Ring size-reactivity relationship in radical ring-opening copolymerisation of thionolactones with vinyl pivalate

Ivanchenko, Oleksandr; Mazières, Stéphane; Poli, Rinaldo; Harrisson, Simon; Destarac, Mathias

doi:10.1039/d2py01153k

Cited by 13 publications

(14 citation statements)

References 32 publications

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“…General Procedure for the Preparation of Poly(TL-co-VP). Based on previous procedures, 21 TL and VP were mixed together with 0.5 mol % VAZO-88 relative to comonomers. The solution was transferred into a Carius tube that was sealed under vacuum after degassing by three freeze−pump−thaw cycles.…”

Section: Synthesis Of 1-(octylsulfanyl)ethan-1-one Tementioning

confidence: 99%

“…■ RESULTS AND DISCUSSION TBL, TVL, and TCL, which were recently reported 21 for the preparation of copolymers with VP, were used in this study. Copolymers of TL with VP were prepared with different fractions of incorporated TL and different ratios between TLs incorporated in thioester or S,O-thioketal forms (Scheme 4).…”

Section: Synthesis Of 1-(octylsulfanyl)ethan-1-one Tementioning

confidence: 99%

“…Copolymers of VP with TCL, TVL, and TBL were prepared as reported in a previous article. 21 Monomer conversions as well as the copolymer microstructure were determined by 1 H NMR following the methods reported in our previous work. 19 For detailed information on the microstructure analysis, see Figures S5−S78; for an example of calculation of N av.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…19 Later, we showed that for unsubstituted thionolactones (TLs) of different ring sizes, copolymerization proceeds in both ring-opened (thioester) and ring-closed (S,Othioketal) forms with vinyl pivalate (VP) (Scheme 2a). 21 The fraction of ring-opened units (Scheme 2b) was calculated for several TLs and varies from 16 to 81% (Scheme 2c). Additionally, 3,6-dimethyl-5-thioxo-1,4-dioxan-2-one (TLD; Scheme 1) has been reported to undergo rROcoP with acrylates, 22,23 styrene, 22,23 and methyl methacrylate.…”

Section: ■ Introductionmentioning

confidence: 99%

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On-Demand Degradation of Thioester/Thioketal Functions in Vinyl Pivalate-Derived Copolymers with Thionolactones

et al. 2023

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Copolymers containing thioester and thioketal groups were obtained by copolymerization of five-to sevenmembered ring thionolactones (TLs) with vinyl pivalate (VP). With the help of a degradation study on thioester and thioketal model compounds, we report the orthogonal reactivity of such incorporated links with thioesters being selectively cleaved by aminolysis and thioketals by peroxides. Orthogonal stepwise degradation of poly(TL-co-VP) copolymers was achieved using isopropylamine and benzoyl peroxide as shown by SEC. Bleach was identified as a universal agent for accelerated degradation. A good correlation between oligomer length after degradation and estimated polymer mass loss is also reported.

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Section: Synthesis Of 1-(octylsulfanyl)ethan-1-one Tementioning

confidence: 99%

Section: Synthesis Of 1-(octylsulfanyl)ethan-1-one Tementioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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On-Demand Degradation of Thioester/Thioketal Functions in Vinyl Pivalate-Derived Copolymers with Thionolactones

et al. 2023

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“…The polymerizations typically required very low temperatures (−78 to −120 °C). Very recently, a few reports on radical polymerizations of cyclic thiocarbonyl compounds indicated that some thionolactones were incorporated into a polymer as a mixture of ring-opened and cyclic structures with and without β-scission, respectively, which depended on the monomer structure and the polymerization conditions. − …”

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confidence: 99%

Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones

Watanabe

Kamigaito

2023

J. Am. Chem. Soc.

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Direct radical addition reactions of thiocarbonyl (CS) groups unaccompanied by β-scission have rarely been reported despite their potential for constructing various sulfur-containing compounds. Herein, we report direct radical copolymerizations of the CS double bonds of simple thioamide derivatives and the CC double bonds of common vinyl monomers to produce novel degradable vinyl polymers that contain thioether units in the backbones. In particular, N-acylated thioformamides copolymerized smoothly with various vinyl monomers, such as methyl acrylate, vinyl acetate, N,N-dimethylacrylamide, and styrene. RAFT copolymerization was also successfully mediated. The resultant copolymers had high glass transition temperatures and were readily degradable under ambient conditions. This work will expand the potential for use of thiocarbonyl compounds in radical reactions and develop novel poly(thioether)-vinyl polymer hybrid materials with unusual properties.

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Umpolung Isomerization in Radical Copolymerization of Benzyl Vinyl Ether with Pentafluorophenylacrylate Leading to Degradable AAB Periodic Copolymers

Kuroda,

Ouchi

2023

Angewandte Chemie

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This study revealed benzyl vinyl ether (BnVE) shows the peculiar isomerization propagation in radical copolymerization with an electron‐deficient acrylate carrying pentafluorophenyl group (PFA). The comonomer pair inherently exhibits the cross‐over propagation feature due to the large difference in electron density. However, the radical species of PFA was found to undergo a backward isomerization to the penultimate BnVE pendant giving benzyl radical species prior to the propagation with BnVE. The isomerization brings a drastic change in the character of growing radical species from electrophilic to nucleophilic, and thus the isomerized benzyl radial species propagates with PFA. Consequently, the two monomers were consumed in the order of AAB (A: PFA; B: BnVE) and the unique periodic consumption was confirmed by the pseudo‐reactivity ratios calculated by the penultimate model: r11 = 0.174 and r21 = 6600 for PFA (M1) with BnVE (M2). The pentafluorophenyl ester groups of the resulting copolymers are transformed into ester and amide groups via alcoholysis and aminolysis post‐polymerization modifications. The unique isomerization in AAB sequence allowed the periodic introduction of benzyl ether structure in the backbone leading to efficient degradation under acid conditions.

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Ring size-reactivity relationship in radical ring-opening copolymerisation of thionolactones with vinyl pivalate

Cited by 13 publications

References 32 publications

On-Demand Degradation of Thioester/Thioketal Functions in Vinyl Pivalate-Derived Copolymers with Thionolactones

On-Demand Degradation of Thioester/Thioketal Functions in Vinyl Pivalate-Derived Copolymers with Thionolactones

Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones

Umpolung Isomerization in Radical Copolymerization of Benzyl Vinyl Ether with Pentafluorophenylacrylate Leading to Degradable AAB Periodic Copolymers

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