Chain Shuttling Copolymerization of Ethylene and Styrene Catalyzed by Rare-earth Metal Complexes

Li-xian Huang; Bo Liu; Dong-mei Cui

doi:10.11777/j.issn1000-3304.2020.20268

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Chain Shuttling Copolymerization of Ethylene and Styrene Catalyzed by Rare-earth Metal Complexes

Research Article | 更新时间：2021-05-07

- Chain Shuttling Copolymerization of Ethylene and Styrene Catalyzed by Rare-earth Metal Complexes
  增强出版
- Acta Polymerica Sinica Vol. 52, Issue 5, Pages: 514-521(2021)
- 作者机构：
  
  1.中国科学院长春应用化学研究所高分子物理与化学国家重点实验室　长春 130022
  2.中国科学技术大学应用化学与工程学院　合肥 230026
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20268
  CLC：
- Published：3 May 2021，
  
  Published Online：9 February 2021，
  
  Received：8 December 2020，
  
  Revised：3 January 2021，
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Li-xian Huang, Bo Liu, Dong-mei Cui. Chain Shuttling Copolymerization of Ethylene and Styrene Catalyzed by Rare-earth Metal Complexes. [J]. Acta Polymerica Sinica 52(5):514-521(2021)
DOI：

Li-xian Huang, Bo Liu, Dong-mei Cui. Chain Shuttling Copolymerization of Ethylene and Styrene Catalyzed by Rare-earth Metal Complexes. [J]. Acta Polymerica Sinica 52(5):514-521(2021) DOI： 10.11777/j.issn1000-3304.2020.20268.

摘要

链穿梭聚合作为一锅法合成多嵌段聚合物的策略引起人们的研究兴趣. 然而，其催化体系的构建难度大，导致实现链穿梭聚合的单体有限. 本文基于三异丁基铝作链转移剂时，稀土金属配合物

催化乙烯/苯乙烯共聚合，得到富含乙烯/苯乙烯交替序列的共聚物且链转移效率接近100%的发现，开展了乙烯/苯乙烯链穿梭聚合的研究. 首先探索配合物

催化乙烯/苯乙烯共聚合，发现所得共聚物中苯乙烯结构单元的含量

4%，因此考察了在不同烷基铝用量时，配合物

催化乙烯均聚合的行为，发现所得聚乙烯的分子量随着[Al]

]

增加呈指数降低，幂指数为−0.778，表明链转移效率低于100%. 采用

/Al

三元体系催化乙烯/苯乙烯共聚合得到双峰分布的聚合物，说明链穿梭聚合没有实现. 进一步筛选发现，配合物

催化乙烯/苯乙烯共聚合时，随着[Al]

]

增加，所得富间规聚苯乙烯序列共聚物的分子呈量指数降低，幂指数为−1.097，接近−1，表明链转移效率接近100%；同时催化体系的TOF值减小. 当[Al

]

≥20时，

/Al

三元体系催化乙烯/苯乙烯共聚合得到单峰分布的乙烯/苯乙烯交替序列和富间规聚苯乙烯序列的多嵌段共聚物，说明成功实现了乙烯/苯乙烯链穿梭共聚合. 通过调节

和

的比例，有效调控了共聚物中乙烯/苯乙烯交替序列和富间规聚苯乙烯序列的组成.

Abstract

As a facile strategy for one pot synthesis of multiblock polymers

chain shuttling polymerization has aroused considerable attention. However

the construction of the corresponding catalytic system is difficult

leading to the limited number of monomers to successfully achieve chain shuttling polymerization. Herein

we conducted the investigation of chain shuttling polymerization of ethylene and styrene on the basis that in the presence of Al

rare-earth metal complex

catalyzed the copolymerization of ethylene and styrene to give the alternating sequence enriched copolymer with the chain transfer efficiency of 100%. Firstly

complex

was employed to catalyze the copolymerization of ethylene and styrene. The styrene content of the afforded copolymer is less than 4%. Thus

ethylene polymerization was conducted under various ratios of [Al]

to [

]

. The molecular weight of the afforded polyethylene exponentially decreased with the increase of [Al]

]

with the power of −0.778

suggesting that the chain transfer efficiency is less than 100%. The ternary catalytic system composed of

and Al

catalyzed the copolymerization of ethylene and styrene to afford copolymers with bimodal molecular weight distributions

indicating the unsuccess of chain shuttling. Then after screening a series of complexes

was found to catalyse the copolymerization of ethylene and styrene with the chain transfer efficiency of 100% as the molecular weights of the afforded copolymers syndiotatic polystyrene sequence enriched exponentially decreased with the increase of [Al]

]

with the power of −1.097. When the ratio of [Al

]

to [

]

was no less than 20

the ternary catalytic system composed of

and Al

catalyzed the copolymerization of ethylene and styrene to afford multi-block copolymers containing alternating sequences and syndiotactic polystyrene sequences with unimodal molecular weight distributions

indicating the success of chain shuttling. The sequence distribution was effectively controlled by adjusting the ratio of

关键词

链穿梭聚合稀土金属配合物序列可控聚合乙烯苯乙烯

Keywords

Chain shuttling polymerizationRare-earth metal complexSequence control polymerizationEthyleneStyrene

references

Arriola D J, Carnahan E M, Hustad P D, Kuhlman R L, Wenzel T T . Science , 2006 . 312 714 - 719 . DOI:10.1126/science.1125268http://doi.org/10.1126/science.1125268 .

Zintl M, Rieger B . Angew Chem Int Ed , 2007 . 46 333 - 335 . DOI:10.1002/anie.200602889http://doi.org/10.1002/anie.200602889 .

Alfano F, Boone H W, Busico V, Cipullo R, Stevens J C . Macromolecules , 2007 . 40 7736 - 7738 . DOI:10.1021/ma7020024http://doi.org/10.1021/ma7020024 .

Kuhlman R L, Wenzel T T . Macromolecules , 2008 . 41 4090 - 4094 . DOI:10.1021/ma8004313http://doi.org/10.1021/ma8004313 .

Zhang M, Carnahan E M, Karjala T W, Jain P . Macromolecules , 2009 . 42 8013 - 8016 . DOI:10.1021/ma9018685http://doi.org/10.1021/ma9018685 .

Kuhlman R L, Klosin J . Macromolecules , 2010 . 43 7903 - 7904 . DOI:10.1021/ma101544nhttp://doi.org/10.1021/ma101544n .

Mohammadi Y, Ahmadi M, Saeb M R, Khorasani M M, Yang P, Stadler F J . Macromolecules , 2014 . 47 4778 - 4789 . DOI:10.1021/ma500874hhttp://doi.org/10.1021/ma500874h .

Vittoria A, Busico V, Cannavacciuolo F D, Cipullo R . ACS Catal , 2018 . 8 5051 - 5061 . DOI:10.1021/acscatal.8b00841http://doi.org/10.1021/acscatal.8b00841 .

Yin X, Gao H, Yang F, Pan L, Wang B, Ma Z, Li Y S . Chinese J Polym Sci , 2020 . 38 1192 - 1201 . DOI:10.1007/s10118-020-2446-2http://doi.org/10.1007/s10118-020-2446-2 .

Pan L, Zhang K Y, Nishiura M, Hou Z M . Angew Chem Int Ed , 2011 . 50 12012 - 12015 . DOI:10.1002/anie.201104011http://doi.org/10.1002/anie.201104011 .

Valente A, Stoclet G, Bonnet F, Mortreux A, Visseaux M, Zinck P . Angew Chem Int Ed , 2014 . 53 4638 - 4641 . DOI:10.1002/anie.201311057http://doi.org/10.1002/anie.201311057 .

Soga K, Lee D H, Yanagihara H . Polym Bull , 1988 . 20 237 - 241.

Mani P, Burns C M . Macromolecules , 1991 . 24 5476 - 5477 . DOI:10.1021/ma00019a042http://doi.org/10.1021/ma00019a042 .

Aaltonen P, Seppala J, Matilainen L, Leskela M . Macromolecules , 1994 . 27 3136 - 3138 . DOI:10.1021/ma00090a004http://doi.org/10.1021/ma00090a004 .

Zhang H, Nomura K . Macromolecules , 2006 . 39 5266 - 5274 . DOI:10.1021/ma060503ahttp://doi.org/10.1021/ma060503a .

Zhang H, Nomura K . J Am Chem Soc , 2005 . 127 9364 - 9365 . DOI:10.1021/ja052198zhttp://doi.org/10.1021/ja052198z .

Nomura K, Okumura H, Komatsu T, Naga N . Macromolecules , 2002 . 35 5388 - 5395 . DOI:10.1021/ma0200773http://doi.org/10.1021/ma0200773 .

Nomura K, Komatsu T, Imanishi Y . Macromolecules , 2000 . 33 8122 - 8124 . DOI:10.1021/ma0011284http://doi.org/10.1021/ma0011284 .

Lee D H, Yoon K B, Kim H J, Woo S S, Noh S K . J Appl Polym Sci , 1998 . 67 2187 - 2198 . DOI:10.1002/(SICI)1097-4628(19980328)67:13<2187::AID-APP9>3.0.CO;2-Ahttp://doi.org/10.1002/(SICI)1097-4628(19980328)67:13<2187::AID-APP9>3.0.CO;2-A .

Wu Q, Ye Z, Gao Q H, Lin S A . Macromol Chem Phys , 1998 . 199 1715 - 1720 . DOI:10.1002/(SICI)1521-3935(19980801)199:8<1715::AID-MACP1715>3.0.CO;2-Khttp://doi.org/10.1002/(SICI)1521-3935(19980801)199:8<1715::AID-MACP1715>3.0.CO;2-K .

Xu G X, Lin S A . Macromolecules , 1997 . 30 685 - 693 . DOI:10.1021/ma960792ahttp://doi.org/10.1021/ma960792a .

Pellecchia C, Pappalardo D, D’Arco M, Zambelli A . Macromolecules , 1996 . 29 1158 - 1162 . DOI:10.1021/ma951152vhttp://doi.org/10.1021/ma951152v .

Oliva L, Mazza S, Longo P . Macromol Chem Phys , 1996 . 197 3115 - 3122 . DOI:10.1002/macp.1996.021971005http://doi.org/10.1002/macp.1996.021971005 .

Oliva L, Izzo L, Longo P . Macromol Rapid Commun , 1996 . 17 745 - 748 . DOI:10.1002/marc.1996.030171010http://doi.org/10.1002/marc.1996.030171010 .

Aaltonen P, Seppala J . Eur Polym J , 1995 . 31 79 - 83 . DOI:10.1016/0014-3057(94)00121-9http://doi.org/10.1016/0014-3057(94)00121-9 .

Aaltonen P, Seppala J . Eur Polym J , 1994 . 30 683 - 687 . DOI:10.1016/0014-3057(94)90116-3http://doi.org/10.1016/0014-3057(94)90116-3 .

Longo P, Grassi A, Oliva L . Macromol Chem Phys , 1990 . 191 2387 - 2396 . DOI:10.1002/macp.1990.021911016http://doi.org/10.1002/macp.1990.021911016 .

Arriola D J, Bokota M, Campbell R E Jr, Klosin J, LaPointe R E, Redwine O D, Shankar R B, Timmers F J, Abboud K A . J Am Chem Soc , 2007 . 129 7065 - 7076 . DOI:10.1021/ja070061yhttp://doi.org/10.1021/ja070061y .

Luo Y, Baldamus J, Hou Z M . J Am Chem Soc , 2004 . 126 13910 - 13911 . DOI:10.1021/ja046063phttp://doi.org/10.1021/ja046063p .

Li X F, Wang X Y, Tong X, Zhang H X, Chen Y Y, Liu Y, Liu H, Wang X J, Nishiura M, He H, Lin Z G, Zhang S W, Hou Z M . Organometallics , 2013 . 32 1445 - 1458 . DOI:10.1021/om3011036http://doi.org/10.1021/om3011036 .

Liu B, Wang L F, Wu C J, Cui D M . Polym Chem , 2019 . 10 235 - 243 . DOI:10.1039/C8PY01326Hhttp://doi.org/10.1039/C8PY01326H .

Chien J C W, Tsai W M, Rausch M D . J Am Chem Soc , 1991 . 113 8570 - 8571 . DOI:10.1021/ja00022a081http://doi.org/10.1021/ja00022a081 .

Lin F, Wang X B, Pan Y P, Wang M Y, Liu B, Luo Y, Cui D M . ACS Catal , 2016 . 6 176 - 185 . DOI:10.1021/acscatal.5b02334http://doi.org/10.1021/acscatal.5b02334 .

Bambirra S, Otten E, Leusen D, Meetsma A, Hessen B Z. . Anorg Allg Chemie , 2006 . 632 1950 - 1952 . DOI:10.1002/zaac.200600145http://doi.org/10.1002/zaac.200600145 .

Chen R H, Yao C G, Wang M Y, Xie H Y, Wu C J, Cui D M . Organometallics , 2015 . 34 455 - 461 . DOI:10.1021/om500992vhttp://doi.org/10.1021/om500992v .

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MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University

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

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology

State Key Laboratory of Effective Utilization of Chemical Resources, Key Laboratory of Carbon Fiber and Functional Polymers of Ministry of Education, College of Materials Science and Engineering, Beijing University of Chemical Technology

College of Materials Science and Engineering, Beijing University of Chemical Technology

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