Formal kinetics of the condensation of polycaproamide and the effect of the nature of the molecular weight regulator on the stability of the polymers under repeated melting

Mizerovskii, L. N.; Paikachev, Yu. S.; Tikhonov, V.Yu.

doi:10.1016/0032-3950(73)90411-5

Polymer Science U.S.S.R.

1973

DOI: 10.1016/0032-3950(73)90411-5

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Formal kinetics of the condensation of polycaproamide and the effect of the nature of the molecular weight regulator on the stability of the polymers under repeated melting

L. N. Mizerovskii

Yu. S. Paikachev

V.Yu. Tikhonov

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Cited by 3 publications

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“…for the temperature dependence of k 2 1 (kg 2 ⋅mole -2 ⋅sec -1 ) obtained in processing the experimental values of k 2 1 reported in [15]. Figure 3 shows that in these conditions, postcondensation takes place very rapidly and consequently the duration of the second stage of synthesis will be determined by the duration of dehydration of the melt and correspondingly the design features of the reactor.…”

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confidence: 95%

Liquid-phase hydrolytic polymerization of caprolactam at 483 K

et al. 2007

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Experimental confirmation of the thermodynamic identity of condensation reactions of amino and carboxyl groups in PCA melt and amorphous phase was obtained. It was shown that the Huggins constant of PCA uniformly increases with an increase in the time the polymer is in the molten state and the moisture content of the melt. The expediency of synthesis of PCA prepolymer in stages with k H ≤ 0.25 for two different values of the moisture content of the melt in a reactor with adjustable water vapor pressure was substantiated.Liquid-phase hydrolytic polymerization of caprolactam (CL) at 483 K, i.e., below the melting point of polycaproamide (PCA), is possible if the moisture content of the polymer melt is at the level of ~1 wt. % [1].If we use the relation inwhich correlates the equilibrium degree of polymerization of the polymer with the initial moisture content of the CL melt ([H 2 O] 0 ), expressed in moles per mole CL converted to linear chain units (base-mole),* and the amide equilibrium constant (K) at the given temperature, then it is possible to show that at 483 K (K = 946 [3], α = 0.92 [3]) and initial CL moisture content of 1 wt. %, the equilibrium degree of polymerization of PCA will be equal to ~125. This is already at the level of a fibre-forming polymer, especially in the case of use of technology that provides for nonaqueous extraction of low-molecular-weight compounds (LMC) in the stage of preparing the polymer for fibre spinning and combined drying demonomerization [4]. For this reason, the question regularly arises concerning the duration of such low-temperature synthesis and the possibility of obtaining a polymer with a Huggins constant (k H ) equal to 0.25, which allows spinning fibres with high physicomechanical indexes [5].The results of a study of the kinetics of polymerization of CL at 483 K and the effect of the duration of synthesis and moisture content of the PCA melt on the value of k H are examined below. . 18 16 113 0 2 0 2. is the initial CL moisture content, g/g; 113.16 and 18 are the molecular weight of CL and water, respectively; α = (1 -LMC) is the degree of conversion of CL in linear chain units and LMC is the equilibrium mass fraction of CL and cyclic oligomers in the polymerizate.0015-0541/07/3901-0007

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Liquid-phase hydrolytic polymerization of caprolactam at 483 K

et al. 2007

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Kinetics of depolymerization of polycaprolactam in the presence of water

Mizerovskii¹,

Bazarov²,

Харитонов³

1974

Polymer Science U.S.S.R.

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On the kinetics of the reversible repolyamidation of polycaproamide below the melting point of the polymer

Mizerovskii¹,

Kuznetsov²,

Bazarov³

et al. 1983

Polymer Science U.S.S.R.

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Formal kinetics of the condensation of polycaproamide and the effect of the nature of the molecular weight regulator on the stability of the polymers under repeated melting

Cited by 3 publications

References 9 publications

Liquid-phase hydrolytic polymerization of caprolactam at 483 K

Liquid-phase hydrolytic polymerization of caprolactam at 483 K

Kinetics of depolymerization of polycaprolactam in the presence of water

On the kinetics of the reversible repolyamidation of polycaproamide below the melting point of the polymer

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