The structure of methacrolein polymers prepared by anionic polymerization

Koton, M.M.; Andreyeva, I.V.; Getmanchuk, Yu. P.; Madorskaya, L.Ya.; Pokrovskii, Ye.I.; Kol'tsov, A. I.; Filatova, V.A.

doi:10.1016/0032-3950(65)90153-x

Cited by 7 publications

(4 citation statements)

References 10 publications

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“…An analogous process was reported by Koton in the electron transfer initiation of methacrolein. [51] By another electronic attack toward the central carbon in the tetrahedron of ( 1), an e sol − is coupled to the ester group of MMA (2). This e sol − is inferred to readily migrate to an incoming MMA due to its electron-deficiency (3,4), after which a weak 𝜎-bond consisting of 𝜋 components may be generated between the tertiary radical and the methylene of MMA (4,5).…”

Section: Proposed Mechanismmentioning

confidence: 99%

Controlled Radical Polymerization Initiated by Solvated Electrons

Li,

Pan,

Xia

et al. 2023

Macromol. Rapid Commun.

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Solvated electron (esol−) is highly reducing species and apt to initiate monomers via one‐electron transfer reaction. Herein, utilizing the esol− solution of Na/hexamethylphosphoramide, radical and anionic initiations were observed respectively, which heavily depended on Na concentrations. Interestingly, this initiation system, in states of lower Na concentrations, higher molar conductivities and less paired esol−, gave rise to a controlled radical polymerization (CRP) to yield polymers with predictable molecular weights and narrow molecular weight distributions (the lowest Ð = 1.25). This CRP presented unique behaviors, like solvent effect, electric field effect and unusual copolymerization phenomenon. A semi‐conjugated radical carrying a negative charge is proposed to be responsible for the CRP. This system gives a distinct way to regulate CRP from current CRPs, and offers new insights into the monomer initiation by esol−.This article is protected by copyright. All rights reserved

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Section: Proposed Mechanismmentioning

confidence: 99%

Controlled Radical Polymerization Initiated by Solvated Electrons

Li,

Pan,

Xia

et al. 2023

Macromol. Rapid Commun.

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“…Similar to other smaller aldehydes with their vapor pressure, MACR is not directly detected in ESI(+)-MS. , Further treatment such as derivatization is needed to detect MACR ESI(+)-MS, but for this study, derivatization of carbonyl was not used to minimize complication and interference. Furthermore, oligomerization in MACR is at a minimum due to the steric hindrance of unsaturated carbon unless it is subjected to a specific catalyst. , …”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, oligomerization in MACR is at a minimum due to the steric hindrance of unsaturated carbon unless it is subjected to a specific catalyst. 95,96 However, the light-induced reaction between 3 2-IC* and MACR occurs, and product peaks appeared at Rt = 0.60, 0.76, and 1.26 min (Figure 4b and d), increasing with irradiation time. Light induced reaction of 2-IC and MACR causes up to a 38% loss of 2-IC within 3 h of the reaction (Figure 4d, Figure S10).…”

Section: Kinetics Of Excited Triplet-state Photosensitizersmentioning

confidence: 97%

Kinetics and Mechanisms of Aqueous-Phase Reactions of Triplet-State Imidazole-2-carboxaldehyde and 3,4-Dimethoxybenzaldehyde with α,β-Unsaturated Carbonyl Compounds

et al. 2022

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Reactions in the atmospheric aqueous phase are an important source of secondary organic aerosols (SOA). Within the present study, the reactions of triplet-state imidazole-2-carboxaldehyde (32-IC*) with methyl vinyl ketone (MVK, R1), methacrolein (MACR, R2), and methacrylic acid (MAA, R3), as well as the reaction of triplet-state 3,4-dimethoxybenzaldehyde (3DMB*) with the unsaturated compounds (MVK, R4), (MACR, R5), and (MAA, R6), in the aqueous phase were investigated using laser flash excitation–laser long path absorption and ultraperformance liquid chromatography coupled with high definition electrospray ionization spectrometry. The second-order reaction constants for 32-IC* were determined to be k 1 = (1.0 ± 0.1) × 109 L mol–1 s–1 at pH 4–5 and 9, k 2 = (1.4 ± 0.4) × 109 L mol–1 s–1 and (1.5 ± 0.1) × 109 L mol–1 s–1 at pH 4–5 and 9, and k 3 = (1.4 ± 0.4) × 109 L mol–1 s–1 and (1.1 ± 0.4) × 108 L mol–1 s–1 at pH 4–5 and 9, respectively. The main products of the [2 + 2] photocycloaddition reactions of 32-IC* with both monomer and dimer of MVK as well as MACR were characterized. Similarly, the [2 + 2] photocycloaddition of the carbonyl of the excited triplet state of 3,4-dimethoxybenzaldehyde (3DMB*) with MVK was observed. The second order rate constants for the reactions of 3DMB* were determined: k 4 = (1.5 ± 0.2) × 108 L mol–1 s–1, k 5 = (2.8 ± 0.5) × 108 L mol–1 s–1, and k 6 = (5.2 ± 1.2) × 106 L mol–1 s–1 at pH 9. The studied reactions show that different triplet photosensitizers react with strongly varying rate constants. Advanced CAPRAM process model studies show that active photosensitizers such as 3DMB* can quickly react with unsaturated organic compounds under deliquesced aerosol conditions modifying SOA, while the quenching with oxygen dominates the excited photosensitizer loss under cloud conditions.

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“…A close analogy to the presently proposed cation-radical mechanism, which yields fused cyclohexane rings, is the anion-radical mechanism, which h a s been proposed in the polymerization of methacrolein in tetrahydrofuran with a sodium naphthalene complex to yield fused tetrahydropyran rings [19]. A one-electron transfer from the naphthalene anion radical to the methacrolein yields a monomer anion radical which propagates by anion and radical addition reactions.…”

Section: Cyclo-and Cyclized Diene Polymers XVIII 443mentioning

confidence: 96%

Cyclo- and Cyclized Diene Polymers. XVIII. Microstructure and Mechanism of Cyclopolymerization of Isoprene and Butadiene with C₂H₅AlCl₂+ TiCl₄Catalyst

Gaylord

Kössler²,

Štolka³

1968

Journal of Macromolecular Science: Part A - Chemistry

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The structure of methacrolein polymers prepared by anionic polymerization

Cited by 7 publications

References 10 publications

Controlled Radical Polymerization Initiated by Solvated Electrons

Controlled Radical Polymerization Initiated by Solvated Electrons

Kinetics and Mechanisms of Aqueous-Phase Reactions of Triplet-State Imidazole-2-carboxaldehyde and 3,4-Dimethoxybenzaldehyde with α,β-Unsaturated Carbonyl Compounds

Cyclo- and Cyclized Diene Polymers. XVIII. Microstructure and Mechanism of Cyclopolymerization of Isoprene and Butadiene with C₂H₅AlCl₂+ TiCl₄Catalyst

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The structure of methacrolein polymers prepared by anionic polymerization

Cited by 7 publications

References 10 publications

Controlled Radical Polymerization Initiated by Solvated Electrons

Controlled Radical Polymerization Initiated by Solvated Electrons

Kinetics and Mechanisms of Aqueous-Phase Reactions of Triplet-State Imidazole-2-carboxaldehyde and 3,4-Dimethoxybenzaldehyde with α,β-Unsaturated Carbonyl Compounds

Cyclo- and Cyclized Diene Polymers. XVIII. Microstructure and Mechanism of Cyclopolymerization of Isoprene and Butadiene with C2H5AlCl2+ TiCl4Catalyst

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Cyclo- and Cyclized Diene Polymers. XVIII. Microstructure and Mechanism of Cyclopolymerization of Isoprene and Butadiene with C₂H₅AlCl₂+ TiCl₄Catalyst