Dear colleagues, we introduce the promising applications of supercritical fluid technology to polymer relating fields. It develops a stateoftheart overview on polymer fundamentals, polymerization reactions and polymer processing. Supercritical carbon dioxide an overview sciencedirect. Polymer synthesis in supercritical carbon dioxide springerlink. Cellulose acetate and supercritical carbon dioxide. The worlds first, multireaction, supercritical flow reactor was. Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the greening of chemistry. Thermal preoxidation of polyacrylonitrile pan fibers is a timeconsuming and energyconsuming step in the production of panbased carbon fibers. This is the first book emphasizing the potential of supercritical carbon dioxide for polymer processes from an engineering point of view. Fundamentals and applications of supercritical carbon dioxide. Aug 05, 2005 recently, supercritical fluids have emerged as more sustainable alternatives for the organic solvents often used in polymer processes. Solubility in supercritical carbon dioxide crc press book.
This problem can be solved by using supercritical carbon dioxide. Department of chemical engineering, south kensington campus, imperial college london, london, sw7 2az, uk. Read supercritical carbon dioxide in polymer reaction engineering. Chapter 6 kinetics of the homopolymerization of vinylidene fluoride. Homogeneous metalbased catalysis in supercritical carbon dioxide as reaction medium. Pdf chemical reactions in supercritical carbon dioxide. Industrial polymer synthesis using supercritical carbon. Preparation and characterization of microcellular polystyrene. The swelling of a poly methyl methacrylate in supercritical carbon dioxide was studied by means of full atomistic classical molecular dynamics simulation. Green sustainable processes using supercritical fluid.
Final report homogeneous catalysis in supercritical carbon. Supercritical carbon dioxide s co 2 is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure carbon dioxide usually behaves as a gas in air at standard temperature and pressure stp, or as a solid called dry ice when frozen. Supercritical carbon dioxide for green polymer chemistry. Controlledliving radical polymerization in dispersed systems. Supercritical carbon dioxide is also emerging as a useful hightemperature refrigerant, being used in new, cfchfcfree domestic heat pumps making use of the transcritical cycle. Pdf the application of supercritical carbon dioxide in continuous, fixed. Apr 22, 2015 generally, the synthesis of polymer nanocomposites are done using solution chemistry, and this may raise serious concerns regarding air and water pollutions. Jun 06, 2012 plasticisation of plga polymer by supercritical carbon dioxide in the criticalmix process. Abstract this work aimed at studying the efficiency of the use of supercritical carbon dioxide scco2 as a swelling agent to disperse sodium benzoate nabz. Supercritical carbon dioxide for sustainable polymer. Evaluation of polymersupported rhodium catalysts in 1 octene.
Polymers are macromolecules with subunits of monomers that react to form long chains or threedimensional structures. Kemmere process development group, department of chemical engineering and chemistry, eindhoven university of technology, po box 5, 5600 mb eindhoven, the netherlands. The use of supercritical carbon dioxide, instead of water, has been examined as a geothermal working fluid. In order to characterize the polymer swelling, we calculated various properties related to the. The integrated use of supercritical carbon dioxide scco 2 and micro and nanotechnologies has enabled new sustainable strategies for the manufacturing of new medications. Reactions in supercritical carbon dioxide s mayadevi cepd division, csirnational chemical laboratory, pune 411 008, india email. Conventional lipophilic monomers, exemplified by methyl.
Supercritical carbon dioxide scco 2 has been shown to serve as an environmentally benign substitute for a number of solvents that are typically used for freeradical reactions. Supercritical carbon dioxide as a green reaction medium for. Meireles lasefidea department of food engineering, fea school of food engineering, unicamp university of. Preparation and characterization of microcellular polystyrene foams processed in supercritical carbon dioxide kelyn a. Nuu other use, unclassified, pep physical, engineering or chemical process, proc process, uses uses supercrit supercrit. Carbon dioxide in its liquid or supercritical state scco2 has a prodigious potential as an environmentally benign reaction medium for sustainable chemical synthesis. Tokyo, japan and pressurized to a supercritical state in the reaction chamber. Oct 07, 2017 in the video above, professor bob expresses his childlike wonder at the almost magical properties of carbon dioxide as a supercritical solvent. In order to characterize the polymer swelling, we calculated various properties related to the density, structure, and dynamics of polymer chains as a function of the simulation time, temperature, and pressure. The result obtained in this study, which reports the preferential lubricating oil impregnation to the surface of crystalline polymer under supercritical carbon dioxide, suggests that the.
In general, the grafting reaction of gma is performed in a melt state due to its simplicity. Sustainable approaches for materials engineering with. Supercritical carbon dioxide an overview sciencedirect topics. The extensive developments in the fields of polymer science are based on the work and discoveries of hermann staudinger, for which, in 1953, he received the nobel prize for chemistry. Molecular dynamics study of the swelling of polymethyl. Eckertspecific intermolecular interaction of carbon dioxide with polymers.
Encapsulation of food compounds using supercritical. The study on af modification in scco 2 processing by an interfacial reaction between glycidylposs and the polar groups on af surface has not yet been. Carbon dioxide is widely used as the solvent of choice for applications such as caffeine and nicotine extraction due to its mild critical temperature, nontoxicity. The process relies on rapid expansion of the clay followed by direct injection into the extruder where the mixture is dispersed into the polymer melt. Polymer extrusion with scco2 chemical modification of polymers in scco2 reduction of residual monomer in latex products using highpressure co2 kemmere and meyer, supercritical carbon dioxide in polymer reaction engineering, wileyvch. View enhanced pdf access article on wiley online library html view. Free radical homopolymerization experiments were conducted with 2methylene1,3dioxepane in supercritical carbon dioxide scco2 using a heterogeneous precipitation polymerization method and aibn. There is also increasing evidence that the application of. Aug 14, 2014 supercritical carbon dioxide scco 2 could be one aspect of a significant and necessary movement towards green chemistry, being a potential replacement for volatile organic compounds vocs. Final report homogeneous catalysis in supercritical. Dispersion polymerizations in supercritical carbon dioxide j. As a nontoxic and environmentally benign green solvent, it has been widely used in the food and pharmaceutical industries for extraction. Carbon dioxide is an environmentally friendly fluid that can be used to replace hazardous or organic. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form.
Owing to the high mass transfer, low viscosity, and low toxicity profile, the supercritical carbon dioxide can be potentially used in polymer processing, which also overcomes the trommsdorff effect. The use of supercritical co2 as a reaction medium, monomer, and catalyst for the synthesis of mostly polycondensation polymers is analyzed. Green scco 2based methodologies are well suited to improve either the synthesis or materials processing leading to the assembly of threedimensional multifunctional constructs. Fluoroacrylate copolymersupported rhodium catalysts for. An improved technique for exfoliating and dispersing. Sep 18, 2006 read supercritical carbon dioxide in polymer reaction engineering. Immediately, the green method using supercritical carbon dioxide scco2 has grabbed the attention of researchers who are responsible to synthesize polymer composites by non. Free radical copolymerization reactions of vinylidene fluoride vdf and hexafluoropropylene hfp were carried out in supercritical carbon dioxide at t 50 c. Green polymer chemistry, biodegradable and renewable polymers, biocatalysts for polymerisations i. It develops a stateoftheart overview on polymer fundamentals, polymerization reactions and polymer processing in supercritical carbon dioxide. Industrial polymer synthesis using supercritical carbon dioxide. Polymerization of vinylidene fluoride in supercritical. Supercritical carbon dioxide scco 2 not only has great solubility and permeability, but also has a relatively high diffusion coefficient, which caused the polymers and fibers to bulge 8,12.
Unfortunately, carbon dioxide has a notoriously poor solubilising power and is famously difficult to handle. Chapter 7 polymer synthesis in supercritical carbon. Copolymerization of vdf and hfp in supercritical carbon. Supercritical carbon dioxideassisted process in synthesis of. Supercritical carbon dioxide scco2 is carbon dioxide that is held beyond supercritical conditions of 31. Carbon dioxide is an attractive solvent alternative for the synthesis of polymers.
Applications of supercritical carbon dioxide as an antisolvent. Selective free radical reactions using supercritical carbon dioxide. Supercritical carbon dioxide is an attractive alternative solvent in place of traditional organic. First, the key themes explored in this thesis are outlined. Solubility in supercritical carbon dioxide crc press book supercritical fluid extraction is an environmentally safe and costeffective alternative to traditional organic solvents. In this work, two supercritical carbon dioxide scco 2 based techniques, such as the semicontinuous supercritical antisolvent process sas and the supercritical fluid phase inversion process, in which scco 2 plays the role of antisolvent, were employed. Hydroformylation of styrene in supercritical carbon dioxide with fluoroacrylate polymer supported rhodium catalysts. For the first time stabilizer free supercritical carbon dioxide scco2 was used as a reaction medium. It is current opinion of most of the people involved in supercritical fluids scfs technology that as the end of the twentieth century has been devoted to enlarge exploitation of compressed gases in separation processes the beginning of the twentyfirst will be mainly aimed to improve their utilisation as solvents for reactions. E dispersion polymerizations supercritical carbon dioxide.
Journal of the american chemical society, 118 1996, pp. The influence of amine oxide catalysis has been investigated in the dispersion polymerisation of 2,4toluenediisocyanate with 1,4butanediol in supercritical carbon dioxide. Transport properties of supercritical carbon dioxide core. Fundamentals and applications of supercritical carbon dioxide sco2 based power cycles aims to provide engineers and researchers with an authoritative overview of research and technology in this area. Polymer plasticisation by supercritical carbon dioxide. Polymers free fulltext study on surface properties of. Mccarthy polymer science and engineering department, university of massachusetts, amherst, massachusetts 01003.
When ammonium carboxylate perfluoropolyether surfactants were used, the formation of polymer particles was observed provided that hfp mole fraction in the feed was not larger than 0. Recently, supercritical fluids have emerged as more sustainable alternatives for the organic solvents often used in polymer processes. Supercritical carbon dioxide can be removed easily from the polymer solution by depressurization during drying of the polymer. Toward upscaled biocatalytic preparation of lactone building blocks for polymer applications. Supercritical carbon dioxide in polymer reaction engineering.
Supercritical carbon dioxide is a promising green alternative to traditional solvents in polymer synthesis due to gaslike transport properties and liquidlike solubility. Encapsulation of food compounds using supercritical technologies. In addition, the improved product quality is also an important concern for its selection 14. We determined that the catalyst is soluble in supercritical carbon dioxide and. Kinetics and mechanism for the reaction of hexafluoroacetylacetone with cuo in supercritical carbon dioxide. University of groningen polymer melt micronisation using.
Supercritical fluids produce practically solventfree products and avoid deteriorating reactions. However, formatting rules can vary widely between applications and fields of interest or study. Supercritical carbon dioxide as a green solvent for processing polymers 3 extraction applications and in polymer synthesis 14. Pdf supercritical carbon dioxide and polymers researchgate. Supercritical fluids especially supercritical carbon dioxide scco 2 is an attractive medium for the synthesis of nanostructured materials due to its favorable properties such as being abundant. Carbon dioxide usually behaves as a gas in air at standard temperature and pressure stp, or as a solid called dry ice when frozen. Supercritical carbon dioxide as a green reaction medium.
Homogeneous phase polymerization of vinylidene fluoride in supercritical carbon dioxide. Supercritical carbon dioxide one of the supercritical fluids, which can be used, is carbon dioxide co2. Supercritical carbon dioxide for sustainable polymer processes dr. Unilab research center of chemical reaction engineering, state key laboratory of chemical engineering, east china university of science and technology, shanghai 200237, china.
In this paper, the effect of temperature on the structures and properties of pan fibers cyclized in the supercritical carbon dioxide scco2 medium was studied. An environmentally benign process, which uses supercritical carbon dioxide scco 2 as a processing aid, is developed in this work to help exfoliate and disperse nanoclay into the polymer matrices. About 20 years ago the first polymerization process using supercritical carbon dioxide was. Meireles lasefidea department of food engineering, fea school of food engineering, unicamp university of campinas, campinas, brazil. Chemical reactions in supercritical carbon dioxide. Supercritical carbon dioxide is an attractive alternative in place of traditional organic solvents. Also, with supercritical co 2, dry polymers can be easily made by merely depressurizing the reactor after polymerization 9, 10. Engineering and technology institute groningen enteg, chemical product. Characterization of engineering plastics plasticized using. Carbon dioxide that is maintained beyond supercritical conditions at 31. Varying the kind of organic solvent used to prepare the polymeric solution, the polymer. Polymer production and processing using supercritical.
Applications of supercritical carbon dioxide in materials. Although co 2 is a greenhouse gas, if it is withdrawn from the environment, used in a process, and then returned to the environment, it does not contribute to the greenhouse effect. Pdf the application of supercritical carbon dioxide in continuous, fixed bed. Pdf molecular glass resists developable in supercritical. Supercritical carbon dioxide s co 2 is a fluid state of carbon dioxide where it is held at or above its critical temperature and critical pressure. Plga is a polymer widely used for drug delivery and as the carbon dioxide becomes supercritical, the.
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