Role of the functionality of activators during isothermal crystallization accompanying the activated anionic polymerization of ϵ-caprolactam

Bolgov, S.A.; Begishev, V.P.; Malkin, A. Ya.; Frolov, V.G.

doi:10.1016/0032-3950(81)90118-0

Cited by 28 publications

(35 citation statements)

References 4 publications

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“…In this study the parameters in the generalized [16][17][18] than that obtained from the Malkin equation and almost independent of the concentration of macroactivator. The apparent reaction order on the monomer concentration was not a first order but about a 1.5 order.…”

Section: Resultsmentioning

confidence: 99%

Adiabatic anionic polymerization of caprolactam in the presence of N‐acylated caprolactam macroactivator: Kinetic study

Yeh

Kuo

Chen

1993

J of Applied Polymer Sci

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In this study, bis t-caprolactam bis-diphenyl methane diisocyanate polypropylene glycol 1000 used as the macroactivator was prepared and well characterized prior to use. The anionic polymerization of e-caprolactam with the macroactivator as a function of the macroactivator concentration was adiabatically carried out. The adiabatic temperature rise method as well as the macrokinetics were used for elucidation of the kinetics of the polymerization. A nonlinear regression technique was used for determining the parameters of the macrokinetic equation. The equilibrium conversion and equilibrium time obtained were 94-96% and 2-9 min depending on the macroactivator concentration. The effects of the concentrations of macroactivator and e-caprolactam on the initial rate, apparent overall reaction rate, and the empirical parameters were studied. A side reaction induced by the transfer of the proton in the isocyanurate group of the macroactivator to caprolactam anion was found. According to this finding, a new reaction kinetic model was proposed by properly modifying the macrokinetic equation. 0 1993 John Wiley & Sons, Inc. I NTRO DU CTI 0 NThe emergence of reaction injection molding (RIM) has been followed by the industry with mounting interest. RIM is based on the injection of monomers or reactive oligomers into a mold followed by a fast polymerization reaction. The attractiveness of the process is in saving energy and capital investments as well as the ease of molding of large, thin-walled, and complicated shapes.' Therefore, the RIM process has been rapidly developed by the automotive industry since Bayer AG of Germany started the Baydur System with polyurethane 20 years ago.' " In 1981 Monsanto Chemical Co. of the US. announced that it was engaged in the development of a RIM system of Nylon 6 for exterior parts of automobile~.~ This aroused great interest and Nylon RIM rapidly grew to be the new second RIM. The Nylon RIM system combines the characteristics of

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Section: Resultsmentioning

confidence: 99%

Adiabatic anionic polymerization of caprolactam in the presence of N‐acylated caprolactam macroactivator: Kinetic study

Yeh

Kuo

Chen

1993

J of Applied Polymer Sci

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“…The equation that was used for separating the heat flux from polymerisation and crystallisation was described by Bolgov et al 10 in which α is the degree of crystallinity at time t , Q 1 is the heat of polymerisation (J · kg −1 ) and Q 2 is the heat of crystallisation (J · kg −1 ).…”

Section: Modellingmentioning

confidence: 99%

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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“…Yields of PolymerizationFigure4 Example of kinetic model predictions vs. adiabatic data: 1 mol % PCC system. Initial reaction temperature is 160°C.yields for polymerization at high initial temperatures (150 and 160°C) are relatively low.…”

mentioning

confidence: 99%

Mechanism and kinetics of adiabatic anionic polymerization of ϵ‐caprolactam in the presence of various activators

Kim

Yoon

et al. 1995

J of Applied Polymer Sci

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SYNOPSISNylon 6 was prepared by adiabatic anionic polymerization of ecaprolactam using hexamethylene dicarbamoyl dicaprolactam (HDC), cyclohexyl carbamoyl caprolactam (CCC), or phenyl carbamoyl caprolactam (PCC) as activators and sodium caprolactamate (NaCL) as a catalyst at various initial reaction temperatures ranging from 130 to 160°C. Adiabatic temperature rise was recorded as a function of polymerization time to investigate polymerization kinetics. Kinetic parameters for polymerization, which are more accurate than data reported to date, could be obtained by fitting the temperature rise data with a new polymerization kinetic equation involving crystallization exotherm and thermal conduction. The polymerization rate highly depended on the chemical structure of the activator used, which indicates that the initiating step where the activator is attacked nucleophilically by NaCL is a very important reaction step, affecting the overall polymerization rate. CCC showed the fastest polymerization rate, whereas HDC and PCC showed the medium and the slowest rate, respectively. The contributions of crystallization exotherm and thermal conduction to the resultant temperature rise during polymerization were significant, when the initial reaction temperature was lower than 140°C. In all cases, the molecular weight obtained from intrinsic viscosity measurement was greater than the expected molecular weight. This may be attributed to the branching and/or crosslinking reaction through Claisen-type condensation reactions. 0

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Role of the functionality of activators during isothermal crystallization accompanying the activated anionic polymerization of ϵ-caprolactam

Cited by 28 publications

References 4 publications

Adiabatic anionic polymerization of caprolactam in the presence of N‐acylated caprolactam macroactivator: Kinetic study

Adiabatic anionic polymerization of caprolactam in the presence of N‐acylated caprolactam macroactivator: Kinetic study

Novel Reaction Kinetic Model for Anionic Polyamide‐6

Mechanism and kinetics of adiabatic anionic polymerization of ϵ‐caprolactam in the presence of various activators

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