Abstract
In Chapter 2, it was assumed that the functional groups of the various oligomers have the same reactivity, independent of the chain length, n, of the molecules on which they are located. Mathematical results derived for step growth polymerization based on the equal reactivity hypothesis were subsequently used to explain the gross kinetic features of the polyesterification of adipic acid with ethylene glycol. Comparison with experimental data sufficiently indicated that the overall polymerization is far more complex and the assumption of the equal reactivity hypothesis is a considerable simplification. This is true not only for polyesterification, but for most step growth polymerization systems.1 In addition, as the polymerization progresses, the viscosity of the reaction mass increases by severalfold and the overall reaction, at some stage depending upon the reactor used, becomes mass transfer controlled.2–5 In diffusion controlled reactions, the method of reactor analysis is quite different and will be discussed in Chapter 5.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
D. H. Solomon, ed. Step Growth Polymerization ,Marcel Dekker, New York (1972).
S. K. Gupta and A. Kumar, Simulation of step growth polymerization, Chem. Eng. Commun. 20, 1–52 (1983).
M. Amon and C. D. Denson, Simplified analysis of the performance of wiped-film polycondensation reactors, Ind. Eng. Chem. Fundam. 19, 415–420 (1980).
S. K. Gupta, N. L. Agarwalla, and A. Kumar, Mass transfer effects in polycondensation reactors wherein functional groups are not equally reactive, J. Appl. Polym. Sci. 27, 1217–1231 (1982).
S. K. Gupta, A. Kumar, and K. K. Agarwal, Simulation of AA’ + B’B reversible polymerization with mass transfer of condensation products, Polymer 23, 1367–1371 (1982).
L. C. Case, Molecular distributions in polycondensations involving unlike reactants. II. Linear distributions, J. Polym. Sci. 29, 455–495 (1958).
R. W. Lenz, C. E. Handlovitz, and H. A. Smith, Phenylene sulfide polymers. III. The synthesis of linear polyphenylene sulfide, J. Polym. Sci. 58, 351–367 (1962).
J. H. Hodkin, Reactivity changes during polyimide formation, J. Polym. Sci. Polym. Chem. Ed. 14, 409–431 (1976).
V. S. Nanda and S. C. Jain, Effect of variation of the bimolecular rate constant with chain length on the statistical character of condensation polymers, J. Chem. Phys. 49,1318–1320 (1968).
G. B. Taylor, The distribution of the molecular weight of nylon as determined by fractionation in a phenol-water system, J. Am. Chem. Soc. 69, 638–644 (1947).
S. I. Kuchanov, M. L. Keshtov, P. G. Halatur, V. A. Vasnev, S. V. Vinogradova, and V. V. Korshak, On the principle of equal reactivity in solution polycondensation, Macromol Chem. 184, 105–111 (1983).
S. K. Gupta, N. L. Agarwalla, P. Rajora, and A. Kumar, Simulation of reversible polycondensations with monomers having reactivities different from that of higher homologs, J. Polym. Sci. Polym. Phys. Ed. 20, 933–945 (1982).
A. Kumar, P. Rajora, N. L. Agarwalla, and S. K. Gupta, Reversible condensation character-ized by unequal reactivities, Polymer 23, 222–228 (1982).
R. Goel, S. K. Gupta, and A. Kumar, Rate of condensation polymerization for monomers having reactivities different from their polymers, Polymer 18, 851–852 (1977).
S. K. Gupta, A. Kumar, and A. Bhargava, Molecular weight distributions and moments for condensation polymerizations characterized by two rate constants, Europ. Polym. J. 15, 557–564 (1979).
S. K. Gupta, A. Kumar, and A. Bhargava, Molecular weight distribution and moments for condensation polymerization of monomers having reactivities different from their homologues, Polymer 20, 305–310 (1979).
A. Kumar, S. K. Gupta, and R. Saraf, Condensation polymerization of ARB type monomers in CSTRs wherein the monomer is R times more reactive than other homologues, Polymer 21, 1323–1326 (1980).
S. K. Gupta, A. Kumar, and R. Saraf, Condensation polymerization in ideal continuous flow-stirred tank reactors of monomers violating the equal reactivity hypothesis, J. Appl. Polym. Sci. 25, 1049–1058 (1980).
A. S. Gupta, A. Kumar, and S. K. Gupta, Condensation polymerization with unequal reactivity in segregated HCSTRs, British Polymer J. 13, 76–81 (1981).
L. H. Peebles, Molecular Weight Distribution in Polymers ,1st ed., Interscience, New York (1971).
K. S. Gandhi and S. V. Babu, Kinetics of step polymerization with unequal reactivities, AIChE J. 25, 266–272 (1979).
H. Kilkson, Generalization of various polycondensation problems, Ind. Eng. Chem. Fundam. 7, 354–363 (1968).
Author information
Authors and Affiliations
Rights and permissions
Copyright information
© 1987 Plenum Press, New York
About this chapter
Cite this chapter
Gupta, S.K., Kumar, A. (1987). Linear Step Growth Polymerization Violating the Equal Reactivity Hypothesis. In: Reaction Engineering of Step Growth Polymerization. The Plenum Chemical Engineering Series. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-1801-9_3
Download citation
DOI: https://doi.org/10.1007/978-1-4613-1801-9_3
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4612-9008-7
Online ISBN: 978-1-4613-1801-9
eBook Packages: Springer Book Archive