• Clean Technology
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• v.11 no.3
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• pp.117-122
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• 2005

N-vinyl caprolactam (NVCL), a kind of N-vinyl amide monomer, must be dissolved in continuous phase ($scCO_2$) for dispersion polymerization in supercritical carbon dioxide. Phase behavior of $CO_2$+NVCL is very important and necessary for determining initial polymerization condition and for monomer extraction from final polymer. There is the limitation of experimental method for obtaining pure properties of the monomer because of the possibility of polymerization. And N-methyl caprolactam (NMCL) is the useful solvent for the gas treating process. In the viewpoint of molecular thermodynamics, NVCL and NMCL have same functional group i.e. ${\varepsilon}$-caprolactam. In the case of NVCL, hydrogen of amide group is substituted with vinyl group and for NMCL, hydrogen of amide group is substituted with methyl group. We suggested modified group contribution method for this ${\varepsilon}$-caprolactam derivatives. This new group contribution parameter was applied to correlate $CO_2$ + N-vinyl caprolactam or N-methyl caprolactam system.

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

• Clean Technology
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• v.10 no.3
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• pp.149-158
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• 2004

Supercritical carbon dioxide is often promoted as an environmentally friendly solvent having useful properties for a wide range of technical and chemical processes. But the limited ability of $CO_2$ to dissolve polar or non-volatile compounds represents a major drawback in many processes, because the key components will often fail to form homogeneous solution under practical conditions. The design of $CO_2$ soluble ($CO_2$-philic) surfactant to aid this process is therefore paramount in these areas, which has advanced the "greening" of demanding yet important applications in dyeing, cleaning of fibers and texiles, polymerization and polymer processing, photoresist removal, electroplating, and chemical synthesis.

• Korean Chemical Engineering Research
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• v.47 no.4
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• pp.453-458
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• 2009

Recently, new methods to synthesize and process polymers without toxic organic solvents are needed in order to solve environmental problems. The use of supercritical carbon dioxide as a solvent for the polymer synthesis is attractive since it is non-toxic, non-flammable, naturally abundant, and the product may be easily separated from the solvent. In this study, we developed the method using super critical $CO_2$ to prepare P(MAA-co-EGMA) hydrogel nanoparticles as an intelligent drug delivery carrier. The effects of concentrations of PtBuMA-PEO as a dispersion stabilizer and AIBN as an initiator on the particle synthesis were investigated. When PtBuMA-PEO concentration increased, the particle size decreased. However, there was no significant difference in the particle size according to the AIBN concentration. There was a drastic change of the equilibrium weight swelling ratio of P(MAA-co-EGMA) hydrogel nanoparticles at a pH of around 5, which is the $pK_a$ of PMAA. At a pH below 5, the hydrogels were in a relatively collapsed state but at a pH higher than 5, the hydrogels swelled to a high degree. In release experiments using Rh-B as a model solute, the P(MAA-co-EGMA) hydrogel nanoparticles showed a pH-sensitive release behavior. At low pH(pH 4.0) a small amount of Rh-B was released while at high pH(pH 6.0) a relatively large amount of Rh-B was released from the hydrogels.

• Journal of the Korean Wood Science and Technology
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• v.43 no.3
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• pp.355-363
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• 2015

Asian lignin was efficiently depolymerized with supercritical ethanol and Ru/C catalyst at various reaction temperature (250, 300, and $350^{\circ}C$). Lignin-oil was subjected to several physicochemical analyses such as GC/MS, GPC, and elemental analysis. With increasing reaction temperature, the yield of lignin-oil decreased from 89.5 wt% to 32.1 wt%. The average molecular weight (Mw) and polydispersity index (Mw/Mn) of lignin-oil obtained from $350^{\circ}C$ (547Da, 1.49) dramatically decreased compare to those of original asian lignin (3698Da, 2.68). This is a clear evidence of lignin depolymerization. GC/MS analysis revealed that the yield of monomeric phenols involving guaiacol, 4-ethyl-phenol, 4-methylguaiacol, syringol, and 4-methysyringol increased with increasing reaction temperature, and these were mostly produced with applying hydrogen gas and Ru/C catalyst (76.1 mg/g of lignin). Meanwhile, the carbon content of lignin-oil increased whereas the oxygen content decreased with increasing reaction temperature, suggesting that hydrodeoxygenation was significantly enhanced at higher temperature.

• Polymer(Korea)
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• v.35 no.1
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• pp.66-71
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• 2011

With the synthesis of hyper crosslinked polymer particle (HCPP), having microporous structure with hydroxyl functional group, synthesized via polymerization reaction consists of three stepssuspension polymerization, hyper crosslinking by Friedel-Craft catalysis and hydrolysis reaction, the effects of the ratio of each monomer, hyper crosslinking conditions and $CO_2$ supercritical drying on the variations of surface morphology, pore size & distribution and BET surface area of HCPP have been investigated. It was observed that the formation of surface crack or fracture of HCPP was intimately related with the degree of hyper crosslinking reaction between microphase separated domains. And the value of BET surface area of HCPP increased with the increase of reaction temperature, time and the amounts of solvent used in hyper crosslinking step. Moreover, $CO_2$ supercritical drying was proven to be a very effective method for removing stabilizer, unreacted monomers and oligomers from HCPP but needed to add methanol as a co-solvent for efficient removing of residual catalyst.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.11a
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• pp.13.1-13.1
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• 2009

에어로젤은 인류가 개발한 소재 중에서 가장 가벼운 고체로, 기공률이 90%이상이고 비표면적은 ~1000m2/g, 기공의 크기는 10nm 크기로 이루어진 나노기공 물질이다. 1931년에 Kisley가 물유리로부터 실리카 에어로젤을 합성한 이래로 실리카 에어로젤에 대한 연구가 가장 많이 이루어져왔으며, 단열소재, 흡음재, 체렌코프우주선 디텍터, 반도체의 초저유전소재, 유출된 석유의 정제, 촉매 등에 대한 응용에 대해서도 연구가 많이 이루어져 왔다. 그리고TiO2와 같은 광촉매 에어로젤 소재, 카본 에어로젤 소재등 다양한 나노기공 소재에 대해서도 연구가 이루어지고 있으며, 카본 에어로젤의 경우 나노기공과 비표면적을이용한 전기이중층 커패시터 (EDLC)에 대한 연구도 이루어지고 이다. 본 연구에서는 첫째로, 실리카 에어로젤에 대한 연구결과를 소개하고 이의 단열소재로서의 응용가능성에대하여 언급하고자 한다. 실리카 에어로젤 나노기공 소재의 경우, 기공크기가 10nm크기로 매우 작고 공기의 자유이동길이와 거의 비슷하여서 대류에 의한 열전달을 낮출 수 있으며, 낮은 고체함량으로 인하여 포논에 의한 열전달을 낮출 수 있기 때문에 단열소재로서 최고의 성능을 나타낸다. 하지만, 문제는 높은 기공률로 인한 기계적인 취약성이 문제이다. 따라서 이를 보완하기 위항 섬유로 에어로젤을 보강할 수 있는데, 이를통하여 에어로젤 나노기공소재와 섬유보강에 의한 복합화에 대하여 말하고자 한다. 또 다른 하나의 연구방법은유기-무기 하이브리드 나노기공 소재를 합성하는 것이다. 여기서는하나의 방법으로 MTEOS-TEOS의 하이브리드화와 초임계 건조공정에 의한 나노기공 소재에 대한 연구결과를소개하고자 한다. 마지막으로 카본 에어로젤 나노기공소재의 합성과 나노기공 구조의 제어 및 물성평가에 대한 것을 말하고자하는데, 본 발표에서는 레소시놀과 포름알데히드를 촉매에 의한 중합반응을 통하여 유기 에어로젤 소재를 합성하고 분위기에서탄소화 공정을 통하여 카본에어로젤을 합성하였다. 또한 금속 니켈을 도입하는 것에 의하여 탄소/니켈 복합 하이브리드 에어로젤 소재를 합성하고 슈퍼커패시터 전기화학 특성에 대한 연구결과를 발표하고자 한다.