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.
White, S.R., Sottos, N.R., Geubelle, P.H., Moore, J.S., Kessler, M.R., Sriram, S.R., Brown, E.N. and Viswanathan, S. ( 2002). Autonomic Healing of Polymer Composites, Nature, 409: 794-797.
2.
Schaubroeck, D., Brughmans, S., Vercaemst, C., Schaubroeck, J. and Verpoort, F. (2006). Qualitative FT-Raman Investigation of the Ring Opening Metathesis Polymerization of Dicyclopentadiene , Journal of Molecular Catalysis A, Chemical, 254: 180-185.
3.
Jones, A.S., Rule, J.D., Moore, J.S., White, S.R. and Sottos, N.R. ( 2006). Catalyst Morphology and Dissolution Kinetics of Self-healing Polymers, Chemistry of Materials, 18: 1312-1317.
4.
Wilson, G.O. , Caruso, M.M., Reimer, N.T., Sottos, N.R. and White, S.R. (2008). Evaluation of Ruthenium Catalysts for Ring-opening Metathesis Polymerization-based Self-healing, Chemistry of Materials, 20: 3288-3297.
5.
Kruger, J., Peetz, L. and Pietralla, M. ( 1978). Brillouin Scattering of Semicrystalline Poly (4-methyl-1-pentene): Study of Surface Effects of Bulk and Film Material, Polymer , 19: 1397-1404.
6.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C. and Pople, J.A. ( 2004). Gaussian 03, Revision C 02, Gaussian Inc., Wallingford, CT.
7.
Becke, A.D. ( 1993). Density-functional Thermochemistry. III. The Role of Exact Exchange, Journal of Chemical Physics, 98: 5648-5652.
8.
Francl, M.M., Pietro, W.J., Hehre, W.J., Binkley, J.S., Gordon, M.S., DeFrees, D.J. and Popple, J.A. ( 1982). Self-consistent Molecular Orbital Methods. XXIII. A Polarization-type Basis Set for Second-row Elements, The Journal of Chemical Physics, 77: 3654-3665.
9.
Hehre, W.J., Ditchfield, R. and Pople, J.A. ( 1972). Self-consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian-type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules, The Journal of Chemical Physics, 56: 2257-2261.
10.
Huang, L. and Kieffer, J. ( 2006). Thermo-mechanical Anomalies and Polyamorphism in B2O3 Glass: A Molecular Dynamics Simulation Study, Physical Review B: Condensed Matter, 74: 224107.
11.
Ionescu, T. , Qi, F., McCabe, C., Striolo, A., Kieffer, J. and Cummings, P. (2006). Evaluation of Forcefields for Molecular Simulation of Polyhedral Oligomeric Silsesquioxanes, Journal of Physical Chemistry B, Focus on Physics, 110: 2502-2510.
12.
Maiti, S., Shankar, C., Geubelle, P.H. and Kieffer, J. ( 2006). Continuum and Molecular-level Modeling of Fatigue Crack Retardation in Self-healing Polymers, Journal of Engineering Materials and Technology, 128: 595-602.
13.
Zhou, J. and Kieffer, J. ( 2008). Simulation of Hexane-functionalized Polyhedral Oligomeric Silsesquioxanes, Journal of Physical Chemistry, 112: 3473-3481.
14.
Barnes, S.E. , Brown, E.C., Corrigan, N., Coates, P.D., Harkin-Jones , E. and Edwards, H.G. (2005). Raman Spectroscopic Studies of the Cure of Dicyclopentadiene (DCPD), Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 61: 2946-2952.
15.
Kieffer, J. , Masnik, J.E., Nickolayev, O. and Bass, J.D. (1998). Structural Developments in Supercooled Alkali Tellurite Melts, Physical Review B, 58: 694-705.
16.
van der Marck, S.C. (1998). Calculation of Percolation Thresholds in High Dimensions for FCC, BCC and Diamond Lattices, International Journal of Modern Physics C, 9: 529-540.
17.
Adlhart, C. , Hinderling, C., Baumann, H. and Chen, P. (2000). Mechanistic Studies of Olefin Metathesis by Ruthenium Carbene Complexes using Electrospray Ionization Tandem Mass Spectrometry, Journal of the American Chemical Society, 122: 8204-8214.
