1:3 ABAA sequence-regulated substituted polymethylenes via alternating radical copolymerization of methyl cinnamate and maleic anhydride followed by post-polymerization reactions

Terao, Yuya; Sugihara, Shizuka; Satoh, Kotaro; Kamigaito, Masami

doi:10.1016/j.eurpolymj.2019.109225

Cited by 5 publications

(3 citation statements)

References 28 publications

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“…As we have proposed, these biobased vinyl compounds can be classified into similar vinyl monomer families, such as nonpolar olefins, styrenes, and acrylic monomers, to those of petroleum-derived monomers, depending on their substituents and structures [ 26 , 27 , 28 , 29 ]. For example, renewable polar monomers with conjugated carbonyl groups, such as tulipalin A and itaconic acid, are considered to be acrylic monomers [ 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ], whereas phenylpropanoids and their derivatives, such as anethole and vinylguaiacol, are considered to be styrenes [ 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. These conjugated monomers are generally reactive in radical polymerizations due to the C=C bonds conjugated with carbonyl or phenyl groups, resulting in relatively stable propagating radical species.…”

Section: Introductionmentioning

confidence: 99%

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

2020

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A series of exo-methylene 6-membered ring conjugated dienes, which are directly or indirectly obtained from terpenoids, such as β-phellandrene, carvone, piperitone, and verbenone, were radically polymerized. Although their radical homopolymerizations were very slow, radical copolymerizations proceeded well with various common vinyl monomers, such as methyl acrylate (MA), acrylonitrile (AN), methyl methacrylate (MMA), and styrene (St), resulting in copolymers with comparable incorporation ratios of bio-based cyclic conjugated monomer units ranging from 40 to 60 mol% at a 1:1 feed ratio. The monomer reactivity ratios when using AN as a comonomer were close to 0, whereas those with St were approximately 0.5 to 1, indicating that these diene monomers can be considered electron-rich monomers. Reversible addition fragmentation chain-transfer (RAFT) copolymerizations with MA, AN, MMA, and St were all successful when using S-cumyl-S’-butyl trithiocarbonate (CBTC) as the RAFT agent resulting in copolymers with controlled molecular weights. The copolymers obtained with AN, MMA, or St showed glass transition temperatures (Tg) similar to those of common vinyl polymers (Tg ~ 100 °C), indicating that biobased cyclic structures were successfully incorporated into commodity polymers without losing good thermal properties.

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Section: Introductionmentioning

confidence: 99%

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

2020

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“…The same authors also obtained a slightly higher reactivity of MCM when copolymerizing it with maleic anhydride. [ 470 ] Alternating copolymers were obtained after 13 days at 60 °C (70% conversion, M n = 16 kg mol −1 ).…”

Section: Polymerization Of (Meth)acrylic Monomers and Analogsmentioning

confidence: 99%

Production and Polymerization of Biobased Acrylates and Analogs

Fouilloux

Thomas

2021

Macromol. Rapid Commun.

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To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high‐potential intermediates are identified: glycerol, lactic acid, and 3‐hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2‐hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high‐performance polymers. Finally, β‐substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater.

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“…[ 22,23 ] The absence of methylene spacer provides good thermal properties. [ 24 ] The dense packing enables fast excimer formation when pyrenes are incorporated. [ 25 ] Our previous study using poly(diisopropyl fumarate) (PDiPF) showed a strong β relaxation, which follows VFT dependence.…”

Section: Introductionmentioning

confidence: 99%

Characteristic Features of α and β Relaxations of Poly(diethyl fumarate) as the Poly(substituted methylene)

Suzuki

Tsuji

Miyata

et al. 2021

Macro Chemistry & Physics

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Recently the β relaxation draws attention because it may act as a precursor of the α relaxation and potentially influences a wide range of properties. In many cases, the weak intensity of the β relaxation limits the experimental investigation. Herein, the β relaxation of poly(diethyl fumarate) (PDEF) using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and dielectric spectroscopy is investigated. Originating from the absence of methylene spacer in the main chain, polyfumarates possess an intense β relaxation. Unlike common vinyl polymers, PDEF shows two distinct steps in DSC measurement corresponding to α and β relaxations. Interestingly, the relative intensities of α and β relaxations depend on the thermal history. The β relaxation of PDEF obtained by dielectric spectroscopy at high temperature is similar to that of poly(methyl methacrylate) (PMMA). However, the β relaxation of PDEF follows the VFT equation rather than the Arrhenius equation at low temperatures. The analysis of PDEF/PMMA blend suggests the local orientation of PDEF chain plays a vital role in the intense β relaxation.

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1:3 ABAA sequence-regulated substituted polymethylenes via alternating radical copolymerization of methyl cinnamate and maleic anhydride followed by post-polymerization reactions

Cited by 5 publications

References 28 publications

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

Biobased Polymers via Radical Homopolymerization and Copolymerization of a Series of Terpenoid-Derived Conjugated Dienes with exo-Methylene and 6-Membered Ring

Production and Polymerization of Biobased Acrylates and Analogs

Characteristic Features of α and β Relaxations of Poly(diethyl fumarate) as the Poly(substituted methylene)

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