Combined Experimental and Simulation Study of the Cure Kinetics of DCPD

Abstract

In this study, the cure kinetics of dicyclopentadiene was investigated using a combination of inelastic light scattering measurements and molecular-scale simulations. Concurrent Brillouin and Raman scattering served to monitor the structural evolution of the curing network as a function of time, both in terms of network connectivity and the concentration of chemical species present. Density functional theory calculations were used to interpret the measured Raman spectra. Comparison of the measured elastic moduli as a function of the degree of cure with those of structures generated using reactive molecular dynamics simulations provides insight into the reaction mechanism. An unexpected dependence of the reaction rate on the catalyst concentration was found.

Self-healing polymeric materials based on microencapsulated healing agents: From design to preparation

“…The ROMP of DCPD in the presence of Grubbs' catalyst was kinetically studied in ref. [221] The ROMP reaction rate was M a n u s c r i p t ! 48 correlated to the square of the concentration of Grubbs' catalyst.…”

A molecular simulation study of the glass transition of cross-linked poly(dicyclopentadiene) networks

“…In particular, the resistance of crosslinked polymers to high strain rate impact events is desirable for many applications. Accordingly, numerous experimental studies of cross-linked polymers, such as epoxy resins, have been conducted with the overall goal of improving impact resistance [1,[4][5][6]. Although epoxy resins are widely used in applications requiring ballistic performance, resins with the high strength and stiffness necessary for structural applications typically have inferior toughness [7].…”

“…These motions have been reported to improve mechanical properties by dissipating energy [9,10] and are well-understood in epoxies and other common network chemistries [11]. But, despite the common use of pDCPD in applications requiring stiffness, impact resistance, and corrosion resistance, such as chemical process equipment and coverings for heavy machinery, its molecular-level behavior is not well-studied [4,8,12,13]. In this work, we analyze the molecular relaxation mechanisms of pDCPD networks which underlie the experimental observations of temperature-and frequency-dependent bulk properties.…”

Preparation and curing behavior of high-stress solid propellant binder based on polydicyclopentadiene

“…2,3 The reaction scheme is shown in Figure 1. 4 PDCPD is a polymer with high modulus, excellent impact strength, and chemical resistance formed by ROMP of DCPD with Grubbs catalyst. 5 These features, along with its resistance to air and water, 6,7 are leading to the widespread use of PDCPD in military, aerospace, transportation, and construction industries.…”

“…This method was not a scientific method to evaluate the curing degree because the surface of PDCPD was easily oxidized by being exposed to air, which leads to an increase of the network density and higher hardness than internal in the polymer. 13,14 Michael 15 used a combination of inelastic light scattering measurements and molecular-scale simulations to investigate the cure kinetics of DCPD and predicted the mechanical properties of the DCPD networks as a function of the curing degree. Lee 16 investigated the conversion and the glass transition temperature ( T g ) during the isothermal cure of endo-DCPD with Grubbs catalyst by differential scanning calorimetry (DSC), and the conversion reached 67% at 20°C for 480 min.…”