Equilibrium in the system polycaproamide-caprolactam-water below the melting point of the polymer

Mizerovskii, L. N.; Kuznetsov, A. K.; Bazarov, Yu. M.; Bykov, A. N.

doi:10.1016/0032-3950(82)90404-x

Cited by 10 publications

(14 citation statements)

References 15 publications

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“…1) that the temperature dependence of quantities K 2 , calculated with Eq. (2) for the 443-483 K temperature range and obtained in many independent studies of the liquid-phase reaction at 493-560 K, is satisfactorily described by one equation [17] …”

Section: Condensation Equilibrium In the Polyamidewater System Below mentioning

confidence: 75%

“…Equation (17) actually applies to the analysis of the kinetics of reversible additional polycondensation of PA-6 in the solid phase, and this not only concerns the direct reaction, but also the reverse reaction which, as noted above, can formally take place with any amide groups and molecules of water in the amorphous phase of the polymer [30,32]. ____________ *In the given case, the concept of readiness also includes the possibility of finding the members of a contact pair at different distances from each other as a result of their vibrational movements.…”

Section: Kinetics Of Reversible Solid-phase Polycondensation Of Polyamentioning

confidence: 99%

“…In our attempts to compare the values of K 3 obtained in studying liquid-and solid-phase polymerization of CL, we came up against [17,27] the problem of the dependence of K 3 , calculated both with Eq. (6) and with Eq.…”

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

“…The duration of the syntheses was 768-816 h at 459 K [29], 368-570 h at 483-443 K [17], and 200 h at 423-463 K [27]. In this study, we used extrapolation of functions [CL] = ƒ(τ -1 ) and [OL] = ƒ(τ -1 ), plotted with the last 4-5 points of the kinetic curves in the region where they went out on a plateau, to τ → ∞ to determine [CL] e and…”

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

“…The values of the equilibrium concentrations of CL and cyclic oligomers in PA-6 undergoing solid-phase additional polymerization [17,29] and depolymerization [29], and in PA-6 modified with 7% AG salt and undergoing additional polymerization [27] are reported in Table 2. The duration of the syntheses was 768-816 h at 459 K [29], 368-570 h at 483-443 K [17], and 200 h at 423-463 K [27].…”

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

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Solid-phase synthesis of polyamide-6

Mizerovskii

Bazarov

2006

Fibre Chem

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678.675:66 09Solid-phase synthesis of PA-6, simultaneously discovered with the reaction of conversion of CL into a polymer and of practical interest primarily as a method for obtaining a polymer constructed of strictly linear macromolecules and containing a minimum amount of CL and especially cyclic oligomers, is not solid-phase in the generally understood meaning of this term. This essentially concerns a set of liquid-phase reactions which differ from ordinary reactions due to the fact that some of the participants and primarily the solvent molecules, which the kinetic segments of transfer chains act as, are free of translational mobility, and the entire reaction volume is in a stressed state due to differences in the coefficients of thermal expansion of amorphous and crystalline microregions of the polymer and the developed process of additional crystallization. The presence of an important reaction volume which persists in a relatively wide temperature range and the very large amplitudes of vibrations of translationally immobile reactive groups makes the process kinetically more advantageous than solid-phase polycondensation of monomeric ε-aminocaproic acid.Low-temperature hydrolytic polymerization of caprolactam (CL) accompanied by crystallization of the polycaproamide formed (PA-6) and the subsequent evolution of the reaction as formally solid-phase was described for the first time in the patent [1] obtained by Hubert and Ludewig in Germany in 1939. The possibility of this process also follows from the sense of the patents [2, 3] obtained by Schlack in Germany in 1938 and in the US in 1941.In 1942, this version of synthesis of PA-6 was used by Staudinger and Warder .4, p. 19/] for obtaining a polymer of rigorously linear structure. However, it has not yet been implemented on the industrial scale due to the lack of an acceptable method of giving the solid polymer a shape convenient for processing it into yarn [5, p. 90].The studies conducted in [1959][1960][1961][1962][1963][1964][1965][1966][1967][1968][1969][1970][1971][1972] showed that Klares ideas [5, p. 90] concerning solid-phase synthesis of PA-6 from ε-aminocaproic acid were also practically unrealizable.The low rate of the process and mainly the very narrow temperature range in which the first stage can take place conversion of the monomer into an oligomer are a stumbling block in this case.Moreover, the research conducted in this period on solid-phase additional polycondensation of demonomerized PA-6 obtained by purely liquid-phase hydrolytic polymerization of CL to significantly increase its molecular weight and correspondingly the physicomechanical indexes of the spun yarns allowed Kudryavtsev, Nosov, and Volokhina to conclude in the second half of the 70s that the technical and economic advantages of solid-phase complete polyamidation of such PA-6 are obvious, but the process and implementation of the process require further development [6].Today solid-phase additional polycondensation is widely used in synthesis of high-molecular-weight polyethy...

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Section: Condensation Equilibrium In the Polyamidewater System Below mentioning

confidence: 75%

Section: Kinetics Of Reversible Solid-phase Polycondensation Of Polyamentioning

confidence: 99%

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

Section: Equilibrium In the Polycaproamidecaprolactam System Below Thmentioning

confidence: 99%

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Solid-phase synthesis of polyamide-6

Mizerovskii

Bazarov

2006

Fibre Chem

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Solid‐State Polymerization

Vouyiouka¹,

Papaspyrides²

2011

Encyclopedia of Polymer Science and Technology

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Solid‐state polymerization (SSP) comprises a bulk polymerization technique industrially applied for step‐growth polymers. It involves heating the starting material (crystalline monomer or prepolymer) in an inert atmosphere or under vacuum, at a temperature below its melting point, permitting the initiation and propagation of typical polymerization reactions. Both chemical and physical steps occur during an SSP process, namely chemical reactions, reactive chain end movement in the amorphous phase, and condensate removal through diffusion. These phenomena are herewith discussed and correlated to operational variables, such as reaction temperature, initial stoichiometry and crystallinity, reacting particles size, condensate content in the surroundings, catalyst's presence. Equipment requirements and pertinent assemblies are also presented, and SSP of the most important polyamides and polyesters is summarized.

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Fundamentals of Solid State Polymerization

Papaspyrides

Vouyiouka

2009

Solid State Polymerization

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Condensation polymers: PET, unsaturated polyesters Ziegler Natta catalysts • Development of new manufacturing methods • Expansion of additives, new catalysts • Development of new sophisticated structures, e.g. nanocomposite, biodegradable materials 1907: The first synthetic polymer: Bakelite was invented 1839: C.Goodyear developed the vulcanization process 1860: Birth of plastics industry: Celluloid, the first man-made thermoplastic, was prepared.

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Equilibrium in the system polycaproamide-caprolactam-water below the melting point of the polymer

Cited by 10 publications

References 15 publications

Solid-phase synthesis of polyamide-6

Solid-phase synthesis of polyamide-6

Solid‐State Polymerization

Fundamentals of Solid State Polymerization

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