Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture

Li-Mei Ren; Cheng-Lin Li; Qi Wang

doi:10.1007/s10118-022-2788-z

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Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture

RESEARCH ARTICLE | Updated：2022-11-16

- Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture
- Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture
- 高分子科学（英文版） 2022年40卷第12期页码：1623-1630
- Affiliations：
  
  a.MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science & Engineering Zhejiang University, Hangzhou 310027, China
  b.Current address: Zhejiang University-University of Edinburgh Institute, Zhejiang University School of Medicine, and Key Laboratory of Tissue Engineering and Regenerative Medicine of Zhejiang Province, Zhejiang University School of Medicine, Hangzhou 310027, China
- Author bio：
  
  wangq@zju.edu.cn
- Funds：
  
  Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-022-2788-z.
- DOI：10.1007/s10118-022-2788-z
  中图分类号：
- 收稿：2022-03-24，
  
  修回：2022-4-27，
  
  录用：2022-5-12，
  
  网络首发：2022-08-17，
  
  纸质出版：2022-12-01
- Accepted：
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Ren, L. M.; Li, C. L.; Wang, Q. Non-linear radical additions-coupling polymerization of monovinyl monomers towards polymer networks: theory, tunability and heritable architecture. Chinese J. Polym. Sci. 2022, 40, 1623–1630

Li-Mei Ren, Cheng-Lin Li, Qi Wang. Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture[J]. Chinese Journal of Polymer Science, 2022, 40(12): 1623-1630.
Ren, L. M.; Li, C. L.; Wang, Q. Non-linear radical additions-coupling polymerization of monovinyl monomers towards polymer networks: theory, tunability and heritable architecture. Chinese J. Polym. Sci. 2022, 40, 1623–1630 DOI： 10.1007/s10118-022-2788-z.

Li-Mei Ren, Cheng-Lin Li, Qi Wang. Non-linear Radical Additions-Coupling Polymerization of Monovinyl Monomers towards Polymer Networks: Theory, Tunability and Heritable Architecture[J]. Chinese Journal of Polymer Science, 2022, 40(12): 1623-1630. DOI： 10.1007/s10118-022-2788-z.

摘要

Non-linear radical additions-coupling polymerization (NLRAsCP) of monovinyl monomers involving both radical addition and coupling reactions generates polymer networks with heritable architecture.

Abstract

Exploring new polymerization strategy for current available monomers is a big challenge in polymer science. Here we re-investigate radical polymerization of monovinyl monomer (MVM) initiated by uniform branched polyfunctional initiator (PFI)

which is termed non-linear radical additions-coupling polymerization (NLRAsCP). In NLRAsCP

both addition and coupling reactions of radical contribute to the construction of the polymer chains

which leads to continuous growth of branch topology. Theoretical analysis of NLRAsCP predicts that the gelation is determined by the functionality of PFI (

)

the extent of initiation of the PFI (

) and the termination factor of radical (

). NLRAsCPs of styrene and methyl methacrylate promoted by Cu(0)/Me

TREN or Mn

(CO)

/visible light were conducted. After the cleavage of incorporated PFI fragment or junctions in the network

the network was transformed to linear chains having almost the same structure as segmental chains in the precursor network. This allows the reverse deducing the network structure from its cleaved products. It has been proven that NLRAsCP includes stepwise initiation of PFI

chain-growth of segmental chains and successive endlinking of macroradicals derived from PFI. The three parameters related to the gelation process

and

were adjusted

via

binary PFI

the feed ratio of [Mn

(CO)

]/[PFI]

and addition of non-homopolymerizable comonomer respectively. The minimum values of

and

and the minimum amount of comonomer required for gelation were determined

which can be applied to estimate

of various macroradicals. NLRAsCP opens a general and facile strategy for synthesis of a variety of polymer networks with heritable architecture by one-pot polymerization of various MVMs.

关键词

Keywords

references

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