Zur polymerisation von methylmethacrylat bis zu hohen umsätzen: Experimentelle untersuchungen zur theorie des trommsdorff‐effektes nach cardenas und o'driscoll

Panke, Dietrich; Stickler, Manfred; Wunderlich, Winfried

doi:10.1002/macp.1983.021840118

Cited by 46 publications

(2 citation statements)

References 27 publications

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“…The algorithmic choices in Figure are studied for NMP of styrene in batch and considering semibatch reactor operation (Case studies 1 and 2, batch FRP of MMA (Case study 3), and PLP of n -butyl acrylate (Case study 4), according to the reaction schemes included in Tables S1–S3 in the Supporting Information. The related (intrinsic) kinetic parameters are also listed in these tables and are all taken from the literature. ,,,,− Note that in Case study 4, we do not use the most recent parameters for photodissociation, backbiting, tertiary propagation, and β-scission , to enable a better link with short-long termination as studied in Marien et al…”

Section: Kinetic Monte Carlo Modeling Detailsmentioning

confidence: 99%

Roadmap for Monomer Conversion and Chain Length-Dependent Termination Reactivity Algorithms in Kinetic Monte Carlo Modeling of Bulk Radical Polymerization

Smit

Marien

Edeleva

et al. 2020

Ind. Eng. Chem. Res.

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Radical polymerization is prone to diffusional limitations on termination, leading to a rate acceleration by the gel-effect and molecular changes, with strong increases in average chain length in free radical polymerization (FRP) and improvement of the end-group functionality in reversible deactivation radical polymerization. What complicates the correct implementation of the termination rates in kinetic modeling studies is (i) the chain length and monomer conversion dependence of the individual (apparent) termination rate coefficients (k t,app,ij values; i,j: chain length) and (ii) the wide variations in macroradical chain length distribution (CLD) types and shapes along the polymerization and upon altering the reaction conditions, including variations in CLD modality and broadness. In this work, we compare four major kinetic Monte Carlo modeling algorithms to sample termination reaction events in bulk radical polymerization, using literature k t,app,ij values. We present a roadmap allowing one to select the most suited algorithm depending on the radical polymerization technique and reaction conditions, therefore opening the pathway to more correct representations of chain length and monomer conversion dependencies in radical polymerization. Case studies are related to bulk nitroxide-mediated polymerization, FRP, and pulsed laser polymerization, following an increasing complexity in the active macroradical CLD type and shape.

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Section: Kinetic Monte Carlo Modeling Detailsmentioning

confidence: 99%

Roadmap for Monomer Conversion and Chain Length-Dependent Termination Reactivity Algorithms in Kinetic Monte Carlo Modeling of Bulk Radical Polymerization

Smit

Marien

Edeleva

et al. 2020

Ind. Eng. Chem. Res.

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“…Letting f be the efficiency factor, one can write Thus, the efficiency factor f of the macroradicals is roughly equal to 0.2. Such a value can be compared to those of micromolecular peroxide initiators like lauryl peroxide 28 (f ) 0.65). The lower efficiency of MI 2 is a classical behavior of peroxide-type macroinitiators 29 compared to similar micromolecular compounds, because radical pairs formed after scission of macroinitiator scissile bonds tend to recombine or disproportion- ate due to slow diffusion out of the cage.…”

Section: Thermodynamics Of the Transfer Reactionmentioning

confidence: 99%

Chain Transfer by the Addition-Fragmentation Mechanism. 6. Radical Polymerization toward the Synthesis of End-Functional Telomers, Macroinitiators, and Block Copolymers

Colombani¹,

Zink²,

Chaumont³

1996

Macromolecules

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Acetal-or peroxyketal-terminated oligomers were prepared via a powerful process and characterized. Methanolysis of alkoxy(oxiranyl)-terminated or peralkoxy(oxiranyl)-terminated precursors were used to obtain the desired structures through an addition-substitution evolution on new chain transfer agents, 3-(cumylperoxy)-3-OY-2-phenyl-1-propene (see Chart 1) with Y ) Me (CPMPP), Y ) Et (CPEPP), and Y ) OCMe2Ph (dCPPP). The free radical polymerization of methyl methacrylate (MMA), styrene (St), and methyl acrylate (MA) in the presence of such peroxyketals and precipitation of the polymer in methanol afforded directly the end-functional polymers. Chain transfer constants (Ctr) for these compounds in the monomer polymerization at 60°C were determined from measurements of degrees of polymerization. Ctr values for CPMPP were determined to be 0.49, 0.92, and 1.94 in MMA, St, and MA, respectively. CPMPP behaves as an ideal transfer agent for styrene at temperatures close to 60°C. The chain transfer activation energies, Ea,tr, for the reactions of PS and PMMA radicals with CPMPP were estimated to be 46.0 and 12.4 kJ‚mol -1 , respectively. The thermolysis activation energies of these peroxyketals, Ea,th ) 134.7 and 127.7 kJ‚mol -1 , respectively, to CPMPP and dCPPP were calculated from the Arrhenius plot of the homolytic decomposition rate constants, kth, at various temperatures. dCPPP was used to design a monofunctional macroinitiator, a precursor of diblock copolymers.

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Kinetics of Radical Polymerization

Russell¹

2010

Encyclopedia of Polymer Science and Technology

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This contribution expounds the principles of radical polymerization (RP) kinetics. It emphasizes the defining population‐balance equations and shows how everything springs from them. As far as possible, an equation‐ rather than modeling‐based approach is advocated, because this provides much greater understanding of kinetics. Numerous examples in support of this philosophy are presented. The treatment covers both steady‐state and nonsteady‐state polymerization and also presents some of the extra considerations involved in acrylate polymerization, copolymerization, and emulsion polymerization. Methods for measuring the values of rate coefficients are naturally elucidated in the wider context of RP kinetics in general. The strengths and limitations of equations and methods are made clear. It is argued that very little defies explanation when proper attention is given to the necessary fundamentals.

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Zur polymerisation von methylmethacrylat bis zu hohen umsätzen: Experimentelle untersuchungen zur theorie des trommsdorff‐effektes nach cardenas und o'driscoll

Abstract: Bei der Definition von kt halten wir uns an die im Angelsachsischen ubliche Beziehung fur die Abbruchgeschwindigkeit R, = 2kt[p7'.

Cited by 46 publications

References 27 publications

Roadmap for Monomer Conversion and Chain Length-Dependent Termination Reactivity Algorithms in Kinetic Monte Carlo Modeling of Bulk Radical Polymerization

Roadmap for Monomer Conversion and Chain Length-Dependent Termination Reactivity Algorithms in Kinetic Monte Carlo Modeling of Bulk Radical Polymerization

Chain Transfer by the Addition-Fragmentation Mechanism. 6. Radical Polymerization toward the Synthesis of End-Functional Telomers, Macroinitiators, and Block Copolymers

Kinetics of Radical Polymerization

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