Citation: Mineto Uchiyama, Masataka Sakaguchi, Kotaro Satoh, Masami Kamigaito. 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 shu

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

Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Furo-cho, Chikusa-ku, Nagoya University, Nagoya 464-8603, Japan

Corresponding author: Kotaro Satoh, satoh@chembio.nagoya-u.ac.jp Masami Kamigaito, kamigait@chembio.nagoya-u.ac.jp
Received Date: 27 December 2018
Revised Date: 22 January 2019
Available Online: 4 March 2019

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 ((n-BuO)₂PO₂H) or 1-octanethiol (n-C₈H₁₇SH) 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 (M_w/M_n ≈ 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 (CH₃SO₃H), 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 (M_w/M_n = 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 (n-BuO)₂PO₂H and n-C₈H₁₇SH, 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.
- Living cationic polymerization,
- Degenerative chain transfer,
- RAFT polymerization,
- Metal free,
- Vinyl ether
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