Reaction Kinetics and Chemorheology of a Highly Reactive PU System

Kim DS; Macosko CW

Korea Polymer Journal, Vol.4, No.1, 54-60, April, 1996

The reaction kinetics and chemorheology of a fast polymerizing thermoset polyurethane (PU) system composed of 4,4-diphenylmethane diisocyanate, poly(propylene oxide) triol, and dibutyltin dialurate (T₁₂) as a catalyst was investigated. The adiabatic temperature rise measurements were carried out to analyze the reaction kinetics of the PU system since polymerization rate was so fast. A second order Arrhenius type reaction kinetic equation could describe well the reaction kinetics of the PU system. The power with respect to the catalyst concentration was about 0.6. Viscosity change of the PU system with low catalyst concentration during isothermal polymerization was measured using a rheometer. A viscosity function was estimated from the rheometer data and the kinetic data through nonlinear regression. The power law index with respect to the weight average molecular weight was dependent on the isothermal cure temperature.

[References]

Aranguren MI, Williams RJJ, Polymer, 27, 425 (1986)
Chen YT, Resin Transfer Molding of Liquid Dicyanate: chemorheology, Molding Experiments, and Wetting Visualization, Ph.D. Thesis, Univ. of Minnesota (1993)
Smith RE, Larsen FN, Long CL, J. Appl. Polym. Sci., 29, 3713 (1984)
Nakagawa H, Wakatsuka S, Tsuge S, Koyama T, Polym. J., 20, 9 (1988)
Kim DS, Kim SC, Polym. Eng. Sci., 34(8), 625 (1994)
Kim DS, Kim SC, Polym. Adv. Technol., 1, 211 (1990)
Mijovic J, Lee CH, J. Appl. Polym. Sci., 37, 889 (1989)
Duffy JV, Hui E, Hartmann B, J. Appl. Polym. Sci., 33, 2959 (1987)
Enns JB, Gillham JK, J. Appl. Polym. Sci., 28, 2831 (1983)
Gonzalez VM, Casillas N, Polym. Eng. Sci., 29(5), 295 (1989)
Prime RB, Thermosets, in Thermal Characterization of Polymer Materials, E.A. Turi, Ed., Academic Press, New York (1981)
Camargo RE, Gonzalez VM, Macosko CW, Tirrell M, Rubber Chem. Technol., 56, 774 (1983)
Pannone MC, Macosko CW, J. Appl. Polym. Sci., 34, 2409 (1987)
Lipshitz SD, Macosko CW, Polym. Eng. Sci., 16, 803 (1976)
Blake JW, Anderson RD, Yang WP, Macosko CW, J. Rheol., 31, 1236 (1987)
Castro JM, Macosko CW, Perry SJ, Polym. Commun., 25, 82 (1984)
Macosko CW, RIM Fundamentals of Reaction Injection Molding, Hanser, Ch. 2 (1989)
Mikkelsen KJ, Macosko CW, J. Elast. Plast., 21, 29 (1989)
Richter EB, Macosko CW, Polym. Eng. Sci., 18, 1012 (1978)
Castro JM, Macosko CW, AIChE J., 28, 250 (1982)
Castro JM, Macosko CW, Soc. Plast. Eng. Tech. Papers, 26, 434 (1980)
Garcia MA, Reactive Mold Filling Modeling, Ph.D. Thesis, Univ. of Minnesota (1991)
Rodriguez F, Principles of Polymer Systems, 2nd Ed., McGraw-Hill, N.Y., pp. 170 (1982)
Macosko CW, Miller DR, Macromolecules, 9, 199 (1976)

[1] Aranguren MI, Williams RJJ, Polymer, 27, 425 (1986)

[2] Chen YT, Resin Transfer Molding of Liquid Dicyanate: chemorheology, Molding Experiments, and Wetting Visualization, Ph.D. Thesis, Univ. of Minnesota (1993)

[3] Smith RE, Larsen FN, Long CL, J. Appl. Polym. Sci., 29, 3713 (1984)

[4] Nakagawa H, Wakatsuka S, Tsuge S, Koyama T, Polym. J., 20, 9 (1988)

[5] Kim DS, Kim SC, Polym. Eng. Sci., 34(8), 625 (1994)

[6] Kim DS, Kim SC, Polym. Adv. Technol., 1, 211 (1990)

[7] Mijovic J, Lee CH, J. Appl. Polym. Sci., 37, 889 (1989)

[8] Duffy JV, Hui E, Hartmann B, J. Appl. Polym. Sci., 33, 2959 (1987)

[9] Enns JB, Gillham JK, J. Appl. Polym. Sci., 28, 2831 (1983)

[10] Gonzalez VM, Casillas N, Polym. Eng. Sci., 29(5), 295 (1989)

[11] Prime RB, Thermosets, in Thermal Characterization of Polymer Materials, E.A. Turi, Ed., Academic Press, New York (1981)

[12] Camargo RE, Gonzalez VM, Macosko CW, Tirrell M, Rubber Chem. Technol., 56, 774 (1983)

[13] Pannone MC, Macosko CW, J. Appl. Polym. Sci., 34, 2409 (1987)

[14] Lipshitz SD, Macosko CW, Polym. Eng. Sci., 16, 803 (1976)

[15] Blake JW, Anderson RD, Yang WP, Macosko CW, J. Rheol., 31, 1236 (1987)

[16] Castro JM, Macosko CW, Perry SJ, Polym. Commun., 25, 82 (1984)

[17] Macosko CW, RIM Fundamentals of Reaction Injection Molding, Hanser, Ch. 2 (1989)

[18] Mikkelsen KJ, Macosko CW, J. Elast. Plast., 21, 29 (1989)

[19] Richter EB, Macosko CW, Polym. Eng. Sci., 18, 1012 (1978)

[20] Castro JM, Macosko CW, AIChE J., 28, 250 (1982)

[21] Castro JM, Macosko CW, Soc. Plast. Eng. Tech. Papers, 26, 434 (1980)

[22] Garcia MA, Reactive Mold Filling Modeling, Ph.D. Thesis, Univ. of Minnesota (1991)

[23] Rodriguez F, Principles of Polymer Systems, 2nd Ed., McGraw-Hill, N.Y., pp. 170 (1982)

[24] Macosko CW, Miller DR, Macromolecules, 9, 199 (1976)