고압에서 폴리(에틸렌/비닐 알코올) 공중합체-용매계의 상거동에 관한 연구

변헌수; 김종배

Journal of the Korean Industrial and Engineering Chemistry, Vol.9, No.3, 424-429, June, 1998

Export Citation

고압에서 폴리(에틸렌/비닐 알코올) 공중합체-용매계의 상거동에 관한 연구

Phase Behavior of Poly(ethylene-co-vinyl alcohol)-Solvent System at High Pressure

변헌수, 김종배

초록

본 연구는 두 가지의 공중합체인 poly(ethylene-co-vinyl alcohol)(PEVA) [9.9mol%와 17.8mol% vinyl alcohol(VA)]에 용매인 에틸렌, 프로판, 프로필렌, 부탄, 1-부텐, 디메틸 에테르(DME) 및 클로로디플로로메탄(CDFM)과의 구름점(cloud-point)을 얻기 위해 온도 230℃와 압력 1,800bar까지 상거동 실험을 수행하였다. 실험장치로는 평형조(view cell)를 이용한 고온, 고압에서 실험할 수 있는 정지형(static type)을 사용하였다. PEVA(9.9mol% VA) -DME계에 있어서 PEVA의 농도를 1.4∼20.0wt%에 걸쳐 변화시킬 때의 압력과 온도에 따른 상거동을 알아보았다. PEVA(17.8mol% VA)-DME계의 압력-온도에 따른 상거동은 1.9∼6.8wt%에 걸친 농도 범위에서 나타내었다. PEVA(9.9mol%와 17.8mol% VA)와 DME간의 혼합물 구름점은 VA와 DME간의 수소결합에 의하여 압력이 480bar 이하에서 나타났다. PEVA(9.9mol%와 17.8 mol% VA)-DME계에 대해 압력-농도(P-x) 등온곡선 관계를 나타내었다. PEVA(9.9mol%와 17.8 mol% VA)와 용매인 에틸렌, 프로판, 프로필렌, 부탄, 1-부텐 및 CDFM과의 상거동은 1,800bar 이하에서 음의 기울기를 보였으며, PEVA(9.9mol% VA)-DME계에 대한 상거동은 80℃에서 160℃ 온도범위에서 온도가 감소함에 따라 압력이 감소하는 양의 기울기를 가짐을 알 수 있었다.

Cloud-point data at 230℃ and 1,800 bar are presented for two poly(ethylene-co-vinyl alcohol)(PEVA) copolymers[9.9mol% and 17.8mol% vinyl alcohol(VA)] in ethylene, propane, propylene, n-butane, 1-butene, dimethyl ether(DME), and chlorodifluromethane(CDFM). The static type experimental apparatus with a view cell has been used for the experiment at the high pressure and temperature. The pressure-temperature (P-T) loops of PEVA(9.9mol% VA) copolymer-DME mixtures are presented at copolymer concentrations of 1.4wt% to 20.0wt%. Also, we presented the phase behavior of PEVA(17.8mol% VA) copolymer-DME system at copolymer concentration of 1.9wt% to 6.8wt%. The cloud-point curves for the PEVA copolymers in dimethyl ether showed single phase above 480 bar as a result of the hydrogen bonding between the vinyl alcohol unit and dimethyl ether. The pressure-concentration(P-x) isotherm loops of PEVA(9.9mol% and 17.8mol% VA)-DME system are obtained. The cloud-point curves for PEVA(9.9mol% and 17.8 mol% VA) copolymers and the ethylene, propane, propylene, n-butane, 1-butene, and CDFM all show negative slopes of phase behavior and are located at pressures below 1,800 bar. For PEVA copolymer-DME system(9.9mol% VA), cloud-point curves show positive slopes that decrease in pressures with decrease in temperature in the temperature range of 80℃ to 160℃.

[References]

Boysen RL, "Kirk-Othmer Encyclopedia of Chemical Technology [Olefin Polymers(High Pressure Polyethylene)]," ed. by M. Grayson, p. 401, Johns Wiley & Sons, New York (1981)
Chen SJ, Economou IG, Radosz M, Macromolecules, 26, 4987 (1992)
Chen SJ, Economou IG, Radosz M, Fluid Phase Equilib., 83, 391 (1993)
Chen SJ, Radosz M, Macromolecules, 25, 3089 (1992)
Gregg CJ, Chen SJ, Stein FP, Radosz M, Fluid Phase Equilib., 83, 375 (1993)
Ratzsch MT, Wagner P, Wohlfarth C, Heise D, Acta Polym., 33, 463 (1982)
Ratzsch MT, Findeison R, Sernow VS, Z. Phys. Chem., 261, 995 (1980)
Ratzsch MT, Wagner P, Wohlfarth C, Gleditzsch S, Acta Polym., 34, 340 (1983)
Luft G, Subramanian NS, Ind. Eng. Chem. Res., 26, 750 (1987)
Meilchen MA, Hasch BM, McHugh MA, Macromolecules, 24, 4874 (1991)
Hasch BM, Meilchen MA, Lee SH, McHugh MA, J. Polym. Sci. B: Polym. Phys., 30, 1365 (1992)
Luft G, Wind RW, Chem. Ing. Tech., 64, 1114 (1992)
Otocka EP, Kwei TK, Macromolecules, 1, 244 (1968)
Kihira Y, Yamamura H, J. Polym. Sci. B: Polym. Phys., 24, 867 (1986)
Earnest TR, MacKnight WJ, J. Polym. Sci. B: Polym. Phys., 16, 143 (1978)
Earnest TR, MacKnight WJ, Macromolecules, 13, 844 (1980)
Buback M, Mahling FO, J. Supercrit. Fluids, 8(2), 119 (1995)
Lee SH, LoStracco MA, Hasch BM, McHugh MA, J. Phys. Chem., 98(15), 4055 (1994)
Byun HS, Hasch BM, McHugh MA, Mahling FO, Busch M, Buback M, Macromolecules, 29(5), 1625 (1996)
Mertdogan CA, Byun HS, McHugh MA, Tuminello WH, Macromolecules, 29(20), 6548 (1996)
Kirom E, "Supercritical Fluids," p. 541, Kluwer Academic Publishers, Dordrecht (1994)
Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases and Liquids," 4th ed., McGraw-Hill Inc., New York (1987)
David RL, "CRC Handbook of Chemistry and Physics," 73rd ed., CRC Press, Boca Raton, FL (1992)
Hasch BM, Byun HS, Lee SH, McHugh MA, Paul JW, Hatch P, Invited Presentation of Dupont Tech. Conference, October, Dupont Co., Houston (1994)
Lee SH, "Cosolvent and Molecular Weight Effects on Acid Copolymer Mixtures," Ph.D. Thesis, The Johns Hopkins University (1995)

[Referenced By]

[1] Boysen RL, "Kirk-Othmer Encyclopedia of Chemical Technology [Olefin Polymers(High Pressure Polyethylene)]," ed. by M. Grayson, p. 401, Johns Wiley & Sons, New York (1981)

[2] Chen SJ, Economou IG, Radosz M, Macromolecules, 26, 4987 (1992)

[3] Chen SJ, Economou IG, Radosz M, Fluid Phase Equilib., 83, 391 (1993)

[4] Chen SJ, Radosz M, Macromolecules, 25, 3089 (1992)

[5] Gregg CJ, Chen SJ, Stein FP, Radosz M, Fluid Phase Equilib., 83, 375 (1993)

[6] Ratzsch MT, Wagner P, Wohlfarth C, Heise D, Acta Polym., 33, 463 (1982)

[7] Ratzsch MT, Findeison R, Sernow VS, Z. Phys. Chem., 261, 995 (1980)

[8] Ratzsch MT, Wagner P, Wohlfarth C, Gleditzsch S, Acta Polym., 34, 340 (1983)

[9] Luft G, Subramanian NS, Ind. Eng. Chem. Res., 26, 750 (1987)

[10] Meilchen MA, Hasch BM, McHugh MA, Macromolecules, 24, 4874 (1991)

[11] Hasch BM, Meilchen MA, Lee SH, McHugh MA, J. Polym. Sci. B: Polym. Phys., 30, 1365 (1992)

[12] Luft G, Wind RW, Chem. Ing. Tech., 64, 1114 (1992)

[13] Otocka EP, Kwei TK, Macromolecules, 1, 244 (1968)

[14] Kihira Y, Yamamura H, J. Polym. Sci. B: Polym. Phys., 24, 867 (1986)

[15] Earnest TR, MacKnight WJ, J. Polym. Sci. B: Polym. Phys., 16, 143 (1978)

[16] Earnest TR, MacKnight WJ, Macromolecules, 13, 844 (1980)

[17] Buback M, Mahling FO, J. Supercrit. Fluids, 8(2), 119 (1995)

[18] Lee SH, LoStracco MA, Hasch BM, McHugh MA, J. Phys. Chem., 98(15), 4055 (1994)

[19] Byun HS, Hasch BM, McHugh MA, Mahling FO, Busch M, Buback M, Macromolecules, 29(5), 1625 (1996)

[20] Mertdogan CA, Byun HS, McHugh MA, Tuminello WH, Macromolecules, 29(20), 6548 (1996)

[21] Kirom E, "Supercritical Fluids," p. 541, Kluwer Academic Publishers, Dordrecht (1994)

[22] Reid RC, Prausnitz JM, Poling BE, "The Properties of Gases and Liquids," 4th ed., McGraw-Hill Inc., New York (1987)

[23] David RL, "CRC Handbook of Chemistry and Physics," 73rd ed., CRC Press, Boca Raton, FL (1992)

[24] Hasch BM, Byun HS, Lee SH, McHugh MA, Paul JW, Hatch P, Invited Presentation of Dupont Tech. Conference, October, Dupont Co., Houston (1994)

[25] Lee SH, "Cosolvent and Molecular Weight Effects on Acid Copolymer Mixtures," Ph.D. Thesis, The Johns Hopkins University (1995)