Estimation of Molecular Weight in Terms of the Gel Effect in Radical Polymerization

In consideration of the modern idea of reptation, it is proposed that the rate of termination is proportional to n−1/2(n=chain length) when n is less than a critical chain length nc, but the rate is proportional to n−2 when n>nc. The molecular weight in terms of the gel effect is calculated by using such a rate. This molecular weight fits sufficiently to the experimental molecular weight obtained previously in a radical polymerization of methyl methacrylate. Further, the rate constant of termination between small polymer radicals is discussed by the free volume theory.

[1]  Katsukiyo Ito.  Relationship between chain termination rate constant and conversion in radical polymerization , 1969 .

[2]  A. Henglein,et al.  Pulsradiolytische messung der geschwindigkeitskonstanten der kombination von polyäthylenoxid-radikalen in wäßriger lösung , 1969 .

[3]  S. Edwards,et al.  Dynamics of concentrated polymer systems. Part 1.—Brownian motion in the equilibrium state , 1978 .

[4]  A. Hamielec,et al.  Bulk polymerization of methyl methacrylate , 1973 .

[5]  J. Klein,et al.  Evidence for reptation in an entangled polymer melt , 1978, Nature.

[6]  Sam F. Edwards,et al.  Dynamics of rod-like macromolecules in concentrated solution. Part 1 , 1978 .

[7]  Katsukiyo Ito.  Estimation of molecular weight distribution based on chain length dependence of termination rate , 1975 .

[8]  H. Yamakawa.  Concentration Dependence of Polymer Chain Configurations in Solution , 1961 .

[9]  A. Tobolsky,et al.  Rates of initiation in vinyl polymerization , 1952 .

[10]  H. Mahabadi,et al.  A new method for evaluation of the characteristic constant for primary radical termination in free radical polymerization , 1979 .

[11]  Kunio Arai,et al.  SIMULATION MODEL FOR THE RATE OF BULK POLYMERIZATION OVER THE COMPLETE COURSE OF REACTION , 1976 .

[12]  F. Bueche.  Viscoelasticity of Poly Methacrylates , 1955 .

[13]  P. Flory.  Principles of polymer chemistry , 1953 .

[14]  P. Gennes.  Reptation of a Polymer Chain in the Presence of Fixed Obstacles , 1971 .

[15]  Katsukiyo Ito.  Evaluation of Termination Rate by Segmental and Translational Diffusions in Radical Polymerizations , 1979 .

[16]  Katsukiyo Ito.  Relationship between polymerization rate and monomer concentration in radical polymerization of vinyl acetate , 1975 .

[17]  S. Edwards,et al.  Dynamics of concentrated polymer systems. Part 2.—Molecular motion under flow , 1978 .

[18]  G. Meyerhoff,et al.  Die thermische Polymerisation von Methylmethacrylat, 1. Polymerisation in Substanz , 1978 .

[19]  Katsukiyo Ito.  Kinetic analysis based on the excluded‐volume effect for radical polymerization , 1974 .

[20]  S. Edwards,et al.  Dynamics of concentrated polymer systems. Part 4.—Rheological properties , 1979 .

[21]  H. Melville,et al.  The kinetics of the polymerization of methyl methacrylate. I. The bulk reaction , 1960 .

[22]  W. Graessley.  Molecular Entanglement Theory of Flow Behavior in Amorphous Polymers , 1965 .

[23]  K. Horie,et al.  Fast Reaction and Micro-Brownian Motion of Flexible Polymer Molecules in Solution , 1973 .

[24]  S. Benson,et al.  The Kinetics of Free Radical Polymerization under Conditions of Diffusion-controlled Termination , 1962 .

[25]  S. Russo,et al.  Radiochemical study of the radical copolymerization of styrene and methyl methacrylate , 1976 .

[26]  A. Tobolsky,et al.  The Thermal Decomposition of 2,2'-Azo-bis-isobutyronitrile, , 1958 .

[27]  G. Schulz.  Über die Beziehung zwischen Diffusionskoeffizient und Geschwindigkeitskonstante bimolekularer Reaktionen in Lösung , 1956 .

[28]  S. Edwards,et al.  Dynamics of rod-like macromolecules in concentrated solution. Part 2 , 1978 .

[29]  Katsukiyo Ito.  Relationship between radical polymerization rate and initiator concentration in various solvents , 1974 .

[30]  J. Klein.  The Onset of Entangled Behavior in Semidilute and Concentrated Polymer Solutions , 1978 .

[31]  K. Horie,et al.  Calorimetric investigation of polymerization reactions. I. Diffusion‐controlled polymerization of methyl methacrylate and styrene , 1968 .

[32]  F. Bueche,et al.  Viscosity, Self‐Diffusion, and Allied Effects in Solid Polymers , 1952 .

[33]  Katsukiyo Ito.  Termination rate constants in radical polymerization , 1970 .

[34]  K. O'driscoll,et al.  High‐conversion polymerization. I. Theory and application to methyl methacrylate , 1976 .

[35]  B. Brooks.  Viscosity effects in the free-radical polymerization of methyl methacrylate , 1977, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[36]  Katsukiyo Ito.  Evaluation of polymerization rate by chain length dependence on polymer–polymer termination and primary radical termination in radical polymerization , 1980 .

[37]  Katsukiyo Ito.  Derivation of distributions of the degree of polymerization by probability theory , 1969 .

[38]  F. N. Kelley,et al.  Viscosity and glass temperature relations for polymer‐diluent systems , 1961 .

[39]  K. O'driscoll,et al.  Absolute Rate Constants in Free-Radical Polymerization. III. Determination of Propagation and Termination Rate Constants for Styrene and Methyl Methacrylate , 1977 .

[40]  Katsukiyo Ito.  Initiator concentration dependence of the autoacceleration of polymerization rate , 1975 .

[41]  Katsukiyo Ito.  Relationship between kinetic chain length and radical polymerization rate , 1976 .