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Received May 13, 2004
Accepted July 30, 2004
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고압상태에서 이산화탄소가 포함된 이성분계 혼합용매에 대한 Poly(L-lactide)와 Polycaprolactone의 상거동
Phase Behavior of Poly(L-lactide) and Polycaprolactone in Binary Mixtures including CO2 at High Pressure
한국과학기술연구원 환경공정연구부 청정기술연구센터, 136-791 서울시 성북구 하월곡동 39-1 1서울대학교 응용화학부, 151-742 서울시 관악구 신림동 산 56-1 2서강대학교 화공생명 공학과, 121-742 서울시 마포구 신수동 1
Environmental & Process Technology Division, Clean Technology Research Center, KIST, 39-1, Hawolgok-dong, Sungbuk-gu, Seoul 136-791, Korea 1School of Chemical Engineering and Institute of Chemical Processes, Seoul National University, San 56-1, Shilim-dong, Gwanak-gu, Seoul 151-742, Korea 2Department of Chemical and Biomolecular Engineering, Sogang University, 1, Shinsu-dong, Mapo-gu, Seoul 121-742, Korea
limjs@sogang.ac.kr
Korean Chemical Engineering Research, October 2004, 42(5), 545-550(6), NONE Epub 18 November 2004
Abstract
본 연구에서는 variable volume view cell이 장착된 상평형 장치를 사용하여 고압 상태의 다양한 용매내에서 생분해성 고분자인 poly(L-lactide)(PLA)와 polycaprolactone(PCL)의 cloud point를 측정하였다. 이때 사용된 용ㅇ매는 HCFC-22, DME(dimethylether)이였으며, 이들 용매에 CO2를 첨가한 HCFC-22+CO2와 DME+CO2의 이성분계 혼합용매에서 CO2의 조성이 변화함에 의해 이 용매내에서 poly(L-lactide)와 polycaprolactone의 상거동에 미치는 영향을 살펴보았다. Poly(L-lactide)의 경우, HCFC-22에 대해 온도 범위가 344-393 K일 때, 4.0-15.0 MPa의 비교적 낮은 압력에서 잘 용해되었으며 HCFC-22와 여기에 CO2를 첨가한 HCFC-22+CO2 혼합용매 모두에서 LCST(lower critical solution temperature)의 상거동을 보여주었다. Polycaprolactone의 경우는 DME와 HCFC-22에 대해 온도 범위가 310-415 K일 때, 각각 압력 범위 13-37 MPa과 3-27 MPa에서 비교적 잘 용해되었으며, DME와 HCFC-22 및 CO2를 첨가한 HCFC-22+CO2와 DME+CO2의 이성분계 혼합용매에서 poly(L-lactide)와 마찬가지로 모두 LCST의 상거동을 보여주었다. CO2 혼합용매내에서 두 물질의 cloud point 압력은 동일한 온도에서 첨가되는 CO2의 양에 비례하여 높아지는 것을 관찰할 수 있었고, 이로서 CO2가 DME와 HCFC-22에 대해 역용매로 사용될 수 있다는 것을 확인할 수 있었다. 또한 CO2의 농도를 변화시킴으로써 poly(L-lactide)와 polycaprolactone의 cloud point를 자유롭게 조절할 수 있다는 것을 알 수 있었다.
We measured cloud points using the high-pressure variable volume cell apparatus for poly(L-lactide)(L-PLA) and polycaprolactone(PCL) in various solvents. The solvents used for dissolving poly(L-lactide) and polycaprolactone were HCFC-22(chlorodifluoromethane) and DME(dimethylether), HCFC-22+CO2, and DME+CO2. In case of L-PLA, it was dissolved well in HCFC-22 in the pressure range 4.0-15.0 MPa and the temperature range 344-393 K, and exhibited LCST(lower critical solution temperature) behavior in HCFC-22 and HCFC-22+CO2. In case of polycaprolactone, it was dissolved well in DME and HCFC-22 in the pressure range 13-37 MPa and 3-27 MPa respectively, in the range 310-415 K, and also exhibited LCST behavior in DME, HCFC-22, HCFC-22+CO2, and DME+CO2. The cloud point pressure of both poly(L-lactide) and polycaprolactone increased proportionally to the amount of CO2 added at the same temperature. According to these results, it was known that CO2 could be used as an anti-solvent, and the cloud point of poly(L-lactide) and polycaprolactone could be controlled by changing the concentration of CO2.
Keywords
References
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