A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids

Mineto Uchiyama; Masataka Sakaguchi; Kotaro Satoh; Masami Kamigaito

doi:10.1007/s10118-019-2233-0

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A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids

ARTICLE | Updated：2021-02-18

- A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids
- A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids
- Chinese Journal of Polymer Science 2019年37卷第9期页码：851-857
- Affiliations：
  
  Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Furo-cho, Chikusa-ku, Nagoya University, Nagoya 464-8603, Japan
- Author bio：
  
  satoh@chembio.nagoya-u.ac.jp (K.S.)
  kamigait@chembio.nagoya-u.ac.jp (M.K.)
- Funds：
  
  This work was supported in part by a JSPS KAKENHI Grant-in-Aid for Early-Career Scientists (No. JP18K14274) for M.U.
- DOI：10.1007/s10118-019-2233-0
  中图分类号：
- 收稿：2018-12-27，
  
  修回：2019-1-22，
  
  录用：2019-1-23，
  
  网络首发：2019-03-04，
  
  纸质出版：2019-09
- Accepted：
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Citation: Uchiyama, M.; Sakaguchi, M.; Satoh, K.; Kamigaito, M. A user-friendly living cationic polymerization: Degenerative chain-transfer polymerization of vinyl ethers by simply using mixtures of weak and superstrong protonic acids. Chinese J. Polym. Sci. 2019, 37, 851–857

Mineto Uchiyama, Masataka Sakaguchi, Kotaro Satoh, et al. A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids[J]. Chinese Journal of Polymer Science, 2019, 37(9): 851-857.
Citation: Uchiyama, M.; Sakaguchi, M.; Satoh, K.; Kamigaito, M. A user-friendly living cationic polymerization: Degenerative chain-transfer polymerization of vinyl ethers by simply using mixtures of weak and superstrong protonic acids. Chinese J. Polym. Sci. 2019, 37, 851–857 DOI： 10.1007/s10118-019-2233-0.

Mineto Uchiyama, Masataka Sakaguchi, Kotaro Satoh, et al. A User-friendly Living Cationic Polymerization: Degenerative Chain-transfer Polymerization of Vinyl Ethers by Simply Using Mixtures of Weak and Superstrong Protonic Acids[J]. Chinese Journal of Polymer Science, 2019, 37(9): 851-857. DOI： 10.1007/s10118-019-2233-0.

摘要

Abstract

Mixtures of a weak protonic acid and a trace amount of superstrong protonic acid were used for the simple control of the cationic polymerization of vinyl ethers

via

a degenerative chain-transfer mechanism

in which the former acid works as a precursor of the chain transfer agent (CTA) or the dormant species and the latter works as a source of the cationic propagating species. The addition of mixtures of phosphoric acid dibutyl ester ((

-BuO)

H) or 1-octanethiol (

-C

SH) and a trace amount of trifluoromethanesulfonic acid (TfOH) to a solution of isobutyl vinyl ether (IBVE) at −78 °C resulted in polymers with controlled molecular weights

which were basically determined by the feed ratio of IBVE to the weak protonic acid

and narrow molecular weight distributions (

≈ 1.1). These results were almost the same as those obtained using their prepared adducts of IBVE as CTAs in the presence of a trace amount of TfOH under similar conditions. Methanesulfonic acid (CH

whose adduct of IBVE has not been isolated due to instability

was similarly used in conjunction with trace TfOH to result in controlled molecular weights but slightly broader MWDs (

= 1.2–1.8). These results indicate that the sulfoxonium ion is also an effective intermediate in the cationic DT polymerization in addition to the phosphonium and sulfonium intermediates derived from (

-BuO)

H and

-C

respectively. The simple living cationic polymerization was thus achieved by using a combination of a weak protonic acid and a trace amount of TfOH

which are both easily available

low cost

free from metal

and easy to handle

without need for preparation of the initiator.

关键词

Keywords

references

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