Solubility Behavior of Copolymers of Tetrahydropyranyl Methacrylate and 1H,1H,2H,2H-Perfluorooctyl Methacrylate in Carbon Dioxide: Effect of Deprotection of THP Groups

Jae Young Heo; Jong Tae Kim; Yong-Seok Jeong; Yeon-Soon Gal; Kwon Taek Lim

Journal of Industrial and Engineering Chemistry, Vol.10, No.3, 389-394, May, 2004

Jae Young Heo, Jong Tae Kim, Yong-Seok Jeong, Yeon-Soon Gal¹, and Kwon Taek Lim^†

Division of Image and Information Engineering, Pukyong National University, Busan 608-736, Korea
¹College of General Educaiton, Kyung Il University, Gyeonsang Bukdo 712-701, Korea

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A series of homopolymer and copolymers, which consist of heat-cleavable tetrahydropyranyl methacrylate (THPMA) and CO₂-philic 1H,1H,2H,2H-perfluorooctyl methacrylate (FOMA), were prepared by group transfer polymerization (GTP). The THPMA units of homo- and copolymers were deprotected to methacrylic acid (MAA) units by thermolysis after the polymerization. The solubilities of the copolymers in CO₂ were examined; the phase behavior of block copolymers was investigated in terms of the cloud pressure. Their solubility was greatly influenced by the copolymer compositions as well as by the extent of deprotection of the THPMA units. As the mole fraction of fluorinated methacrylate in the copolymers decreases, the cloud point curves shift to higher pressures.

Keywords:semifluorinated copolymer;carbon dioxide;group transfer polymerization

[References]

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Dicker IB, Cohen GM, Farnham WB, Hertler WR, Laganis ED, Sogah DY, Macromolecules, 23, 4034 (1990)
Simmons HE, Hertler WR, Sauer BB, J. Appl. Polym. Sci., 52(6), 727 (1994)
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[Referenced By]

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[2] Kompella UB, Koushik K, Crit. Rev. Ther. Drug Carrier Syst., 18, 173 (2001)

[3] Montero GA, Smith CB, Hendrix WA, Butcher DL, Ind. Eng. Chem. Res., 39(12), 4806 (2000)

[4] Kiran E, Brennecke JF, ACS Symposium Series 514; American Chemical Society: Washington, D.C., p. 238 (1993)

[5] Sihvonen M, Jarvenpaa E, Hietaniemi V, Huopalahti R, Trends Food Sci. Technol., 10, 217 (1999)

[6] McHardy J, Sawan SP, Supercritical Fluid Cleaning Fundamentals, Technology and Applications, pp. 5-30, Noyes, Westwood, NJ (1998)

[7] Shim JJ, Johnston KP, J. Phys. Chem., 95, 353 (1991)

[8] Iezzi A, Bendale P, Enicj RM, Turberg M, Brady J, Fluid Phase Equilib., 52, 307 (1990)

[9] Holefling TA, Enicj RM, Beckman EJ, J. Phys. Chem., 95, 7127 (1991)

[10] Lepilleur C, Beckman EJ, Macromolecules, 30(4), 745 (1997)

[11] Canelas DA, Betts DE, DeSimone JM, Yates MZ, Johnston KP, Macromolecules, 31(20), 6794 (1998)

[12] Shaffer KA, Jones TA, Canelas DA, Desimone JM, Wilkinson SP, Macromolecules, 29(7), 2704 (1996)

[13] O'Shea KE, Kirmse KM, Fox MA, Johnston KP, J. Phys. Chem., 95, 7863 (1991)

[14] Shah VM, Hardy BJ, Stern SA, J. Polym. Sci. B: Polym. Phys., 24, 2033 (1986)

[15] Kazarian SG, Vincent MF, Bright FV, Liotta CL, Eckert CA, J. Am. Chem. Soc., 118(7), 1729 (1996)

[16] Lepilleur C, Beckman EJ, Schonemann H, Krukonis VJ, Fluid Phase Equilib., 134(1-2), 285 (1997)

[17] Mertdogan CA, DiNoia TP, McHugh MA, Macromolecules, 30(24), 7511 (1997)

[18] Hoggan E, Desimone JM, Carbonell RG, Polym. Prepr., (Am. Chem. Soc., Div. Polym. Mater. Sci. Eng. Part 2), Aug., 22, 218 (1999)

[19] Sundararajan N, Yang S, Ogino K, Valiyaveettil S, Wang J, Zhou X, Ober CK, Obendorf SK, Allen RD, Chem. Mater., 12, 41 (2000)

[20] Hertler WR, U.S. Patent, 5,072,029 (1991)

[21] Dicker IB, Cohen GM, Farnham WB, Hertler WR, Laganis ED, Sogah DY, Macromolecules, 23, 4034 (1990)

[22] Simmons HE, Hertler WR, Sauer BB, J. Appl. Polym. Sci., 52(6), 727 (1994)

[23] Kearns JE, McLean CD, Solomon DH, J. Macromol. Sci.-Chem., A8, 673 (1974)

[24] Lowe AB, Billingham NC, Armes SP, Macromolecules, 31(18), 5991 (1998)