• Clean Technology
• /
• v.18 no.2
• /
• pp.123-143
• /
• 2012

Supercritical fluid technology (SFT) is recently one of the most new techniques, which has been interested various fields of related chemical industries. SFT is the most effective and practical technology with eco-friendly, energy-savings, and high efficiency as the technique using the advantages of supercritical fluid such as high solvation power, solubility, mass transfer rate, and diffusion rate. Especially, it is necessary to analyze, evaluate, and develop the potential of application techniques using SFT with these characterizations. Therefore in this review, the phase behavior in supercritical fluid at high temperature and pressure of monomers/polymers for the optimization of polymerization process are briefly described, and the preparation of molecularly imprinted polymers (MIPs) in supercritical fluid using supercritical polymerization and the performance evaluation of MIPs are introduced.

• Polymer(Korea)
• /
• v.35 no.4
• /
• pp.284-288
• /
• 2011

For the purpose of the pre-industry production of poly(L-lactide) (PLLA) and full understanding of the supercritical polymerization system, large scale polymerization of L-iactide initiated by 1-dodecano/stannous 2-ethyl-hexanoate (DoOH/Sn(Oct)$_2$) was carried out in supercritical chlorodifluoromethane under various reaction conditions (time, temperature and pressure)and reactants (monomer and supercritical solvent) concentrations. A 3 L sized-reactor system was used throughout this study. The monomer conversion increased to 72% on increasing reaction time to 5 h. The molecular weight of PLLA product also increased to 68000 g/moi over the same period. An increase in monomer concentration resulted in a higher molecular weight, up to 144000 g/mol and 97% of monomer conversion. Raising the reaction pressure from 130 to 240 bar also resulted in an increased monomer conversion and molecular weight. To increase heat resistivity of PLLA, methanol treatment and heat-vacuum methods were evaluated. Both of them successfully improved the heat resistivity property of PLLA.

• Macromolecular Research
• /
• v.16 no.2
• /
• pp.120-127
• /
• 2008

Glycidyl methacrylate linked poly(dimethylsiloxane) (GMA-PDMS) was synthesized and used as a stabilizer for the dispersion polymerization of methyl methacrylate (MMA) in supercritical $CO_2$. This study examined the effect of the concentrations of the stabilizer, 2,2'-azobisisobutyronitrile (AIBN) initiator, and MMA on the yield, molecular weight, and morphology of the poly(methyl methacrylate) (PMMA) product. PMMA was obtained in 94,6% yield using only 0,87 wt% GMA-PDMS, When the AIBN concentration was increased from 025 to 1.06 wt%, the molecular weight and particle size of the PMMA decreased from 56,600 to 21,600 and from 4.1 to $2.7{\mu}m$, whereas the particle size distribution increased from 1.3 to 1.9. The $M_n$ of the PMMA product ranged from 41,600 and 55,800 under typical polymerization conditions. The PMMA particle diameter ranged from 1.8 to $11.0{\mu}m$ and the particle size distribution ranged from 1.4 to 1.8.

• Clean Technology
• /
• v.12 no.2
• /
• pp.62-66
• /
• 2006

Poly($\small{L}$-Lactide)(PLLA) was prepared by a ring-opening polymerization of $\small{L}$-Lactide with various polydimethylsiloxane(PDMS) based copolymers as a stabilizer in supercritical carbon dioxide($scCO_2$). The block copolymeric stabilizers were synthesized by group transfer polymerization (GTP) by using PDMS macroinitiator. PLLA was found to be produced with fairly low molecular weight distribution as confirmed by gel permeation chromatography(GPC) analysis. Scanning electron microscopy (SEM) results showed that sub-micron size Poly($\small{L}$-lactide)(PLLA) particles were formed by suspension polymerization.

• Korean Chemical Engineering Research
• /
• v.43 no.1
• /
• pp.21-26
• /
• 2005

Experimental researches on the preparation of porous polymeric monoliths in supercritical carbon dioxide have been performed and the effects of monomer and polymerization parameters on the physical properties of the monolith prepared were examined. Polymerizations were carried out in the high pressure stainless steel reactor with sapphire window to show the phase change during the polymerization reaction, and continuous and dry porous monolithic polymer could be obtained. The specific surface area of monolithic polymer increased with monomer contents in reaction mixture and reaction pressure. The Rockwell hardness could be enhanced by the addition of co-monomer MMA in reaction mixtures.

• Clean Technology
• /
• v.12 no.4
• /
• pp.191-197
• /
• 2006

Polymerization in supercritical carbon dioxide has been getting attention since it is easier to separate the remaining reactants from product polymer and since it is a cleaner process that produces neither wastewater nor air pollutants, compared to the conventional polymerization processes. In this study, poly(vinyl acetate) (PVAc) that is necessary in producing poly(vinyl alcohol) (PVA) with a lot of industrial applications was manufactured in the presence of supercritical carbon dioxide for the second time in the world. A poly(dimethylsiloxane)(PDMS)-derivative surfactant and three initiators were employed in the polymerization of vinyl acetate (VAc) at 338.15 K and 34.5 MPa. Investigation was carried out to find out the effect of the amounts and types of initiators and surfactants as well as the effect of reaction time on the yield and the molecular weight of PVAc. The weight average molecular weight (Mw) of PVAc was in the range of 60,000 ~ 140,000 g/mol, and the number average molecular weight was in the range of 30,000 ~ 70,000 g/mol. The yield of PVAc was spread over 10 ~ 80%, based on the amount of VAc monomer.

• Journal of the Society of Cosmetic Scientists of Korea
• /
• v.36 no.1
• /
• pp.17-32
• /
• 2010

This review shows the design and the development of new $CO_2$-soluble hydrocarbon copolymers which can be used as effective stabilizers for successful dispersion polymerizations of bio-compatible materials in supercritical carbon dioxide ($scCO_2$). The basic concepts of supercritical fluid including its solvent properties and applications in polymer synthesis are described. We report the facile synthesis of highly soluble hydrocarbon based copolymers, prepared with good control via controlled free radical polymerization from readily accessible and commercially available monomers. The phase behaviour of these materials was monitored in pure $CO_2$ to investigate how the molecular weights and the composition of the copolymers affect their solubility in $CO_2$. Their activity as a stabilizer was then tested in dispersion polymerization of N-vinyl pyrrolidone in $CO_2$ at various reaction conditions to identify the key parameters required for a successful dispersion stabilization of growing PVP particles. Some prospective potentials of this research which can be applied in developing new polymer materials in an environmentally-friendly fashion for use in cosmetics are also discussed.

• Journal of Environmental Science International
• /
• v.13 no.3
• /
• pp.319-325
• /
• 2004

An experimental study on the preparation of monolithic porous polymers by environmentally friend process in supercritical carbon dioxide has been carried out. Polymerization mixture composed of a cross-linking monomer, initiator and functional co-polymer was charged in the reactor with sapphire window. After the system was purged with a flow of $CO_2$ for 15 min, the reactor was pressurized with liquid $CO_2$ up to 100 bars. The reactor was isolated from and placed back to the system via quick connector for shaking until the mixture had become fully homogeneous. The reactor was then heated and pressurized to the required reaction conditions and left overnight. After cooling and $CO_2$ evacuation, the polymer was removed from the reactor as dry, white, continuous monoliths. The effect of experimental conditions on the physical properties of porous polymer was systematically examined, and it was found that monomer content had a major effect on the physical properties of the polymers.

• Elastomers and Composites
• /
• v.34 no.4
• /
• pp.350-359
• /
• 1999

Conversion and oil-yield of a used automotive tire sample in supercritical decomposition and extraction for three solvents such as water, 28% ammoina solution and ammonia, were compared. Supercritical extraction with ammonia gave the highest conversion and oil-yield at the same temperature and pressure. In this paper, supercritical ammonia was used as major solvent and tetralin acting as hydrogen-donor, was used as cosolvent. As the amount of tetralin increased, oil-yield was Increased. When a tire sample was extracted by supercritical ammonia, oil-yield was 48.8% at $280^{\circ}C$, 22.3MPa. But when the weight ratio of tetralin to tire sample (weight of tetralin/weight of tire sample) was 5, oil-yield was 61.2% at $280^{\circ}C$ and 22.3 MPa. These phenomena indicate that as radicals produced in supercritical decomposition become stable, the polymerization and the second decomposition of products may be inhibited. Supercritical extraction of a tire sample swollen by tetralin gave high oil-yield although the amount of tetralin was a little.

• Macromolecular Research
• /
• v.17 no.1
• /
• pp.51-57
• /
• 2009

Using glycidyl methacrylate-linked poly(dimethylsiloxane), methyl methacrylate was polymerized in supercritical $CO_2$. The effects of $CO_2$ pressure, reaction time, and mixing on the yield, molecular weight, and molecular weight distribution (MWD) of the poly(methyl methacrylate) (PMMA) products were investigated. The shape, number average particle diameter, and particle size distribution (PSD) of the PMMA were characterized. Between 69 and 483 bar, the yield and molar mass of the PMMA products showed a trend of increasing with increasing $CO_2$ pressure. However, the yield leveled off at around 345 bar and the particle diameter of the PMMA increased until the pressure reached 345 bar and decreased thereafter. With increasing pressure, MWD became more uniform while PSD was unaffected. As the reaction time was extended at 207 bar, the particle diameter of PMMA decreased at $0.48{\pm}0.03%$ AIBN, but increased at 0.25% AIBN. Mixing the reactant mixture increased the PMMA yield by 18.6% and 9.3% at 138 and 207 bar, respectively.