Vinyl Polymerization. 393. Radical Polymerization of Vinyl Monomer Initiated by Aliphatic Aldehyde

Ouchi, Tatsuro; Murayama, Noriyuki; Imoto, Minoru

doi:10.1246/bcsj.53.748

Cited by 19 publications

(4 citation statements)

References 5 publications

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“…Previous studies have shown that solvent can influence the initiation ,− step in thermal polymerization of acrylates and methacrylates. Ouchi et al found that several aldehydes could initiate the polymerization of methyl acrylate. Kaim , later reported that cyclohexanone (CHo) can also initiate polymerization of several vinyl monomers, such as acrylamide, n -butyl acrylate, and MMA.…”

Section: Introductionmentioning

confidence: 99%

Computational Study of Cyclohexanone–Monomer Co-initiation Mechanism in Thermal Homo-polymerization of Methyl Acrylate and Methyl Methacrylate

et al. 2012

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This paper presents a systematic computational study of the mechanism of cyclohexanone-monomer co-initiation in high-temperature homopolymerization of methyl acrylate (MA) and methyl methacrylate (MMA). Previous experimental studies of spontaneous thermal homopolymerization of MA and MMA showed higher monomer conversion in the presence of cyclohexanone than xylene. However, these studies did not reveal the initiation mechanism(s) or the initiating species. To identify the initiation mechanism and the initiating species, we explore four different mechanisms, (1) Kaim, (2) Flory, (3) α-position hydrogen transfer, and (4) Mayo, using first-principles density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) calculations. Transition-state geometries for each mechanism are determined using B3LYP/6-31G* and assessed with MP2/6-31G*. Activation energies and rate constants are calculated using transition-state theory. The harmonic oscillator approximation and tunneling corrections are applied to compute the reaction rate constants. This study indicates that α-position hydrogen transfer and Mayo mechanisms have comparable barriers and are capable of generating monoradicals for initiating polymerization of MA and MMA; these two mechanisms can cause cyclohexanone-monomer co-initiation in thermal polymerization of MA and MMA.

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Section: Introductionmentioning

confidence: 99%

Computational Study of Cyclohexanone–Monomer Co-initiation Mechanism in Thermal Homo-polymerization of Methyl Acrylate and Methyl Methacrylate

et al. 2012

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“…In these polymerization systems, the interaction between the carbonyl oxygen in the additive carbonyl compound and the amide group in the AAm monomer seems to play an important role in the initiation and propagation steps. It has been reported that some types of active methylene containing compounds such as aldehyde and ketones induced the radical polymerization of polar vinyl monomers (9)(10)(11). For instance, the polymerization of methyl methacrylate (MMA) was induced by cyclohexanone, and its mechanism was proposed to involve the hydrogen radical transfer from ketone to MMA (12,13).…”

Section: Introductionmentioning

confidence: 99%

Polymerization of Acrylamide in Aqueous Solution of Poly(N‐isopropylacrylamide) at Lower Critical Solution Temperature

Ishifune

Suzuki

Yamane

et al. 2008

Journal of Macromolecular Science, Part A

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Acrylamide (AAm) was found to polymerize in a solution of poly(N-isopropylacrylamide) (PNIPAAm) in water at around its lower critical solution temperature (LCST) (328C) without any initiators. This phenomenon was specifically observed in aqueous solutions of the polymers having LCST such as PNIPAAm and poly(methylvinylether) (PMVE). AAm polymerized only when PNIPAAm and AAm were dissolved in water below LCST of PNIPAAm and then the solution was warmed up to the polymerization temperature (408C). On the other hand, the polymerization of AAm did not proceed when AAm was added into aqueous PNIPAAm solution during and after the phase separation above 328C. Furthermore the polymerizability of AAm was remarkably affected by the concentration and molecular weight of the PNIPAAm additives. Under the condition of lower PNIPAAm concentration (0.30 mol/L), the increase in the molecular weight of PNIPAAm considerably increased the molecular weight of the resulting PAAm but decreased the yield of PAAm. Under the condition of higher PNIPAAm concentration (0.60 mol/L) the polymerizability was not so affected by the molecular weight of PNIPAAm, while the molecular weight of PAAm formed by using higher molecular weight PNIPAAm was higher than those of PAAm formed by using lower molecular weight PNIPAAm. Moreover, the molecular weight of PAAm formed by the PNIPAAm induced polymerization of AAm was much higher than that of the polymer obtained by the radical polymerization using AIBN in THF or VA-061 in water.

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“…has been the subject of many publications [1][2][3][4][5][6][7][8]. has been the subject of many publications [1][2][3][4][5][6][7][8].…”

Section: Introductionmentioning

confidence: 99%

Study on Copolymerization of Acrylamide With Styrene Initiated by Methyl Ethyl Ketone and Its Derivatives in Comparison With Conventional Radical Initiator

Zhong

Ishifune

Yamashita

2000

Journal of Macromolecular Science, Part A

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Copolymerization of acrylamide (AAm) with styrene (St) was carried out in the presence of methyl ethyl ketone (MEK), methyl isopropyl ketone (MIK) and t-butyl methyl ketone (tBMK) without any conventional initiator in tetrahydrofuran (THF) at 60¡C. The copolymerization of AAm with St proceeded readily in the presence of the MEK, MIK, and tBMK, while no copolymerization of AAm with St proceeded in the absence of these ketones under the same conditions and no homo-polymerization of St proceeded even in the presence of the ketones. The reactivity ratio of monomer AAm (r 1 ) is smaller than that of St (r 2 ) in all of the copolymerization systems, and increases as the order: MEK < MIK < tBMK. The conversion of the copolymerizations increases as the same order described above. The interaction

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Vinyl Polymerization. 393. Radical Polymerization of Vinyl Monomer Initiated by Aliphatic Aldehyde

Cited by 19 publications

References 5 publications

Computational Study of Cyclohexanone–Monomer Co-initiation Mechanism in Thermal Homo-polymerization of Methyl Acrylate and Methyl Methacrylate

Computational Study of Cyclohexanone–Monomer Co-initiation Mechanism in Thermal Homo-polymerization of Methyl Acrylate and Methyl Methacrylate

Polymerization of Acrylamide in Aqueous Solution of Poly(N‐isopropylacrylamide) at Lower Critical Solution Temperature

Study on Copolymerization of Acrylamide With Styrene Initiated by Methyl Ethyl Ketone and Its Derivatives in Comparison With Conventional Radical Initiator

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