Detailed copolymerization propagation kinetics of homogeneous phase VDF–HFP copolymerization in supercritical CO2

Siegmann, Rebekka; Drache, Marco; Beuermann, Sabine

doi:10.1016/j.jfluchem.2014.01.002

Cited by 10 publications

(25 citation statements)

References 39 publications

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“…k p ijk in Scheme refers to the addition of monomer k to a macroradical consisting of monomer i in the penultimate unit and monomer unit j as terminal unit at the chain end. The penultimate unit model has been applied to numerous copolymerization systems against data obtained by PLP–SEC, e.g., in refs . To describe the copolymerization behavior, six parameters are employed in addition to the homopropagation rate coefficients: r 11 = k p111 / k p112 , r 21 = k p211 / k p212 , s 1 = k p211 / k p111 , r 22 = k p222 / k p221 , r 12 = k p122 / k p121 , and s 2 = k p122 / k p222 .…”

Section: Introductionmentioning

confidence: 99%

“…Previously, it was shown that the combination of pulsed laser initiated polymerization and subsequent analysis of the resulting polymer by size‐exclusion chromatography (PLP–SEC method) allows for the determination of k p copo . After establishing appropriate reaction conditions, k p copo is derived from Equation

L = k_{normalp}^{copo} \cdot c_{normalM} \cdot t

with c M being the monomer concentration, t the time between two subsequent laser pulses, and L the number of propagation steps derived from the point of inflection of the molar mass distribution (MMD).…”

Section: Introductionmentioning

confidence: 99%

“…It has been shown that these data may be estimated applying the principle of universal calibration. For details on the PLP–SEC method, the reader is referred to the cited publications . The determination of L and c M for the IP‐GMA copolymerization system is outlined in the Supporting Information.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Brandl

Drache

Schier

et al. 2017

Macromol. Rapid Commun.

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Pulsed-laser polymerization combined with polymer analysis by NMR and size-exclusion chromatography is used to study the radical copolymerization kinetics of isoprene (IP) with glycidyl methacrylate (GMA). The copolymer is characterized by a close-to-alternating microstructure, with the addition of IP leading to a significant decrease in the composition-averaged propagation rate coefficient. A rigorous fitting strategy is developed to fit a mixed penultimate model to the data, with the selectivity of the IP, but not the GMA, macroradical dependent on the penultimate unit.

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Section: Introductionmentioning

confidence: 99%

L = k_{normalp}^{copo} \cdot c_{normalM} \cdot t

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Brandl

Drache

Schier

et al. 2017

Macromol. Rapid Commun.

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“…Die Kalibrierung erfolgt mit Polystyrol‐Standards (PSS). Absolute Molmassen werden basierend auf dem Prinzip der universellen Kalibrierung berechnet , . Die folgenden Mark‐Houwink‐Parameter werden genutzt: a (PS) = 0,69; K (PS) = 0,013 mL g −1 ; a (PVDF) = 0,68 und K (PVDF) = 0,018 mL g −1 .…”

Section: Experimentellesunclassified

“…Es stellt sich ein Gleichgewicht zwischen wachsenden und schlafenden Polymerketten ein [14]. [17,18]. Die folgenden Mark-Houwink-Parameter werden genutzt: a(PS) = 0,69; K(PS) = 0,013 mL g -1 ; a(PVDF) = 0,68 und K(PVDF) = 0,018 mL g -1 .…”

Section: Introductionunclassified

Semibatch Emulsion Polymerization of Vinylidene Fluoride

Brandl

Beuermann

2018

Chemie Ingenieur Technik

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Die vielseitigen Eigenschaften von Polyvinylidenfluorid ermöglichen ein breites Anwendungsspektrum von der Automobilindustrie bis zur Medizin. Die halbkontinuierliche Emulsionspolymerisation von Vinylidenfluorid wurde untersucht. Die Rührergeschwindigkeit und der Reaktionsdruck wurden variiert, um einen effizienten Eintrag des gasförmigen Monomers in die Reaktionsmischung zu erzielen. Polymere mit enger Molmassenverteilung wurden aus Iodtransferpolymerisationen erhalten. Die Größen der Latexteilchen wurden mittels dynamischer Lichtstreuung und Feldemissionselektronenmikroskopie ermittelt.

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Advanced Kinetic Parameter Fit Applied to Radical Copolymerizations

Hosemann

Drache

Beuermann

2016

Macromolecular Symposia

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Summary The approach used for fitting kinetic coefficients to experimental polymerization data is of minor importance as long as the simulation of the quantities to be compared is sufficiently fast. Whenever the simulation is slowed down, for example due to transfer to polymer reactions involved, the fit has to be performed using as few iteration steps as possible. In this work, the simulation aims for the relation between branching and radius of gyration, therefore the kinetic simulation is coupled with a random walk approach, enlarging the computational demands further. A Markov Chain fit is used, enabling an optimal usage of the resources.

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Detailed copolymerization propagation kinetics of homogeneous phase VDF–HFP copolymerization in supercritical CO2

Cited by 10 publications

References 39 publications

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Propagation Kinetics of Isoprene–Glycidyl Methacrylate Copolymerizations Investigated via PLP–SEC

Semibatch Emulsion Polymerization of Vinylidene Fluoride

Advanced Kinetic Parameter Fit Applied to Radical Copolymerizations

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