.Soybean oil triglycerides (SOT) can be used for the synthesis of rigid polymers. This research investigates the potential of using dense (sub/supercritical) CO2 in the reaction medium for the addition of functional groups to SOT. As an alternative and novel method, the reaction of SOT with KMnO4 in the presence of water and dense CO2 is presented. Dense CO2 is utilized to bring the soybean oil and aqueous KMnO4 solution into contact. Experiments are done at 10, 25, 34.5, 50 oC and 2.5, 5, 7, 11, 16MPa. Effects of temperature, pressure, NaHCO3 addition, and KMnO4 amount on the conversion (depletion by bond opening) of soybean-triglyceride double bonds (STDB) are investigated. The highest STDB conversions, about 40%, are obtained at the near-critical conditions of CO2. The addition of NaHCO3 enhances the conversion; one mole of NaHCO3 per mole of KMnO4 gives the highest benefit. Increasing KMnO4 up to 10% increases the conversion of STDB.

Sub/Supercritical Carbon Dioxide Reaction Soybean Oil Triglyceride KMnO4

Akgerman A, Lin B, Homogeneous and catalytic reactions in supercritical fluids, in: Bertucco, A., ed., CISF-99 5th Conference on Supercritical Fluids and Their Applications, 289 (1999)
Arunajatesan V, Subramaniam B, Hutchenson KW, Herkes FE, Chem. Eng. Sci., 56(4), 1363 (2001) 
Aydogan S, Hydroxylation of soybean triglycerides in sub/supercritical carbon dioxide, M.Sc. Thesis, Bo azici University, stanbul, Turkey (2001)
Baiker A, Chem. Rev., 99, 453 (1999) 
Biermann U, Friedt W, Lang S, Luhs W, Machmuller G, Metzger JO, Ruschgen Klass M, Schafer HJ, Schneider MP, Angew. Chem.-Int. Edit., 39, 2206 (2000) 
Brennecke JF, Nature, 389(6649), 333 (1997) 
Buback M, Kinetics and selectivity of chemical processes in fluid phases, in: Kiran, E. and Levelt Sengers, J.M. H., eds., Supercritical Fluids, Kluwer Academic Publishers, Netherlands, 481 (1994)
Clifford AA, Reactions in supercritical fluids, in: Kiran, E. and Levelt Sengers, J. M. H., eds., Supercritical Fluids, Kluwer Academic Publishers, Netherlands, 449 (1994)
Cocero MJ, Gonzales S, Perez S, Alonso E, J. Supercrit. Fluids, 19, 39 (2000) 
Dinjus E, Fornika R, Scholz M, Organic chemistry in supercritical fluids, in: van Eldik, R. and Hubbard, C. D., eds., Chemistry Under Extreme or Non-Classical Conditions, Wiley, New York, 219 (1997)
Eckert CA, Ziger DH, Johnston KP, Kim S, J. Phys. Chem., 90, 2738 (1986) 
Eckert CA, Knutson BL, Debenedetti PG, Nature, 383(6598), 313 (1996) 
Eggers R, JAOCS, 62, 1222 (1985) 
Ellington JB, Park KM, Brennecke JF, Ind. Eng. Chem. Res., 33(4), 965 (1994) 
Fischer A, Mallat T, Baiker A, J. Catal., 182(2), 289 (1999) 
Gray WK, Smail FR, Hitzler MG, Ross SK, Poliakoff M, J. Am. Chem. Soc., 121(46), 10711 (1999) 
Hadida S, Super MS, Beckman EJ, Curran DP, J. Am. Chem. Soc., 119(31), 7406 (1997) 
Hautal WH, Chemosphere, 43, 123 (2001) 
Ikushima Y, Saito N, Arai M, J. Phys. Chem., 96, 2293 (1992) 
Ikushima Y, Saito N, Hatakeda K, Sato O, Chem. Eng. Sci., 51(11), 2817 (1996) 
Jessop PG, Ikariya T, Noyori R, Nature, 368(6468), 231 (1994) 
Jessop PG, Hsiao Y, Ikariya T, Noyori R, J. Am. Chem. Soc., 118(2), 344 (1996) 
Jessop PG, Leitner W, Supercritical fluids as media for chemical reactions in: Jessop, P.G. and Leitner, W., eds., Chemical Synthesis Using Supercritical Fluids, Wiley-VCH, New York, 1 (1999)
Karakas G, Dogu T, Somer TG, Ind. Eng. Chem. Res., 36(11), 4445 (1997) 
Knutson BL, Dillow AK, Liotta CL, Eckert CA, Kinetics of a diels-alder reaction in supercritical propane, in: Hutchenson, K.W. and Foster, N. R., eds., Innovations in Supercritical Fluids, ACS Symposium Series 608, American Chemical Society: Washington,166 (1995)
Lapworth A, Mottram EN, J. Chem. Soc., 127, 1628 (1925)
Lee BM, Veriansyah B, Kim SH, Kim JD, Lee YW, Korean J. Chem. Eng., 22(4), 579 (2005)
Lee HC, In JH, Kim JH, Hwang KY, Lee CH, Korean J. Chem. Eng., 22(6), 882 (2005)
Marr R, Gamse T, Chem. Eng. Prog., 39, 19 (2000) 
Morrison RT, Boyd RN, Organic chemistry, Prentice Hall, New Jersey (1992)
Nam SC, Kim GJ, Korean J. Chem. Eng., 21(3), 582 (2004)
Oliveira D, Oliveira JV, J. Supercrit. Fluids, 19(2), 141 (2001) 
Palo DR, Erkey C, Ind. Eng. Chem. Res., 37(10), 4203 (1998) 
Park CY, Ryu YW, Kim C, Korean J. Chem. Eng., 18(4), 475 (2001)
Park JH, Park SD, Korean J. Chem. Eng., 19(6), 960 (2002)
Phiong HS, Lucien FP, Adesina AA, J. Supercrit. Fluids, 25, 155 (2003) 
Poliakoff M, George MW, Howdle SM, Inorganic and related chemical reactions in supercritical fluids, in: van Eldik, R. and Hubbard, C. D., eds., Chemistry Under Extreme or Non-Classical Conditions, Wiley, New York, 189 (1997)
Poliakoff M, George MW, Chemical reactions as a continuous process in supercritical fluids, in: Perrut, M. and Subra, P. eds., Proceedings of the 5th Meeting on Supercritical Fluids, Materials and Natural Products Processing, Tome 2: Natural Products, Advanced Processes Reactions and Various, 833 (1998)
Renslo AR, Weinstein RD, Tester JW, Danheiser RL, J. Org. Chem., 62, 4530 (1997) 
Rezaei K, Temelli F, J. Supercrit. Fluids, 19, 263 (2001) 
Savage PE, Gopalan S, Mizan TI, Martino CJ, Brock EE, AIChE J., 41(7), 1723 (1995) 
Sherman J, Chin B, Huibers PDT, Galcia-Valls R, Hatton TA, Environ. Health Perspect., 106, 253 (1998)
Srinivas P, Mukhopadhyay M, Ind. Eng. Chem. Res., 33(12), 3118 (1994) 
Stahl E, Quirin KW, Gerard D, Dense gases for extraction and refining, Translation from the German Edition by Ashworth M.R. F., Springer-Verlag, Berlin (1988)
Tegetmeier A, Dittmar D, Fredenhagen A, Eggers R, Chem. Eng. Process., 39(5), 399 (2000) 
Wai CM, Hunt F, Ji M, Chen X, J. Chem. Educ., 75, 1641 (1998)
Wang SN, Kienzle F, Ind. Eng. Chem. Res., 39(12), 4487 (2000) 
Weinstein RD, Renslo AR, Danheiser RL, Harris JG, Tester JW, J. Phys. Chem., 100(30), 12337 (1996) 
Weinstein RD, Renslo AR, Danheiser RL, Tester JW, J. Phys. Chem. B, 103(15), 2878 (1999) 
Wiebe R, Chem. Rev., 29, 475 (1941) 
Wiebe R, Gaddy VL, J. Am. Chem. Soc., 62, 815 (1940) 
Wool R, Kusefo lS, Palmese G, Khot S, Zhao R, High modulus polymers and composites from plant oils, U.S. Patent 6,121,398, Sep. 19 (2000)