Rheokinetic studies for the reaction injection molding of polydicyclopentadiene

Ng, Hendra; Manas‐Zloczower, Ica; Shmorhun, M.

doi:10.1002/pen.760341109

Cited by 18 publications

(7 citation statements)

References 14 publications

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“…The nth-order reaction model is more general and allows for better fits to the data by letting the order of the reaction be determined empirically. The most complex models investigated require four fitting parameters and including both the nth-order autocatalysis model and the expanded Prout-Tompkins (autocatalytic) model [10,11]. Ng and ManasZloczower [11] used the Prout-Tompkins model for a DCPD-based reaction injection molding (RIM) system and found good agreement with experimental results using an adiabatic temperature rise method where the rate of temperature change is related to the rate of reaction through an energy balance for the adiabatic case.…”

Section: Model Performancementioning

confidence: 96%

Cure kinetics of the ring‐opening metathesis polymerization of dicyclopentadiene

Kessler¹,

White²

2002

J. Polym. Sci. A Polym. Chem.

207

149

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Abstract:The cure kinetics of polydicyclopentadiene (pDCPD) prepared by ringopening metathesis polymerization with three different concentrations of Grubbs' catalyst was examined using differential scanning calorimetry (DSC). The experimental data were used to test several different phenomenological kinetic models. The data are best modeled with a "model-free" isoconversional method. This analysis reveals that the activation energy increases significantly for degree of cure greater than 60%. Catalyst concentration is shown to have a large effect on the cure kinetics.

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Section: Model Performancementioning

confidence: 96%

Cure kinetics of the ring‐opening metathesis polymerization of dicyclopentadiene

Kessler¹,

White²

2002

J. Polym. Sci. A Polym. Chem.

207

149

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“…The curing kinetics of the endo-DCPD system have been recently investigated by several researchers. 12−14 Ng et al 12 investigated the rheokinetics of a DCPD-based RIM system and the effect of mixing and initial material temperature on the reaction kinetics; the Sestak-Berggren model (SB model) agreed well with the experimental data, which indicates that the SB model is well suited to describe the reaction kinetics of the DCPD-based system. Kessler et al 13 analyzed the curing kinetics of endo-DCPD with different concentrations of Grubbs' catalyst and tested several reaction models.…”

Section: Introductionmentioning

confidence: 93%

Curing Kinetics and Mechanical Properties of endo-Dicyclopentadiene Synthesized Using Different Grubbs’ Catalysts

Yang

Lee

2014

Ind. Eng. Chem. Res.

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Isothermal curing of endo-dicyclopentadiene (endo-DCPD) using the first and second generation Grubbs’ catalysts as the polymerization initiators was studied by means of differential scanning calorimetry (DSC) according to model-free isoconversional and model-fitting approaches. It revealed that the two Grubbs’ catalysts exhibited apparent differences in ring-opening metathesis polymerization (ROMP) of endo-DCPD. The second generation catalyst was more efficient in catalytic activity for overall ROMP of endo-DCPD than the first generation catalyst, as evident from the reaction rate and fractional conversion (α). The model-free isoconversional method showed similar dependence of the activation energy (E α) on α for the two catalyst systems; however, the second generation catalyst system involved a higher E α, up to α ≈ 0.8, above which the E α value suddenly drops with increase of conversion. The model-fitting method of the ROMP was satisfactorily described by the decelerating reaction and the autocatalytic reaction mechanisms for the first and the second generation catalyst systems, respectively. The effect of diffusion-control was incorporated into the model-fitting method to describe the ROMP reaction throughout the entire conversion. For fully cured samples (poly-DCPD), the first generation catalyst system has higher cross-linking density and lower tensile toughness relative to the second generation. Dynamic mechanical behaviors were also different for poly-DCPD formed using the two catalysts.

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“…While DCPD ROMP kinetics have been previously explored using thermal and rheokinetic analysis, (31,(51)(52)(53)(54)(55) there is little literature on the use of spectroscopy to follow the progress of the ROMP reaction. (56)(57)(58)(59) Figure 4 shows the spectra of DCPD pre-and post-curing at 30 °C.…”

Section: Pure Dcpd Curing Kineticsmentioning

confidence: 99%

Concurrent curing kinetics of an anhydride-cured epoxy resin and polydicyclopentadiene

Rohde

Robertson

Krishnamoorti

2015

Polymer

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The development of interpenetrating polymer networks provides a route to create tough materials that maintain high strength and stiffness, suitable for meeting the demands of an offshore wind turbine environment. This work has focused on a system composed of diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin, contributing high tensile strength and modulus, and polydicyclopentadiene (polyDCPD), which has a higher toughness and impact strength as compared to other thermoset polymers. In situ Fourier transform infrared spectroscopy was used to explore the reaction kinetics in neat, diluted and sequentially cured mixtures of epoxy resin and polyDCPD. There were significant differences in the rate of network formation in the two neat systems, as the rate of anhydride curing of the epoxy was extremely slow at the temperatures required for reasonably measurable dicyclopentadiene (DCPD) ring-opening metathesis polymerization. The dissimilar kinetics of these two systems were leveraged in the design of a sequential curing protocol in which the DCPD was first cured in the presence of the epoxy resin components, followed by curing of the epoxy resin at an elevated temperature. The curing kinetics of the macroscopically phase separated domains of the epoxy resin components in the presence of the polyDCPD network behaved as expected for a diluted epoxy resin. These results provide the kinetic basis for future studies to prepare interpenetrating polymer networks which employ thermodynamic control of phase separation such as through the addition of compatibilizing molecules.

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Rheokinetic studies for the reaction injection molding of polydicyclopentadiene

Cited by 18 publications

References 14 publications

Cure kinetics of the ring‐opening metathesis polymerization of dicyclopentadiene

Cure kinetics of the ring‐opening metathesis polymerization of dicyclopentadiene

Curing Kinetics and Mechanical Properties of endo-Dicyclopentadiene Synthesized Using Different Grubbs’ Catalysts

Concurrent curing kinetics of an anhydride-cured epoxy resin and polydicyclopentadiene

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