톨루엔용매계에서 폴리에테르와 방향족 디이소시아네이트의 반응속도론

이현주; 김광

Polymer(Korea), Vol.22, No.4, 528-535, July, 1998

Export Citation

톨루엔용매계에서 폴리에테르와 방향족 디이소시아네이트의 반응속도론

The Reaction Kinetics of Aromatic Diisocyanates with Polyether in Toluene

이현주, 김광

초록

Polyoxypropylene glycol(PPG), polytetramethylene ether glycol(PTMG), glycolpropylene(GP)과 4,4'-diphenyl methane diisocyanate(MDI), toluene diisocyanate(TDI)의 동시반응 속도론을 연구하였으며, 자료는 Baker와 Sato의 방법에 따라 분석하였다. Polyether diol과 방향족 diisocyanate의 속도상수 K와 K'를 측정하였다. MDI-PTMG계는 2차 및 3차 반응 속도식에 뚜렷하게 일치하였다. TDI-PTMG계의 실험자료는 2차 속도식에 일치하였으나, 이론접근식에는 잘 맞지 않았다. TDI-PTMG계의 E'₄-E'₃ 값은 MDI-PTMGE계의 E'₂-E'₁ 값보다 5배 낮았다.

The kinetics of spontaneous reaction of 4,4'-diphenyl methane diisocyanate (MDI), and toluene diisocyanate(TDI) with polyoxypropylene glycol(PPG), polytetramethylene ether glycol(PTMG), and glycol propylene(GP) were studied, and the data were treated by a method developed by Baker and Sate. The rate constants, K and K' of aromatic diisocyanate with polyether diol were determined. The reaction of MDI-PTMG system apparently followed second and third order kinetics in good agreement. The reactions of TDI-PTMG system followed these kinetics experimentally but did not follow theoretically. The difference of E'₄-E'₃ of TDI-PTMG was smaller about 5 times than E'₂-E'₁ values of MDI-PTMG system.

Keywords:Polyether-diol;Aromatic diisocyanate;Prepolymer;Kinetics

[References]

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[2] Camberin Y, Pascault JP, Letoffe JM, Claudy P, J. Polym. Sci. B: Polym. Phys., 20, 1445 (1982)

[3] Doyle EN, "The Development and Use of Polyurethane Products," p. 93, McGraw-Hill, Co., Inc., New York (1984)

[4] Hepburn C, "Polyurethane Elastomers," p. 3-4, Applied Science Publishers, London (1982)

[5] Oertel G, "Polyurethane Handbook," Hanser Publishers (1985)

[6] Pearson RG, J. Chem., 45(10), 643 (1968)

[7] Yen MS, Kuo SC, J. Appl. Polym. Sci., 61(10), 1639 (1996)

[8] Petrovic ZS, Javni I, J. Polym. Sci., 27, 545 (1989)

[9] Davis TL, Farnum JM, This J., 56, 883 (1934)

[10] Baker JW, Holdsworth JB, J. Chem. Soc., 8, 713 (1947)

[11] Baker JW, Gaunt J, J. Am. Chem. Soc., 9, 27 (1949)

[12] Burkus J, Eckert CF, J. Am. Chem. Soc., 80, 5948 (1957)

[13] Kaplan M, J. Chem. Eng. Data, 6, 272 (1961)

[14] Westheimer FH, Jones WA, Lad RA, J. Chem. Phys., 19, 178 (1942)

[15] French D, This J., 72, 4806 (1950)

[16] MaMillan WG, This J., 79, 4838 (1957)

[17] Sato M, J. Am. Chem. Soc., 82, 3893 (1960)

[18] Kajiyama T, Mcknight WJ, Macromolecules, 2, 254 (1969)

[19] Greenshields JN, Peters RH, Stepto RFT, J. Am. Chem. Soc., 21, 5101 (1964)

[20] Dyer E, Taylor HA, Mason SJ, Samson J, This J., 71, 4106 (1949)

[21] Saunders JH, Friseh KC, "High Polymer: Polyurethane Chemistry and Technology," vol. 16, part 1, p. 1, 129, Interscience Publishers, New York (1969)

[22] Levenspiel O, "Chemical Reaction Engineering," vol. II, p. 32, Tower Press, Seoul (1972)