Laser-flash-initiated polymerization as a tool for evaluating (individual) kinetic constants of free-radical polymerization—5. Complete analysis by means of a single experiment

Olaj, Oskar Friedrich; Schnöll‐Bitai, Irene

doi:10.1016/0014-3057(89)90022-0

Cited by 125 publications

(68 citation statements)

References 13 publications

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“…Actually, such dependence is suggested to be significant only for the addition of the first few monomer units, i.e., at the shortest chain lengths. [8][9][10] If this is the case, the long chain value, fully independent upon the chain length,…”

Section: Introductionmentioning

confidence: 96%

Initiation Kinetics in Free‐Radical Polymerization: Prediction of Thermodynamic and Kinetic Parameters Based on ab initio Calculations

Dossi

Storti

Moscatelli

2010

Macro Theory & Simulations

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Initiation kinetics in free radical polymerization is investigated using density functional theory. Thermodynamic and kinetic parameters of the initiation reactions are predicted, and the role of the initiators in the polymerization process is evaluated. Methyl acrylate, methyl methacrylate, acrylonitrile, and styrene homo‐polymerizations with different initiators are studied. Reaction enthalpy and activation energy for each reaction between monomer and the radical fragments arising from the initiators have been determined. The initiation kinetic constants for all of these initiation reactions are evaluated and compared with both computational and experimental propagation kinetic constants of each monomer.magnified image

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Section: Introductionmentioning

confidence: 96%

Initiation Kinetics in Free‐Radical Polymerization: Prediction of Thermodynamic and Kinetic Parameters Based on ab initio Calculations

Dossi

Storti

Moscatelli

2010

Macro Theory & Simulations

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“…The need for an experimental procedure that provided an accurate estimation of the individual rate coefficients of the reactions that govern the FRP encouraged the development of the pulsed laser polymerization (PLP) technique [4]. Since its invention in the late 1980s, PLP-based techniques have substantially improved the quality of the experimental measurements of rate parameters in FRP, particularly for propagation reactions.…”

Section: Introductionmentioning

confidence: 99%

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

2015

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Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP) with growing interest. Nowadays, quantum chemistry (QC) can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

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“…In particular, it exerts a direct influence on the molecular weight of the polymer formed. 9,20 Olaj et al determined that the chain length ͑L O ͒ is given by…”

Section: Storage Of Diffraction Gratingsmentioning

confidence: 99%

“…Olaj et al 9 developed the pulsed-laser polymerization method as a tool for evaluating individual kinetic constants of free-radical polymerization. The free-radical propagation rate coefficients of methyl methacrylate were measured with visible light wavelengths.…”

Section: Introductionmentioning

confidence: 99%

Hologram recording in polyvinyl alcohol/acrylamide photopolymers by means of pulsed laser exposure

et al. 2002

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The variation in transmittance produced when a photopolymer is irradiated with a pulsed laser is analyzed and experimental results obtained when diffraction gratings are stored using pulsed exposure are presented. In either case, the influence of the energy of the irradiation pulse, the number of pulses, and the pulse repetition rate were studied. The photopolymer used was an acrylamide͞polyvinyl alcohol dry film with a yellow eosin-thiethanol-amine mixture as a photoinitiator system. The recording of the gratings was performed by use of a holographic copying process. The samples were exposed and holograms recorded with a collimated beam from a frequency-doubled Nd:YAG ͑532 nm͒ Q-switched laser. Our initial results show that it is possible to obtain diffraction gratings with a diffraction efficiency of 60% and a refractive index modulation up to 2.8 ϫ 10 Ϫ3. The energetic sensitivities achieved are close to those obtained with the same material and continuous irradiation without a preprocessing of the gratings.

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Laser-flash-initiated polymerization as a tool for evaluating (individual) kinetic constants of free-radical polymerization—5. Complete analysis by means of a single experiment

Cited by 125 publications

References 13 publications

Initiation Kinetics in Free‐Radical Polymerization: Prediction of Thermodynamic and Kinetic Parameters Based on ab initio Calculations

Initiation Kinetics in Free‐Radical Polymerization: Prediction of Thermodynamic and Kinetic Parameters Based on ab initio Calculations

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

Hologram recording in polyvinyl alcohol/acrylamide photopolymers by means of pulsed laser exposure

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