Synthesis of isotactic poly[α-(hydroxymethyl)acrylate] by anionic polymerization of the protected monomer

Kohsaka, Yasuhiro; Yamamoto, Kazuki; Suzawa, Kazuha; Kitayama, Tatsuki

doi:10.1007/s00289-016-1813-1

Cited by 6 publications

(3 citation statements)

References 25 publications

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“…Since we have investigated the polymerization chemistry of α-functionalized acrylate [18,19], the anionic polymerization of DMDO have been investigated [17] in order to understand the isotacticspecific polymerization behavior of α-(alkoxymethyl)acrylate [20][21][22]. DMDO also have an aspect of a cyclic hemiacetal ester.…”

Section: Scheme 1 Rops Of Dmdo and Mβblmentioning

confidence: 99%

Synthesis of poly(conjugated ester)s by ring-opening polymerization of cyclic hemiacetal ester bearing acryl skeleton

Kohsaka

Yamashita

Matsuhashi

et al. 2019

European Polymer Journal

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Section: Scheme 1 Rops Of Dmdo and Mβblmentioning

confidence: 99%

Synthesis of poly(conjugated ester)s by ring-opening polymerization of cyclic hemiacetal ester bearing acryl skeleton

Kohsaka

Yamashita

Matsuhashi

et al. 2019

European Polymer Journal

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“…Such reactions have already been reported for some polyesters that undergo MCS via the amination of pendant groups. 40,41 To apply this concept to vinyl polymers, copolymerization of 1 42 and CKA 2 43 was proposed (Scheme 1). 1 and 2 were expected to form statistically alternating sequences, 37,39 as predicted by the classical Alfrey-Price Q-e scheme.…”

mentioning

confidence: 99%

Fast and Selective Main-Chain Scission of Vinyl Polymers using the Domino Reaction in the Alternating Sequence for Trans-esterification

Kohsaka,

Toyama,

Kawauchi

2024

Preprint

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This communication reports on vinyl polymers capable of selective and fast main-chain scission (MCS). The trick is the domino reaction in an alternating sequence of methyl 2-(trimethylsiloxymethyl)acrylate and 5,6-benzo-2-methylene-1,3-dioxepane, a cyclic ketene acetal for radical ring-opening polymerization. Removal of the trimethylsilyl group using Bu4N+‧F− readily led to MCS via irreversible transesterification of the ester backbone, affording a five-membered lactone fragment. The molar mass decreased drastically within 5 min, and no side reactions were observed. Control experiments suggest that the formation of a five-membered ring via a domino reaction is critical for fast and selective MCS. The terpol-ymers with methyl methacrylate and styrene also exhibited a large decrease in molar mass within 5 min. In addition, MCS was also observed for the heterogeneous reaction system in acidic aqueous media; treatment of the binary copolymer in a 50 wt% acetic acid solution resulted in a significant decrease in molar mass after 30 min. These results suggest efficient construction of degradable sites using a binary monomer system corresponding to the pendant trigger and ester backbone. Because this molecular design, which uses a combination of simple monomers, is applicable to terpolymers containing other vinyl monomers, it can provide various degradable vinyl polymers.

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“…Such reactions have already been reported for some polyesters that undergo MCS via the amination of pendant groups. 44,45 To apply this concept to vinyl polymers, copolymerization of 1 46 and CKA 2 47 was proposed. 1 and 2 were expected to form statistically alternating sequences, 41,40 as predicted by the classical Alfrey−Price Q−e scheme (Table S2).…”

mentioning

confidence: 99%

Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification

Kohsaka,

Toyama,

Kawauchi

et al. 2024

ACS Macro Lett.

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This communication reports on vinyl polymers capable of selective and fast main-chain scission (MCS). The trick is the domino reaction in an alternating sequence of methyl 2-(trimethylsiloxymethyl)acrylate and 5,6-benzo-2-methylene-1,3dioxepane, a cyclic ketene acetal for radical ring-opening polymerization. Removal of the trimethylsilyl group using Bu 4 N + • F − readily led to MCS via irreversible transesterification of the ester backbone, affording a five-membered lactone fragment. The molar mass decreased drastically within 5 min, and no side reactions were observed. Control experiments suggest that the formation of a five-membered ring via a domino reaction is critical for fast and selective MCS. The terpolymers with methyl methacrylate and styrene also exhibited a large decrease in molar mass within 5 min. In addition, MCS was also observed for the heterogeneous reaction system in acidic aqueous media; treatment of the binary copolymer in a 50 wt % acetic acid solution resulted in a significant decrease in molar mass after 30 min. These results suggest efficient construction of degradable sites using a binary monomer system corresponding to the pendant trigger and ester backbone. Because this molecular design using a binary monomer system provides selective and fast MCS for terpolymers containing other vinyl monomers, it can provide various degradable vinyl polymers.

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Synthesis of isotactic poly[α-(hydroxymethyl)acrylate] by anionic polymerization of the protected monomer

Cited by 6 publications

References 25 publications

Synthesis of poly(conjugated ester)s by ring-opening polymerization of cyclic hemiacetal ester bearing acryl skeleton

Synthesis of poly(conjugated ester)s by ring-opening polymerization of cyclic hemiacetal ester bearing acryl skeleton

Fast and Selective Main-Chain Scission of Vinyl Polymers using the Domino Reaction in the Alternating Sequence for Trans-esterification

Fast and Selective Main-Chain Scission of Vinyl Polymers Using the Domino Reaction in the Alternating Sequence for Transesterification

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