Controlled Alternating Copolymerization of (Meth)acrylates and Vinyl Ethers by Using Organoheteroatom‐Mediated Living Radical Polymerization

Mishima, Eri; Yamago, Shigeru

doi:10.1002/marc.201100089

Cited by 55 publications

(26 citation statements)

References 48 publications

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“…However, in some exceptional cases, a combination of monomers, the vinyl groups of which are electron‐deficient and donating, alternating sequences can be obtained; this is particularly true when both monomers are either non‐ or hardly homopolymerizable. The former group includes 1,2‐disubstituted monomers possessing electron‐withdrawing groups, such as maleic anhydride,8–12 maleimides,13–22 fumarates,23, 24 and fumaronitrile,25, 26 whereas the latter group includes vinyl ethers,27, 28 vinyl sulfides,29 and non‐polar olefins 30. In addition to the occurrence of such spontaneous alternating sequences governed by the inherent monomer reactivities, the use of Lewis acid additives or polar solvents can enhance the formation of alternating sequences.…”

Section: Introductionmentioning

confidence: 99%

1:2‐sequence‐regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol

Matsuda

Satoh

Kamigaito

2013

J. Polym. Sci. A Polym. Chem.

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Naturally occurring bulky terpenes, such as (þ)-and (-)-limonene and (-)-b-pinene, were quantitatively copolymerized with maleimide (MI) derivatives (i.e., phenyl-, cyclohexyl-, ethyl-, and unsubstituted-MI) in PhC(CF 3 ) 2 OH solvent via selective 1:2alternating propagation governed by the penultimate effect, which resulted in 1:2-sequence regulated polymers with relatively high glass transition temperatures and optical activities. Similar petroleum-derived bulky olefins possessing cyclohexenyl, cyclohexyl, or additional a-methyl substituents were copolymerized with phenylmaleimide via preferential 1:2-alternating propagation with a slightly lower selectivity. A further decrease in the bulkiness of nonpolar olefins increased the 1:1-alternating sequence. The copolymerization of limonene and acrylonitrile also proceeded approximately via 1:1-alternating propagation, in which the penultimate effect was less observable. Furthermore, when methylene chloride was used instead of fluorinated alcohol for the copolymerization of limonene and phenylmaleimide, the length of the sequence of MI units increased. Thus, in addition to the characteristic MI skeleton, the bulky and rather specific structure of either limonene or b-pinene induces 1:2-selective propagation via the penultimate effect, whereas the fluoroalcohol diminishes the homopropagation of MI via a hydrogen bonding interaction with the MI unit. RAFT copolymerization of limonene and various MI derivatives in PhC(CF 3 ) 2 OH successfully proceeded to give the end-to-end 1:2-sequence-regulated copolymer with a selective initiating sequence and predominant capping sequence using an appropriate RAFT agent.

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Section: Introductionmentioning

confidence: 99%

1:2‐sequence‐regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol

Matsuda

Satoh

Kamigaito

2013

J. Polym. Sci. A Polym. Chem.

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“…These include high monomer versatility [25–27], good compatibility with polar functional groups and solvents [28–29], and facile living-end transformation for the synthesis of block copolymers [30–34] and end-functional polymers [35–36]. Furthermore, we recently reported that photochemical stimuli were efficient in the activation of organotellurium dormant species, and that TERP proceeded under mild thermal conditions to give highly controlled polymers [37].…”

Section: Introductionmentioning

confidence: 99%

Organotellurium-mediated living radical polymerization under photoirradiation by a low-intensity light-emitting diode

Nakamura¹,

Yamago²

2013

Beilstein J. Org. Chem.

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SummaryA low-intensity (6 W) light-emitting diode (LED) effectively activated an organotellurium chain transfer agent and the dormant species, promoting well-controlled radical polymerization. The use of the LED provided many advantages over the previously reported high-intensity Hg lamp, including high energy efficiency during the polymerization, and easy availability of the low-cost light source. Structurally well-defined poly(methyl methacrylate), poly(methyl acrylate), and polystyrene, with narrow molecular weight distributions, were synthesized under LED irradiation with or without a neutral density filter.

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“…Another of the authors developed TERP [18,[31][32][33] with features such as high monomer versatility, [34][35][36][37] high compatibility with functional groups, [38] as well as high flexibility in copolymer synthesis [39] and polymer chain-end modifications. [40][41][42] Whereas TERP mainly proceeds by the DT mechanism like RAFT (Scheme 1b), [32] it does not involve as table intermediate radical during the DT process.…”

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confidence: 99%

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

et al. 2017

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The first successfully controlled radical polymerization (CRP) of ethylene is reported using several organotellurium chain-transfer agents (CTAs) under mild conditions (70 8 8C, 200 bar of ethylene) within the concept of organotellurium-mediated radical polymerization (TERP). In contrast to preceding works on CRPs of ethylene applying reversible addition-fragmentation chain-transfer (RAFT), the TERP system provided ah igh livingness and chain-end functionalization of polyethylene chains.Molar-mass distributions with dispersities between 1.3 and 2.1 were obtained up to average molar masses of 5000 gmol À1 .Asinthe RAFT system, the high reactivity of the growing polyethylenyl radical led to an inherent side reaction. Fort he presented TERP systems, however,this side reaction did not result in dead chains,while it could even be effectively suppressed by ag ood choice of the CTA.

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Controlled Alternating Copolymerization of (Meth)acrylates and Vinyl Ethers by Using Organoheteroatom‐Mediated Living Radical Polymerization

Cited by 55 publications

References 48 publications

1:2‐sequence‐regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol

1:2‐sequence‐regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol

Organotellurium-mediated living radical polymerization under photoirradiation by a low-intensity light-emitting diode

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

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