The exothermal effects of superimposed processes of activated anionic polymerization of ε-caprolactam and crystallization of the polymer formed

Malkin, A. Ya.; Beghishev, V. P.; Bolgov, S.A.

doi:10.1016/0032-3861(82)90340-8

Cited by 23 publications

(26 citation statements)

References 1 publication

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“…The kinetic parameters describing the activator C/initiator M system are shown in Table 4. If the average kinetic values E and n , as shown in Table 5, comply well with literature 4, 6, 15, 16. Also the adiabatic temperature during polymerisation, 51 °C, is consistent with the values found in literature 5, 9, 14, 17–21.…”

Section: Resultssupporting

confidence: 90%

“…When the results with a correlation coefficient higher than 90% are considered, it can be seen that more consistent parameters with a low covariance are obtained than compared with the model of Malkin (see Table 5). Also, the activation energy of 71.1 kJ · mol −1 is comparable with the results found in literature4, 6, 15, 16…”

Section: Resultssupporting

confidence: 90%

“…From the results, as shown in Figure 12, a second‐order relationship between the initial temperature of the resin mixture and B 0 can be observed: the lower the initial temperature of the resin mixture, the higher the autocatalytic factor. It is known that a lower initial temperature favours crystallisation,9, 10, 15 which also results in a higher autocatalytic behaviour. This complies with the results shown in Figure 10 where for a T 0 of 140 °C (which is obtained for an initial temperature of the resin of mixture of 85 °C), the rate of crystallisation is maximum.…”

Section: Resultsmentioning

confidence: 99%

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Novel Reaction Kinetic Model for Anionic Polyamide‐6

Teuwen

Geenen

Bersee

2012

Macro Materials & Eng

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Semi‐adiabatic temperature measurements are recorded and used to define semi‐empirical equations for the simulation and prediction of the anionic polyamide‐6 (APA‐6) reaction kinetics. The resin mixture used has a long infusion window before the reaction starts. The prediction of the induction time and its corresponding initial temperature of reaction is explored. By means of this semi‐empirical approach and an optimised fitting procedure, the reaction kinetics of APA‐6 can successfully be described. The adiabatic polymerisation can be predicted on the basis of an autocatalytic Kamal‐Sourour model for thermoset resins, and the crystallisation can be described using the isothermal crystallisation model.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 90%

Section: Resultsmentioning

confidence: 99%

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Novel Reaction Kinetic Model for Anionic Polyamide‐6

Teuwen

Geenen

Bersee

2012

Macro Materials & Eng

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“…The fact that B is decreasing with the increase in concentration of the MDI-capped poly(ethy1ene glycol) agrees qualitatively with the equation derived by Malkin, et aZ., (21), although their equation predicts a much larger rate of decrease for B when the concentration of activator increases. This difference may arise because of the large change in the properties of the mixture.…”

Section: (9) R Trsupporting

confidence: 85%

Kinetic studies of the polymerization of nylon‐6 block copolymers

Limtasiri

Grossman

Huang

1988

Polymer Engineering & Sci

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The kinetics of the activated anionic polymerization of caprolactam to nylon‐6 and its copolymers has been studied. Nylon‐6 block copolymer and nylon‐6 were prepared at various initial reaction temperatures (140°C to 165°C) by anionic polymerization in an adiabatic dewar flask. Different concentrations of poly(ethylene oxide) (PEO) in 4,4′‐diphenyl methane diisocyanate (MDI)‐capped PEO and 1 mole percent MDI, in a caprolactam solution, were used as the activators with the catalyst, the sodium salt of caprolactam. The kinetics of the reaction were analyzed from an adiabatic temperature rise. A new method was applied to determine the rate parameters. The activation energy, Ea, of nylon‐6 and nylon‐6 block copolymers were found to be 22 kcal/mole. The collision frequency factor, Ao, steadily decreased and the autocatalytic constant, Bo, decreased to a constant value of 16 with the introduction of PEO. However, it was found that the order of reaction, n, was almost a constant value at the second order for all experiments.

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“…The validity of Avrami model on the modelling isothermal crystallisation of PA6 has been well presented in literatures [33][34][35][36].…”

Section: Avrami Modelmentioning

confidence: 85%

Anionic polymerisation of caprolactam: process monitoring and reaction kinetic studies

Yang¹

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Reactive processing of PA6 (in-situ anionic polymerization of caprolactam-APCL) enables the production of high performance composite with high mechanical property, good weldability, and recyclability for structural, aerospace and automotive applications.Compare to melt processing, reactive processing enables shorter cycle time, lower processing temperature and pressure. This makes reactive processing a promising new manufacturing technique capable of addressing mass markets.Unfortunately, the insufficient study on influences of processing conditions and reaction kinetics have limited the commercial implementation of the reactive system. This work aims to investigate the processing parameter effect on polymer properties and validate the reaction kinetic models of small scale isothermal polymerization. Experiments were carried out using Differential Scanning Calorimetry (DSC) for the in-situ monitoring of polymerization and crystallization under different processing conditions. Results show that the increase in initiator, activator concentration and polymerization temperature lead to the increase in reaction rate and drop in crystallinity. Whilst this behaviour was expected, the research also shows that the polymer conversion exhibits a far more complex behaviour. For low temperatures, it appears that the monomer conversion is inhibited by early crystallisation whereas for high temperatures the reaction equilibrium shifts towards the monomer state.The derived polymerisation and crystallisation heat flows were used for validation of kinetic models including Kamal-Sourour and Malkin model for polymerisation, Kim model for crystallisation. All experiment data support the validity of Kamal-Sourour model in describing the kinetic development of polymerisation reaction using C1-C20P catalyst system. With the parameters identified from this work, Kamal-Sourour model accurately predict the polymerisation rate under different processing conditions. On the contrast, Malkin polymerisation model failed to give meaningful modelling of the same process. Though Kim crystallisation model gave excellent simulation of the crystallisation process during APCL, the physical meaning of parameter is yet to be determined.

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The exothermal effects of superimposed processes of activated anionic polymerization of ε-caprolactam and crystallization of the polymer formed

Cited by 23 publications

References 1 publication

Novel Reaction Kinetic Model for Anionic Polyamide‐6

Novel Reaction Kinetic Model for Anionic Polyamide‐6

Kinetic studies of the polymerization of nylon‐6 block copolymers

Anionic polymerisation of caprolactam: process monitoring and reaction kinetic studies

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