Combined experimental and simulation study of the cure kinetics of DCPD

Abstract

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 provide insight into the reaction mechanism. An unexpected dependence of the reaction rate on the catalyst concentration was found.

Keywords

cross-linked polymer networks light scattering molecular dynamics simulation

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References

White SR , Sottos NR , Geubelle PH , Moore JS , Kessler MR , Sriram SR , et al. Autonomic healing of polymer composites. Nature 2002; 409: 794-797.

Schaubroeck D. , Brughmans S. , Vercaemst C. , Schaubroeck J. and Verpoort F. Qualitative FT-Raman investigation of the ring opening metathesis polymerization of dicyclopentadiene. J Mol Catal A Chem 2006; 254: 180-185.

Jones AS , Rule JD , Moore JS , White SR and Sottos NR Catalyst morphology and dissolution kinetics of self-healing polymers. Chem Mater 2006; 18: 1312-1317.

Wilson GO , Caruso MM , Reimer NT , Sottos NR and White SR Evaluation of ruthenium catalysts for ring-opening metathesis polymerization-based self-healing. Chem Mater 2008; 20: 3288-3297.

Kruger J. , Peetz L. and Pietralla M. Brillouin scattering of semicrystalline poly(4-methyl-1-pentene): study of surface effects of bulk and film material. Polymer 1978; 19: 1397-1404.

Frisch MJ , Trucks GW , Schlegel HB , Scuseria GE , Robb MA , Cheeseman JR , et al. Gaussian 03, Revision C.02. Wallingford, CT: Gaussian, Inc, 2004.

Becke AD Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 1993; 98: 5648-5652.

Francl MM , Pietro WJ , Hehre WJ , Binkley JS , Gordon MS , DeFrees DJ , et al. Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for second-row elements. J Chem Phys 1982; 77: 3654-3665.

Hehre WJ , Ditchfield R. and Pople JA Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules. J Chem Phys 1972; 56: 2257-2261.

10.

Huang L. and Kieffer J. Thermo-mechanical anomalies and polyamorphism in B2O3 glass: a molecular dynamics simulation study. Phys Rev B 2006; 74: 224107.

11.

Ionescu T. , Qi F. , McCabe C. , Striolo A. , Kieffer J. and Cummings P. Evaluation of force fields for molecular simulation of polyhedral oligomeric silsesquioxanes. J Phys Chem B 2006; 110: 2502-2510.

12.

Maiti S. , Shankar C. , Geubelle PH and Kieffer J. Continuum and molecular-level modeling of fatigue crack retardation in self-healing polymers. J Eng Mater Technol 2006; 128: 595-602.

13.

Zhou J. and Kieffer J. Simulation of hexane-functionalized polyhedral oligomeric silsesquioxanes . J Phys Chem 2008; 112: 3473-3481.

14.

Barnes SE , Brown EC , Corrigan N. , Coates PD , Harkin-Jones E. and Edwards HG Raman spectroscopic studies of the cure of dicyclopentadiene (DCPD). Spectrochim Acta A Mol Biomol Spectrosc 2005; 61: 2946-2952.

15.

van der Marck SC Calculation of percolation thresholds in high dimensions for FCC, BCC and diamond lattices. Int J Modern Phys C 1998; 9: 529-540.

16.

Adlhart C. , Hinderling C. , Baumann H. and Chen P. Mechanistic studies of olefin metathesis by ruthenium carbene complexes using electrospray ionization tandem mass spectrometry. J Am Chem Soc 2000; 122: 8204-8214.

17.

Kieffer J. , Masnik JE , Nickolayev O. and Bass JD Structural Developments in Supercooled Alkali Tellurite Melts. Phys Rev B 1998; 58: 694-705.