica 52(3):287-296(2021) DOI： 10.11777/j.issn1000-3304.2020.20204.

摘要

采用活性阴离子聚合方法研究了硅氢基功能化的1

1-二苯基乙烯(DPE)衍生物1-(4-二甲基硅氢苯基)-1-苯乙烯(DPE-SiH)与异戊二烯(Ip)在苯中的共聚反应，采用多种方法对序列分布、竞聚率和表观速率常数等进行测定. 结果表明无调节剂下共聚物链中异戊二烯的插入量远多于DPE-SiH，DPE-SiH主要分布在聚合物链末端，得到了一种梯度共聚物，竞聚率

=9.28，2种单体的表观速率常数分别为

=0.00134 min

−1

，

=0.01421 min

−1

，Ip在无调节剂条件下的共聚中表现出高活性. 同时研究了添加调节剂(

N′N'N'N

-四甲基乙二胺(TMEDA)和叔丁醇钾(

-BuOK))后的共聚物链中的序列分布，加入调节剂TMEDA和

-BuOK后得到了交替共聚物，实现了DPE-SiH和Ip单元在共聚物链中的序列调控，且对链中Ip单元的微观结构含量进行了调控，对形成交替共聚物的原因做了探讨，并通过Gaussian模拟探究了活性中心对Ip微观结构具有选择性的机理以及调节剂对活性中心的作用机理.

Abstract

The alternating regulation of living anionic copolymerization of 1-(4-dimethylsiloxphenyl)-1-styrene (DPE-SiH) and isoprene (Ip) was studied. By combining

in situ

H-NMR with MALDI-TOF MS technologies

the sequence distribution and apparent rate constant of monomers in the copolymer

as well as the reactivity ratio of Ip were determined. The results showed that the amount of DPE-SiH unit entering in the copolymer was less than that of Ip

and the site of DPE-SiH unit was mainly gathered at the end of copolymer when without the addition of regulators. Meanwhile

the gradient copolymer was obtained with the reactivity ratio

=9.28. The apparent rate constants of DPE-SiH and Ip unit were

=0.00134 min

−1

and

=0.01421 min

−1

respectively. In addition

the sequence distribution characteristics of the two monomers in the copolymer chain after the addition of the regulators [

N'N'N'N

-tetramethylethylenediamine (TMEDA) and potassium

tert

-butoxide (

-BuOK)] were investigated. The copolymer with the alternating sequence feature was obtained when the regulator TMEDA and

-BuOK were added

achieving the sequence control of DPE-SiH and Ip unit in the copolymer chain. Meanwhile

the alternating entry of two monomers in the copolymer chain and the improvement of

trans

-1

4 Ip contents of copolymer were attributed to the “space-limited” living species resulted by the addition of regulators according to the results of Gaussian simulation.

关键词

活性阴离子聚合交替序列调控1-(4-二甲基硅氢苯基)-1-苯乙烯异戊二烯

Keywords

Living anionic polymerizationAlternating sequence control1-(4-Dimethylsiloxphenyl)-1-styreneIsoprene

references

Weiss J, Li A, Wischerhoff E, Laschewsky A . Polym Chem , 2012 . 3 ( 2 ): 352 - 361 . DOI:10.1039/c1py00422khttp://doi.org/10.1039/c1py00422k .

Rosales A M, McCulloch B L, Zuckermann R N, Segalman R A . Macromolecules , 2012 . 45 ( 15 ): 6027 - 6035 . DOI:10.1021/ma300625bhttp://doi.org/10.1021/ma300625b .

Bazzi H S, Bouffard J, Sleiman H F . Macromolecules , 2003 . 36 ( 21 ): 7899 - 7902 . DOI:10.1021/ma034683phttp://doi.org/10.1021/ma034683p .

Zhang Liuqiao(张留乔), Huang Zhihao(黄智豪), Zhang Zhengbiao(张正彪), Zhu Xiulin(朱秀林) . Acta Polymerica Sinica(高分子学报) , 2018 . ( 9 ): 1144 - 1154 . DOI:10.11777/j.issn1000-3304.2018.18101http://doi.org/10.11777/j.issn1000-3304.2018.18101 .

Lutz J F . Polym Chem , 2010 . 1 ( 1 ): 55 - 62 . DOI:10.1039/B9PY00329Khttp://doi.org/10.1039/B9PY00329K .

Lutz J F, Ouchi M, Liu D R, Sawamoto M . Science , 2013 . 341 ( 6146 ): 1238149 DOI:10.1126/science.1238149http://doi.org/10.1126/science.1238149 .

Chen Lifeng(陈李峰), He Junpo(何军坡) . Acta Polymerica Sinica(高分子学报) , 2015 . ( 8 ): 973 - 981 . DOI:10.11777/j.issn1000-3304.2015.15059http://doi.org/10.11777/j.issn1000-3304.2015.15059 .

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 .

Yuki H, Hotta J, Okamoto Y, Murahash . S. Bull Chem Soc Jpn , 1967 . 40 ( 11 ): 2659 - 2663 . DOI:10.1246/bcsj.40.2659http://doi.org/10.1246/bcsj.40.2659 .

Liu P, Ma H, Huang W, Shen H, Wu L, Li Y, Wang Y . Polymer , 2016 . 97 167 - 173 . DOI:10.1016/j.polymer.2016.05.015http://doi.org/10.1016/j.polymer.2016.05.015 .

Liu P, Ma H, Huang W, Han L, Hao X, Shen H, Bai Y, Li Y . Polym Chem , 2017 . 8 ( 11 ): 1778 - 1789 . DOI:10.1039/C6PY02229Dhttp://doi.org/10.1039/C6PY02229D .

Wang Q, Ma H, Sang W, Han L, Liu P, Shen H, Huang W, Gong X, Yang L, Wang Y, Li Y . Polym Chem , 2016 . 7 ( 18 ): 3090 - 3099 . DOI:10.1039/C6PY00085Ahttp://doi.org/10.1039/C6PY00085A .

Ishizone T, Frey H . Macromol Chem Phys , 2017 . 218 ( 12 ): 1700217 DOI:10.1002/macp.201700217http://doi.org/10.1002/macp.201700217 .

Hong K, Uhrig D, Mays J W . Curr Opin Solid Station Mater Sci , 1999 . 4 ( 6 ): 531 - 538 . DOI:10.1016/S1359-0286(00)00011-5http://doi.org/10.1016/S1359-0286(00)00011-5 .

Ren L, Liu K, He Q, Ou E, Lu Y, Xu W . RSC Adv , 2016 . 6 ( 57 ): 51533 - 51543 . DOI:10.1039/C6RA07508Hhttp://doi.org/10.1039/C6RA07508H .

Brummelhuis N, Weck M . ACS Macro Lett , 2012 . 1 ( 10 ): 1216 - 1218 . DOI:10.1021/mz300428nhttp://doi.org/10.1021/mz300428n .

Li J, He J . ACS Macro Lett , 2015 . 4 ( 4 ): 372 - 376 . DOI:10.1021/acsmacrolett.5b00125http://doi.org/10.1021/acsmacrolett.5b00125 .

Grune E, Appold M, Mueller A H E, Gallei M, Frey H . ACS Macro Lett , 2018 . 7 ( 7 ): 807 - 810 . DOI:10.1021/acsmacrolett.8b00390http://doi.org/10.1021/acsmacrolett.8b00390 .

Ma H W, Wang Q Y, Sang W, Han L, Liu P B, Chen J, Li Y, Wang Y R . Macromol Rapid Commun , 2015 . 36 ( 8 ): 726 - 732 . DOI:10.1002/marc.201400660http://doi.org/10.1002/marc.201400660 .

Ureta E, Smid J, Szwarc M . J Polym Sci, Part A: Polym Chem , 1966 . 4 ( 9 ): 2219 - 2228 . DOI:10.1002/pol.1966.150040916http://doi.org/10.1002/pol.1966.150040916 .

Zhang Y, Han L, Ma H, Yang L, Liu P, Shen H, Li C, Li Y . Polymer , 2019 . 169 95 - 105 . DOI:10.1016/j.polymer.2019.02.033http://doi.org/10.1016/j.polymer.2019.02.033 .

Sang W, Ma H, Wang Q, Hao X, Zheng Y, Wang Y, Li Y . Polym Chem , 2016 . 7 ( 1 ): 219 - 234 . DOI:10.1039/C5PY01562Fhttp://doi.org/10.1039/C5PY01562F .

Yang L, Han L, Ma H, Shen H, Li C, Zhang S, Lei L, Hao X, Li Y . Eur Polym J , 2019 . 120 109212 DOI:10.1016/j.eurpolymj.2019.08.039http://doi.org/10.1016/j.eurpolymj.2019.08.039 .

Huang W, Ma H, Han L, Liu P, Yang L, Shen H, Hao X, Li Y . Macromolecules , 2018 . 51 ( 10 ): 3746 - 3757 . DOI:10.1021/acs.macromol.8b00666http://doi.org/10.1021/acs.macromol.8b00666 .

Ma H, Han L, Li Y . Macromol Chem Phys , 2017 . 218 ( 12 ): 1600420 DOI:10.1002/macp.201600420http://doi.org/10.1002/macp.201600420 .

Natalello A, Hall J N, Eccles E A L, Kimani S M, Hutchings L R . Macromol Rapid Commun , 2011 . 32 ( 2 ): 233 - 237 . DOI:10.1002/marc.201000482http://doi.org/10.1002/marc.201000482 .

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

Brooks P P, Natalello A, Hall J N, Eccles E A L, Kimani S M, Bley K, Hutchings L R . Macromol Symp , 2013 . 323 ( 1 ): 42 - 50 . DOI:10.1002/masy.201100111http://doi.org/10.1002/masy.201100111 .

Yuki H, Okamoto Y . Bull Chem Soc Jpn , 1969 . 42 ( 6 ): 1644 - 1649 . DOI:10.1246/bcsj.42.1644http://doi.org/10.1246/bcsj.42.1644 .

Ma Q, Han L, Ma H, Liu P, Shen H, Yang L, Li C, Hao X, Li Y . Polymer , 2019 . 184 121907 DOI:10.1016/j.polymer.2019.121907http://doi.org/10.1016/j.polymer.2019.121907 .

Chang S, Han L, Ma H, Bai H, Li C, Liu P, Yang L, Shen H, Li C, Zhang S . Macromol Chem Phys , 2019 . 220 ( 15 ): 1900052 DOI:10.1002/macp.201900052http://doi.org/10.1002/macp.201900052 .

Yuki H, Okamoto Y . Bull Chem Soc Jpn , 1970 . 43 ( 1 ): 148 - 151 . DOI:10.1246/bcsj.43.148http://doi.org/10.1246/bcsj.43.148 .

Hutchings L R, Brooks P P, Parker D, Mosely J A, Sevinc S . Macromolecules , 2015 . 48 ( 3 ): 610 - 628 . DOI:10.1021/ma5016038http://doi.org/10.1021/ma5016038 .

Quirk R P, Garces C, Collins S, Dabney D, Wesdemiotis C, Dudipala V . Polymer , 2012 . 53 ( 11 ): 2162 - 2167 . DOI:10.1016/j.polymer.2012.03.029http://doi.org/10.1016/j.polymer.2012.03.029 .

Sato H, Ono A, Tanaka Y . Polymer , 1977 . 18 ( 6 ): 580 - 586 . DOI:10.1016/0032-3861(77)90059-3http://doi.org/10.1016/0032-3861(77)90059-3 .

Ma Q, Leng X, Han L, Liu P, Li C, Zhang S, Lei L, Ma H, Li Y . Polym Chem , 2020 . 11 ( 15 ): 2708 - 2714 . DOI:10.1039/D0PY00259Chttp://doi.org/10.1039/D0PY00259C .

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College of Chemistry, Zhengzhou University

State Key Laboratory of Polymer Physics and Chemistry, Changchun Institue of Applied Chemistry, Chinese Acadamy of Sciences

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State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology

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