On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

Mavroudakis, Evangelos; Cuccato, Danilo; Moscatelli, Davide

doi:10.3390/polym7091483

Cited by 44 publications

(39 citation statements)

References 154 publications

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“…The reasons of the formation of alternate polymers by MA and olefins are still unclear in detail. The methods of quantum chemistry based on the density functional theory were successfully used for the analysis of different radical polymerization processes [50][51][52], including homo-and copolymerization of acrylates [53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70][71], acrylamides [70,72,73], and acrylonitrile [74]. However, as far as we know, DFT-based methods have not been extensively used for visualization and comprehensive analysis of the free radical alternating copolymerization of donor and cyclic acceptor monomers, except the publications of Matsumoto et al, devoted to the copolymerization of N-methylmaleimide (MMI) with olefins [75], and MA with 2,4-dimethylpenta-1,3-diene [76].…”

Section: Introductionmentioning

confidence: 99%

DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins

2020

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The free radical copolymerization of electron-acceptor and electron-donor vinyl monomers represents a particular case of sequence-controlled polymerization. The reactions of maleic anhydride (MA) or related compounds (acceptor comonomers) with α-olefins (donor comonomers) result in the formation of the alternating copolymers that have clear prospects for petrochemical and biomedical applications. However, in contrast to the well-established polymerization of acrylate monomers, these processes have not been studied theoretically using the density functional theory (DFT) calculations. In our research, we performed a comprehensive theoretical analysis of the free radical copolymerization of MA and closely related maleimide with different structural types of olefins at mpw1pw91/6-311g(d) level of the DFT. The results of our calculations clearly indicated the preference of the alternating reaction mode for the copolymerization of MA with α-olefins, isobutylene and prospective unsaturated monomers, as well as methylenealkanes. The DFT modeling of the thermally induced Alder-ene reaction between MA and olefins allowed to exclude this reaction from the scope of possible side processes at moderately high temperatures. Comparative analysis of MA and N-methylmaleimide (MMI) reactivity shown that the use of MMI instead of MA makes no sense in terms of the reaction rate and selectivity.

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Section: Introductionmentioning

confidence: 99%

DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins

2020

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“…Over the recent years, some attempts were made to compute absolute rate coefficients (e.g., refs. ) using quantum chemistry. In many cases, solvent effects were simply not taken into account, or no comparison was made between different solvents.…”

Section: Introductionmentioning

confidence: 99%

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Deglmann

Hungenberg²,

Vale

2018

Macro Reaction Engineering

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Authors want to communicate that there is a typing error in the following sentence in paragraph 4.5:The largest medium effects of combinatorial origin are expected for systems with either (v S /v M ) >> 1, i.e., for large monomers such as iBoMA in small solvents like CO 2 , or systems with (v S /v M ) << 1, i.e., for the smallest monomer ethylene in large solvents like ILs.should read as follows:The largest medium effects of combinatorial origin are expected for systems with either (v S /v M ) << 1, i.e., for large monomers such as iBoMA in small solvents like CO 2 , or systems with (v S /v M ) >> 1, i.e., for the smallest monomer ethylene in large solvents like ILs.All presented results remain unchanged and correct; they are not affected by this oversight.

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“…Even the application of various quantum chemical tools over the recent years to compute absolute rate coefficients (e.g., refs. [22][23][24] ) does not offer a general explanation for the medium effect.…”

Section: Introductionmentioning

confidence: 96%

“…Until now, no general and quantitative theory of the solvent and concentration effect on k p is available. Even the application of various quantum chemical tools over the recent years to compute absolute rate coefficients (e.g., refs …”

Section: Introductionmentioning

confidence: 99%

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties

Deglmann

Hungenberg²,

Vale

2016

Macro Reaction Engineering

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The effect of solvents and monomer concentration on rate coefficients of propagation in radical polymerization has received tremendous interest during recent years, but a quantitative explanation and method of prediction of the medium effect is still missing. In this paper, it is shown that the thermodynamic formulation of the transition state theory is able to explain such effects almost quantitatively for a wide variety of monomers and solvents, including not only organic solvents but also less common solvents like ionic liquids or water, and monomers ranging from styrene to water‐soluble monomers like acrylic acid or N‐vinylformamide and also bulky monomers like isobornyl methacrylate. The medium effect is dictated by the activity coefficient of the monomer as well as by the ratio of the activity coefficients of the growing chain and the transition state. The solvent and concentration effects are, thus, a consequence of the degree of nonideality of the system. This interpretation based on the thermodynamics of real solutions offers for the first time a straightforward method to estimate the propagation rate coefficient of a given monomer in various solvents once the corresponding coefficient in bulk monomer is known.

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On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

Cited by 44 publications

References 154 publications

DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins

DFT Modeling of the Alternating Radical Copolymerization and Alder-Ene Reaction between Maleic Anhydride and Olefins

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties: A Quantitative Thermodynamic Interpretation

Dependence of Propagation Rate Coefficients in Radical Polymerization on Solution Properties

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