Simulation of RAFT Dispersion Polymerization in Supercritical Carbon Dioxide

Jaramillo‐Soto, Gabriel; Castellanos-Cárdenas, M. Luz; García-Morán, Pedro R.; Vivaldo‐Lima, Eduardo; Luna‐Bárcenas, Gabriel; Penlidis, Alexander

doi:10.1002/mats.200800006

Cited by 19 publications

(28 citation statements)

References 44 publications

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“…Modeling studies on RAFT polymerization have been carried out widely with different methods 6–23. Using the method of moment, Wang and Zhu developed a kinetic model for RAFT polymerization predicting the monomer conversion, average molecular weight, and polydispersity of polymer chains 20, 24.…”

Section: Introductionmentioning

confidence: 99%

“…Monteiro gave a detailed description of RAFT process in which all possible reactions from initiation to four‐arm star formation were included, to provide a comprehensive analysis of influencing factors on the chain growth and polydispersity 16, 25. Besides the method of moment, a program package PREDICI® was also employed for the simulation of RAFT process 9, 13, 17, 19, 23, 26, 27. Monte Carlo method, a popular method for polymerization simulation, has also been employed for the modeling research on RAFT polymerization 8, 11, 18…”

Section: Introductionmentioning

confidence: 99%

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Modeling analysis of chain transfer in reversible addition‐fragmentation chain transfer polymerization

Gao

Zhu

2011

J of Applied Polymer Sci

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The validity of simplifying the reversible addition-fragmentation chain transfer (RAFT) polymerization as a degenerative chain transfer process was verified in this work. The simplified chain transfer mechanism enabled the direct modeling investigation of chain transfer coefficient in the RAFT polymerization. It also gave the analytical expressions for concentration, chain length, and polydispersity of various chain species. The comparison between the simulations based on chain transfer mechanism and those from general RAFT mechanism showed that this simplified mechanism can accurately predict RAFT polymerization in the absence of side reactions to adduct radicals other than fragmentation. However, significant errors are introduced at high conversion when side reactions to adduct are present. The chain transfer coefficient of RAFT agent is the key factor in RAFT polymerization. The polydispersity is more sensitive to chain transfer coefficient at low conversion. At high conversion, however, the polydispersity is mainly determined by termination, which can be controlled by RAFT agent concentration and the selection of initiator. At last, an analytical equation is derived to directly estimate chain transfer coefficient of RAFT agent from the experimental data.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modeling analysis of chain transfer in reversible addition‐fragmentation chain transfer polymerization

Gao

Zhu

2011

J of Applied Polymer Sci

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“…This goal is achieved by comparing the experimentally measured reaction rates of VDF and HFP precipitation copolymerization reactions in scCO 2 , with calculations carried out using a detailed and comprehensive two‐loci model and the simplified one‐locus models used by Ahmed et al [22]. Among the many proposed two‐loci models [23–27], the one recently proposed by Costa et al [17, 18] is used here because already successfully applied to the system under examination.…”

Section: Introductionmentioning

confidence: 99%

The rate of polymerization in two loci reaction systems: VDF‐HFP precipitation copolymerization in supercritical carbon dioxide

Costa

Storti

Morbidelli

et al. 2011

Polymer Engineering & Sci

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When the copolymerization of vinylidene fluoride (VDF) and hexafluoropropylene (HFP) is carried out in supercritical carbon dioxide (scCO 2) under heterogeneous conditions, the reaction occurs both in the continuous CO 2-rich phase and in the dispersed polymer-rich phase. The two phases being characterized by different values of reactant concentrations and kinetic parameters, one would expect that the reaction kinetics is affected by the polymer phase holdup in the reactor. However, the reaction rate is almost insensitive to the amount of produced polymer, at least at specific reaction conditions. This apparent contradiction is discussed and clarified in this paper by a series of comparative simulations carried out using different models, accounting for the reaction in one single phase (one-locus) or in two phases (two-loci). This analysis provides general procedures which can be used to design experimental investigations able to identify the number of reaction loci for a given heterogeneous polymerization system. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers

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“…Nevertheless, such drawback is somehow counterbalanced by the easy recovery of very pure polymer by simple depressurization at the end of the reaction, without any need of polymer purification steps. Many papers and reviews have been published addressing the main features of the polymer/scCO 2 thermodynamics,2, 3 as well as those of polymer synthesis, modeling of polymerization kinetics, and polymer processing in scCO 2 4–11…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics

Costa¹,

Storti²,

Morbidelli³

et al. 2011

Macro Reaction Engineering

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A kinetic model is developed for the heterogeneous free-radical copolymerization of vinylidene fluoride and hexafluoropropylene in supercritical CO 2. The model accounts for polymerization in both the dispersed (polymer-rich) phase and in the continuous (polymer-free) supercritical phase, for radical interphase transport, diffusion limitations, and chain-length-dependent termination in the polymer-rich phase. A parameter evaluation strategy is developed and detailed to estimate most of the kinetic parameters a priori while minimizing their evaluation by direct fitting. The resulting model predictions compare favorably with the experimental results of conversion and MWD at varying monomer feed composition, monomer concentration, interphase area, and pressure of the system. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Simulation of RAFT Dispersion Polymerization in Supercritical Carbon Dioxide

Cited by 19 publications

References 44 publications

Modeling analysis of chain transfer in reversible addition‐fragmentation chain transfer polymerization

Modeling analysis of chain transfer in reversible addition‐fragmentation chain transfer polymerization

The rate of polymerization in two loci reaction systems: VDF‐HFP precipitation copolymerization in supercritical carbon dioxide

Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics

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