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Gabriel Jaramillo‐Soto M. Luz Castellanos‐Crdenas Pedro R. García‐Morn Eduardo Vivaldo‐Lima Gabriel Luna‐Brcenas Alexander Penlidis 《Macromolecular theory and simulations》2008,17(6):280-289
The RAFT radical polymerization of vinyl monomers in supercritical carbon dioxide was modeled using the Predici® simulation package. The sensitivity of polymerization responses on formulation and process variables was analyzed. The simulations were carried out using kinetic and physical parameters corresponding to the polymerization of methyl methacrylate in supercritical carbon dioxide, using AIBN as initiator, at 65 °C and 200 bar, and using values of the addition and fragmentation kinetic rate constants of a “typical” RAFT agent, as reference conditions. This is the first report in the literature addressing the modeling or simulation of RAFT polymerization in supercritical carbon dioxide.
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Shi-Ping Zhan Xing Huang Qi-Cheng Zhao Li Chen Wei-Min Hou Song Zhang 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1070-1074
Dispersion polymerization of lactides and lactones has been studied and has received a great deal of attention used to prepare biodegradable polymers in supercritical carbon dioxide (ScCO2). The triblock copolymers of poly(?-caprolactone) PCL-polydimethylsiloxane (PDMS)-poly(?-caprolactone) PCL by the feed ratio of 1:2:1 and 1:3:1, respectively were synthesized to be used as the stabilizers in the dispersion polymerization of L-lactide. The fine poly(L-lactide) (PLLA) powders were obtained at the concentrations of 3% to 5%w/w (stabilizer/monomer). The results demonstrated that the triblock copolymers were the effective stabilizers for the dispersion polymerization of L-lactide. It was also found that the cooling process had a significant effect on the particle size of the fine powders. In order to obtain the best PLLA powders, it would be necessary to use the cooling process with stirring. 相似文献
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In an attempt to reduce the emission of hazardous VOCs, SCFs have been intensively investigated as alternative solvents during the last two decades. In this study, the application of reaction calorimetry, an efficient tool to obtain kinetic and safety data, is presented on the free radical dispersion polymerization of MMA in scCO2. The effect of three major parameters with respect to the reaction evolution are studied, namely of stirrer type and stirring speed, the monomer and CO2 concentration and the stabilizer concentration. The effective formation of the dispersion as well as the balance between the polymer formed in the continuous phase or inside the particles are key features of this analysis.
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Iraís A. Quintero‐Ortega Gabriel Jaramillo‐Soto Pedro R. García‐Morán M. Luz Castellanos‐Cárdenas Gabriel Luna‐Bárcenas Eduardo Vivaldo‐Lima 《大分子反应工程》2008,2(4):304-320
A comparison of kinetic models for dispersion polymerization of MMA and styrene in supercritical CO2 is presented. The limiting case of solution polymerization, as a simplified case, was also addressed. Calculation of the partition of components between the continuous and dispersed phases was emphasized. Experimental data for the solution and dispersion polymerizations of styrene and MMA, using different types of stabilizers, were used to guide the study. Although all the models analyzed can be considered as “adequate” in representing the behavior of the system, some of their strengths and drawbacks have been highlighted.
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Pedro R. García‐Morán Gabriel Jaramillo‐Soto Martha E. Albores‐Velasco Eduardo Vivaldo‐Lima 《大分子反应工程》2009,3(1):58-70
A study on the effect of process conditions and composition of the reacting mixture on the kinetics and particle properties in the copolymerization of styrene and divinylbenzene in supercritical carbon dioxide is presented. Polystyrene‐block‐polydimethylsiloxane and Krytox 257 FSL (Dupont) were used as stabilizers, and their performance compared. A 38 mL, high‐pressure view cell, equipped with one frontal and two lateral sapphire windows, was used as the reacting vessel. The polymer product was characterized for total monomer conversion, gel content, molecular weight averages of the sol fraction and particle size distribution. Acceptable polymerization rates and partially‐agglomerated spherical particles were produced under the conditions tested.
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Philipp A. Mueller Giuseppe Storti Massimo Morbidelli Charalampos A. Mantelis Thierry Meyer 《Macromolecular Symposia》2007,259(1):218-225
Summary: Experiments of methyl methacrylate dispersion polymerization are carried out in a reaction calorimeter using PDMS-mMA as surfactant. Different stabilizer concentrations from 0 to 10 wt% with respect to monomer have been considered in order to control particle morphology. The analysis by scanning electron microscopy reveals a definite decrease of the total particle surface area at decreasing stabilizer concentration. At the same time, the analysis of the polymer microstructure by gel permeation chromatography shows a trend of the average molecular weight towards smaller values. In particular, a second mode at low molecular weights has been observed leading to bimodal molecular weight distributions. The experimental results are compared with simulation results obtained through a detailed kinetic model developed in previous studies. 1 The key role of the radical exchange between continuous and dispersed phases is confirmed. 相似文献
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本文主要介绍了超临界近5年来超临界二氧化碳中的有机反应研究的最新进展,包括加氢反应、氧化反应、羰基化反应、碳碳键形成反应、酯化反应和酶催化反应的研究现状;同时,还介绍了超临界二氧化碳作为反应底物用于合成碳酸酯和氨基甲酸酯的研究进展;并对未来的发展进行了展望。 相似文献
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Organic reactions in supercritical carbon dioxide (scCO2) have facilitated great progress in recent years . ScCO2, as an environmentally friendly reaction medium, may be a substitute for 1 volatile and toxic organic solvents and show some special advantages. Firstly, CO2 is inexpensive, nonflammable, nontoxic and chemical inert under many conditions. Secondly, scCO2 possesses hybrid properties of both liquid and gas, to the advantage of some reactions involving gaseous reagents. Control o… 相似文献
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A general,green and efficient method for the synthesis of transdiiodoalkenes in CO2(sc) has been developed.Trans-diiodoalkenes were obtained stereospecifically in quantitative yields via diiodination of both electron-rich and electron-deficient alkynes in the presence of KI,Ce(SO4)2 and water in supercritical carbon dioxide [CO2(sc)]at 40℃. 相似文献
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Jun LIU Hong Ping LI Zhi Min LIU Bu Xing HAN* Hai Ke YAN Center for Molecular Science Institute of Chemistry Chinese Academy of Sciences Beijing 《中国化学快报》2001,(5)
Over the past decade there has been a growing interest in using supercritical fluids (SCFs) to promote reactions and to replace hazardous solvents with environmentally benign solvents, such as supercritical CO2 and H2O. Many reactions in SCFs have been studied1, including polymerization in scCO22. It is known that a small change in the pressure near critical point of a fluid causes a significant change in density-dependent properties such as the solubility parameter, viscosity, and dielect… 相似文献
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本文对超临界二氧化碳(ScCO2)中进行的聚合反应进行了综述。评述了ScCO2作为聚合反应介质的优点,以及在ScCO2中可进行的聚合反应类型,包括均相聚合、沉淀聚合、分散聚合、乳液及反相乳液聚合、阳离子聚合、开环聚合、熔融态缩聚、溶液-凝胶聚合、聚合物混合合成、链催化转移聚合、氧化-偶合反应聚合、氮氧自由基可控活性聚合、原子转移自由基聚合、可逆加成-断裂链转移、电化学聚合、原子转移聚合与酶催化开环聚合两种活性聚合在ScCO2中同时聚合、二氧化碳作为原料共聚合等。 相似文献
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Performance degradation under environmental conditions currently limits the practical utility of perovskite-based solar cells. The moisture stability of CH3NH3PbI3 perovskite films and solar cells was measured during exposure to three different levels of relative humidity. The films were crystallized at two different temperatures with and without simultaneous exposure to supercritical carbon dioxide. The film crystallinity, optical absorption, and device photoconversion efficiency was measured over time for three relative humidity levels and both crystallization methods. It was determined that film crystallization in supercritical CO2 resulted in significant improvement in moisture stability for films processed at 50 °C, but negligible improvement in stability for films processed at 100 °C. 相似文献