Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents

Zheng-Yi Zhang; Zan Yang; Yun Liao; Sai-Hu Liao

doi:10.1007/s10118-024-3085-9

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Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents

RESEARCH ARTICLE | Updated：2024-05-11

- Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents
  Enhanced Publication
- Chinese Journal of Polymer Science Vol. 42, Issue 6, Pages: 711-717(2024)
- Affiliations：
  
  a.Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108, China
  b.State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
  c.Beijing National Laboratory for Molecular Sciences, Beijing 100190, China
- Author bio：
  
  shliao@fzu.edu.cn or shliao@xmu.edu.cn
- Funds：
- DOI：10.1007/s10118-024-3085-9
  CLC： M
- Received：25 November 2023，
  
  Accepted：21 December 2023，
  
  Online First：25 January 2024，
  
  Published：01 June 2024
- Accepted：
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Zhang, Z. Y.; Yang, Z.; Liao, Y.; Liao, S. H. Organic Brønsted acid-catalyzed stereoselective cationic RAFT polymerization: the effect of RAFT agents. Chinese J. Polym. Sci. 2024, 42, 711–717

Zheng-Yi Zhang, Zan Yang, Yun Liao, et al. Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents[J]. Chinese Journal of Polymer Science, 2024, 42(6): 711-717.
Zhang, Z. Y.; Yang, Z.; Liao, Y.; Liao, S. H. Organic Brønsted acid-catalyzed stereoselective cationic RAFT polymerization: the effect of RAFT agents. Chinese J. Polym. Sci. 2024, 42, 711–717 DOI： 10.1007/s10118-024-3085-9.

Zheng-Yi Zhang, Zan Yang, Yun Liao, et al. Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents[J]. Chinese Journal of Polymer Science, 2024, 42(6): 711-717. DOI： 10.1007/s10118-024-3085-9.

摘要

In the Brønsted acid-catalyzed stereoselective cationic RAFT polymerization

even though the stereoselectivity of the polymerization is mainly governed by the bulky anion derived from the acid catalyst (PADI)

the RAFT agent was also found influential. High isotacticity (up to 90% m) was achieved by optimizing the RAFT agents.

Abstract

The tacticity of vinyl polymers is a key factor affecting the properties of materials. Recently

organic Brønsted acids have been demonstrated as effective catalysts for the development of highly stereoselective cationic reversible addition-fragmentation chain transfer (RAFT) polymerizations of vinyl ethers

in which the use of RAFT agents could allow the control the molecular weight and tacticity of polymer pr

oducts simultaneously. However

the effect of RAFT agents on the tacticity-regulation remains elusive and lacks of investigation. In this study

we synthesized four types of RAFT agents and evaluated their influence in the stereoselective cationic polymerization of isobutyl vinyl ether in the presence of PADI as a Brønsted acid catalyst

which unveils that the Z group of RAFT agents could not only affect the polydispersity of the products

but also exert a profound effect on the stereoselectivity. After extensive screening of the RAFT agents

high stereoregularity (isotacticity

90%

) was obtained when using dithiocarbonate ester-type RAFT agents with a benzyloxy Z group.

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