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

Liborio I. Costa; Giuseppe Storti; Massimo Morbidelli; Loredana Ferro; Alessandro Galia; Onofrio Scialdone; Giuseppe Filardo

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

机译：VDF和HFP在超临界二氧化碳中的共聚：沉淀和分散动力学建模的可靠方法

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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.

机译：建立了偏二氟乙烯和六氟丙烯在超临界CO_2中异质自由基共聚的动力学模型。该模型考虑了分散相（富含聚合物）相和连续（无聚合物）超临界相中的聚合反应，自由基相间传输，扩散限制以及富聚合物相中依赖链长的终止。制定并详细制定了参数评估策略，以先验估计大多数动力学参数，同时通过直接拟合最小化它们的评估。在不同的单体进料组成，单体浓度，相间面积和系统压力下，所得的模型预测与转化率和MWD的实验结果相比具有优势。

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《Macromolecular reaction engineering》 |2012年第1期|p.24-44|共21页
作者
Liborio I. Costa; Giuseppe Storti; Massimo Morbidelli; Loredana Ferro; Alessandro Galia; Onofrio Scialdone; Giuseppe Filardo;
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作者单位

Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse 10, 8093 Zurich, Switzerland, Polymer Application and Test Center, Sulzer Chemtech, Sulzerallee 48, P.O. Box 65, 8404 Winterthur,Switzerland;

Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse io, 8093 Zurich, Switzerland;

Institute for Chemical and Bioengineering, ETH Zurich, Wolfgang-Pauli-Strasse io, 8093 Zurich, Switzerland;

Dipartimento di Ingegneria Chimica Gestionale Informatica e Meccanica, Universita di Palermo, Viale delle Scienze Ed.6, 90128 Palermo, Italy;

Dipartimento di Ingegneria Chimica Gestionale Informatica e Meccanica, Universita di Palermo, Viale delle Scienze Ed.6, 90128 Palermo, Italy;

Dipartimento di Ingegneria Chimica Gestionale Informatica e Meccanica, Universita di Palermo, Viale delle Scienze Ed.6, 90128 Palermo, Italy;

Dipartimento di Ingegneria Chimica Gestionale Informatica e Meccanica, Universita di Palermo, Viale delle Scienze Ed.6, 90128 Palermo, Italy;

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正文语种 eng
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diffusion; fluoropolymers; heterogeneous polymerization; modeling; supercritical carbon dioxide;

机译：扩散;含氟聚合物;非均相聚合造型;超临界二氧化碳;

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专利

1. The Rate of Polymerization in Two Loci Reaction Systems: VDF-HFP Precipitation Copolymerization in Supercritical Carbon Dioxide [J] . Liborio I. Costa, Giuseppe Storti, Massimo Morbidelli Polymer engineering and science . 2011,第10期

机译：在两个位点反应系统中的聚合速率：超临界二氧化碳中的VDF-HFP沉淀共聚
2. Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: Experimental Analysis of the Reaction Loci [J] . Costa L. Ivano, Storti Giuseppe, Morbidelli Massimo, Macromolecules . 2010,第23期

机译：VDF和HFP在超临界二氧化碳中的共聚反应位点的实验分析
3. Modeling of the homogeneous free-radical copolymerization kinetics of fluoromonomers in carbon dioxide at supercritical conditions [J] . Quintero-Ortega IA, Vivaldo-Lima E, Gupta RB, Journal of Macromolecular Science. Pure and Applied Chemistry . 2007,第1a3期

机译：超临界条件下二氧化碳中含氟单体的均相自由基共聚动力学模型
4. Evaluation of the Performance of a Kinetic Model for Free-Radical Copolymerization of Vinyl/Divinyl Monomers in Supercritical Carbon Dioxide [C] . Irais A. Quintero-Ortega, Pedro R. Garcia-Moran, Gabriel Jaramillo-Soto, US-Mexico Symposium on Advances in Polymer Science . 2009

机译：乙烯基/二乙烯基单体在超临界二氧化碳中的自由基共聚的动力学模型的性能评价
5. Kinetics and mechanisms of the ligand substitution reactions of cyclopentadienyl M tetracarbonyl, indenyl M tetracarbonyl, M = niobium or tantalum, and molybdenum(2) (carbon monoxide)(6) [mu-eta(5),eta(5)-cyclopentadienylide-carbon alkyl(2)-cyclopentadienylide] with tributylphosphine, triphenylphosphine and triphenylphosphite. Photo-assisted carbonylation of supercritical ethane, ethane and methane in supercritical carbon dioxide by trans-chlorocarbonylbis(trimethylphosphine)rhodium(I). [D] . Lukmanova-Kline, Dinara Maratovna. 2001

机译：动力学和机制的环戊二烯基M四羰基，茚基M四羰基，M =铌或钽和钼（2）（一氧化碳）（6）[mu-eta（5），eta（5）-cyclopentadienylide-碳烷基（2）-环戊二烯基]与三丁基膦，三苯基膦和亚磷酸三苯酯。通过反氯羰基双（三甲基膦）铑（I）在超临界二氧化碳中对超临界乙烷，乙烷和甲烷进行光辅助羰基化。
6. Extraction of Triterpenic Acids and Phytosterols from Apple Pomace with Supercritical Carbon Dioxide: Impact of Process Parameters Modelling of Kinetics and Scaling-Up Study [O] . Łukasz Woźniak, Anna Szakiel, Cezary Pączkowski, 2018

机译：用超临界二氧化碳从苹果渣中提取三萜酸和植物甾醇：工艺参数的影响动力学建模和放大研究
7. Copolymerization of VDF and HFP in Supercritical Carbon Dioxide: A Robust Approach for Modeling Precipitation and Dispersion Kinetics [O] . Costa L, Storti G, Morbidelli M, 2012

机译：VDF和HFP在超临界二氧化碳中的共聚：沉淀和分散动力学建模的可靠方法
8. Development of the ANL Plant Dynamics Code and Control Strategies for the Supercritical Carbon Dioxide Brayton Cycle and Code Validation with Data from the Sandia Small-Scale Supercritical Carbon Dioxide Brayton Cycle Test Loop. [R] . A. Sienicki B. Moisseytsev 2011

机译：利用桑迪亚小型超临界二氧化碳布雷顿循环试验环数据开发超临界二氧化碳布雷顿循环和代码验证的aNL工厂动力学规范和控制策略。

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

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