Role of magnesium complexes in the anionic polymerization of hexano-6-lactam

Arnoldová, Petra; Brus, Jiřı́; Prokopová, Irena; Brožek, Jiřı́

doi:10.1515/epoly.2006.6.1.867

Cited by 3 publications

(3 citation statements)

References 8 publications

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“…This confirms the accepted point of view that during the polymerization of e-caprolactam with CLMgBr, the disproportion reaction takes place with the in situ formation of CL 2 Mg and MgBr 2 [4,5,25,29,[31][32][33]. On the other hand, an exponential increase of M v with yield was already observed at moderate monomer conversions (i.e., 50-60%) for CLMgBr (Fig.…”

Section: E-caprolactam Magnesium Bromidesupporting

confidence: 87%

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Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

et al. 2011

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The activated anionic ring-opening polymerization of e-caprolactam initiated by 0.35 mol% of combined initiator, i.e., equimolar mixture of magnesium di(e-caprolactamate) (CL 2 Mg) with magnesium halides (MgCl 2 , MgBr 2 , and MgI 2 ) as well as of e-caprolactam magnesium bromide (CLMgBr) in the presence of 0.35 mol% of N-acetyl-e-caprolactam as an activator has been investigated in the temperature range 140-200°C. It was found that the reaction rate increased while the apparent activation energy decreased in the following series: CL 2 Mg/ MgCl 2 \ CL 2 Mg/MgBr 2 * CLMgBr \ CL 2 Mg/MgI 2 . In addition, the poly(ecaprolactam)s prepared with CL 2 Mg/MgX 2 (MgX 2 = MgCl 2 , MgBr 2 , and MgI 2 ) are characterized by slightly higher thermal stability than polymers obtained with CLMgBr as initiator. These observations were explained in terms of the coordination of Lewis acids (MgX 2 , where X = Cl, Br, and I) with imide carbonyl of N-acyllactam end groups leading to the increase of their reactivity and stability.

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Section: E-caprolactam Magnesium Bromidesupporting

confidence: 87%

“…Finally, the formation of the complexes of MgBr 2 with e-caprolactam [31] and various model compounds [32,33] has unambiguously been proven by different analytical techniques. Evidently, the change of the nature of added salt (MgBr 2 ) would influence the reactivity of growing species as well as the reaction rate significantly.…”

Section: Introductionmentioning

confidence: 95%

Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

et al. 2011

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“…While both initiators offer caprolactamates in reaction with CL, CLMgBr offers advantages in terms of ease of handling, lower acidity and less moisture sensitivity when compared with CLNa [18]. In addition, the use of CLMgBr can significantly supress the generation of cyclic oligomers [19].…”

Section: Viscosity Changementioning

confidence: 99%

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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Ethyl magnesium bromide as an efficient anionic initiator for controlled polymerization of ε-caprolactone

Malinová

Brožek

2013

Polym. Bull.

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Role of magnesium complexes in the anionic polymerization of hexano-6-lactam

Cited by 3 publications

References 8 publications

Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

Activated anionic ring-opening polymerization of ε-caprolactam with magnesium di(ε-caprolactamate) as initiator: effect of magnesium halides

Anionic polymerisation of caprolactam: process monitoring and reaction kinetic studies

Ethyl magnesium bromide as an efficient anionic initiator for controlled polymerization of ε-caprolactone

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