Anionic polymerization of Lewis acid-activated methyl methacrylate by enamines

Miyamoto, Masatoshi; Kanetaka, Shin-Ya

doi:10.1002/(sici)1099-0518(19991001)37:19<3671::aid-pola2>3.0.co;2-3

Cited by 5 publications

(3 citation statements)

References 20 publications

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“…11 Moreover, polymerization using enamines/ bulky organoaluminum compounds has also been reported. 12 Since 2006, the growing interest in the FLP chemistry led to the development of a LP polymerization reaction utilizing aluminum-based Lewis acids, which is a promising technique in terms of activity, selectivity, control, monomer scope, and polymer topology. 13−23 Mechanistically, it is reasonable to assume that the Lewis base undergoes a Michael addition to the monomer activated by the Lewis acid, which can also stabilize the formed enolates, initiating and propagating anionic polymerization.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Since then, there have been several studies on LP polymerizations, including the synthesis of syndiotactic polymethacrylates and block copolymers and mechanistic investigations . Moreover, polymerization using enamines/bulky organoaluminum compounds has also been reported . Since 2006, the growing interest in the FLP chemistry led to the development of a LP polymerization reaction utilizing aluminum-based Lewis acids, which is a promising technique in terms of activity, selectivity, control, monomer scope, and polymer topology. − Mechanistically, it is reasonable to assume that the Lewis base undergoes a Michael addition to the monomer activated by the Lewis acid, which can also stabilize the formed enolates, initiating and propagating anionic polymerization. , Highly interacting LPs also exhibit high activities. , Thus, classical LPs, which have not received much attention, show potential as effective initiators and catalysts.…”

Section: Introductionmentioning

confidence: 99%

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Lewis Pair Radical Polymerization “On-Water”

et al. 2020

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An unprecedented radical polymerization of various (meth)acrylates, diethyl acrylamide, and 4-vinylpyridine initiated by Lewis pair (LP) catalysts, specifically PPh3/Cu(OTf)2 or PPh3/Sn(OTf)2, is reported herein. The reaction occurred at the interface between monomer and water phases, namely, “on-water”, at room temperature. The polymerization of (meth)acrylates “on-water” was significantly more efficient than the reaction in organic solvents or in bulk. It was determined that the propagation occurs via a single electron transfer, which was evidenced by the inhibition of the reaction by the addition of trace amounts of phenols or phenothiazine. Additionally, MALDI-TOF-MS analysis revealed the occurrence of disproportionation termination. Initiation at the interface was supported by various polymerization studies. Specifically, a higher rate of polymerization of methacrylates was observed for hydrophilic monomers. Moreover, the polymerizations in a mixed solvent of water and MeOH indicated that the heterogeneous system is critical. The generation of a PPh3 radical cation following a single electron transfer from LP was not plausible. Instead, we propose a mechanism involving a Michael addition of PPh3 to monomers activated by Lewis acids “on-water” to generate Cu(II) or Sn(II) enolates and/or free radical as propagating species.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Lewis Pair Radical Polymerization “On-Water”

et al. 2020

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“…Recently Fraser 17 has used copper ATRP (atom transfer radical polymerization) catalysts with quadridentate amine ligands to synthesise PMMA in which tacticity followed Bernoullian statistics. Highly syndiotactic PMMA was obtained by Kanetaka, 18 using enamine initiators in combination with MeAl(BHT) 2 .…”

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Syndio-rich poly(methyl methacrylate) from the anionic polymerisation of methyl methacrylate in the presence of novel organoaluminium amides

2001

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Zwitterionic Polymerization

Suzuki¹

2013

Encyclopedia of Polymer Science and Technology

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A zwitterion conducts the polymerization as the key intermediate, which is formed by the reaction between neutral electrophile and nucleophile, or as the monomer itself, which is prepared and isolated before use. The latter case is known in a limited number of articles. On the other hand, a number of examples have been reported for the former case, which is categorized into the following three patterns: (1) Propagation takes place from one site of a zwitterion, accordingly, which is the initiating species to give homopolymer. There is a case that a cyclic polymer is produced by the backbiting. (2) A zwitterion is formed to activate a monomer and reacts with a neutral initiator as well as the same functional group at the polymer terminal for the propagation reaction. In these two patterns, amine, phosphine, or N ‐heterocyclic carbene work as the initiator and the activator, respectively. (3) No catalyst copolymerization takes place by the reactions between zeitterionic intermediates, which are produced by the combination of a nucleophilic monomer with an electrophilic monomer. The monomers that appear in these three patterns involve electron‐deficient and electron‐rich olefinic compounds including qiunone and allene, heterocumulenes such as isocyanate and carbon disulfide, and heterocyclic compounds such as lactone, oxirane, amino acid N ‐carboxyanhydride, cyclic imino ether, cyclic phosphite, and cyclic phophonite.

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Anionic polymerization of Lewis acid-activated methyl methacrylate by enamines

Cited by 5 publications

References 20 publications

Lewis Pair Radical Polymerization “On-Water”

Lewis Pair Radical Polymerization “On-Water”

Syndio-rich poly(methyl methacrylate) from the anionic polymerisation of methyl methacrylate in the presence of novel organoaluminium amides

Zwitterionic Polymerization

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