Preliminary observations on the copolymerisation of acceptor monomer:donor monomer systems under microwave irradiation

• Authors: Christopher Fellows
• Languages of publication: EN

Abstracts

EN

The mechanistic rationalisation of specific ‘microwave effects’ previously reported in a range of chemical reactions suggests that they may be observable in the freeradical copolymerisation of comonomer pairs capable of forming donor-acceptor complexes. Polymerisation under microwave irradiation is carried out for several comonomer pairs with weak donor-acceptor interactions, and no acceleration in rate or change in degree of alternation attributable to changes in propagation are observed. An increase in reaction rate of 150–200 % is observed for all systems, with trends in molecular weight suggesting this was due to an increase in radical flux. This is consistent with earlier reports of rate enhancement for free-radical polymerisations using the initiator 2,2′-azobis-isobutyronitrile, and it is proposed that microwave irradiation may reduce the amount of geminate radical recombination.

Keywords

EN

Free-radical polymerisation; copolymerisation; microwave effect

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2005
• Volume: 3
• Issue: 1
• Pages: 40-52

Dates

published

1 - 3 - 2005

online

1 - 3 - 2005

Contributors

author

Christopher Fellows

References

• [1] M. Nuchter, A. Ondruschka, U. Jungnickel and J. Muller: “Organic processes initiated by non-classical energy sources”, J. Phys. Org. Chem., Vol. 13, (2000), pp. 579–586. http://dx.doi.org/10.1002/1099-1395(200010)13:10<579::AID-POC272>3.0.CO;2-M[Crossref]
• [2] N. Elander, J.R. Jones, S.-Y. Lu and S. Stone-Elander: “Microwave-enhanced radiochemistry”, Chem. Soc. Rev., Vol. 29, (2000), pp. 239–249. http://dx.doi.org/10.1039/a901713e[Crossref]
• [3] L. Bagnell, M. Bliese, T. Cablewski, C.R. Strauss and J. Tsanaktsidis: “Environmentally Benign Procedures for the Preparation and Isolation of 3-Methylcyclopent-2-en-1-one”, Aust. J. Chem., Vol. 50, (1997), pp. 921–926. http://dx.doi.org/10.1071/C97097[Crossref]
• [4] A. Loupy and L. Perreux: “A tentative rationalisation of microwave effects in organic synthesis according to the reaction medium, and mechanistic considerations”, Tetrahedron, Vol. 57, (2001), pp. 9199–9223. http://dx.doi.org/10.1016/S0040-4020(01)00905-X[Crossref]
• [5] C. Gabriel, S. Gabriel, E.H. Grant, B.S.J. Halstead and D.M.P. Mingos: “Delectric parameters relevant to microwave dielectric heating”, Chem. Soc. Rev., Vol. 27, (1998), pp. 213–224. http://dx.doi.org/10.1039/a827213z[Crossref]
• [6] N. Kuhnert: “Microwave-Assisted Reactions in Organic Synthesis-Are there any Non-thermal Microwave Effects”, Angew. Chem. Int. Ed. Engl., Vol. 41, (2002), pp. 1863–1865. http://dx.doi.org/10.1002/1521-3773(20020603)41:11<1863::AID-ANIE1863>3.0.CO;2-L[Crossref]
• [7] C.R. Strauss: “Microwave-Assisted Reactions in Organic Synthesis-Are there any Non-thermal Microwave Effects? Response”, Angew. Chem. Int. Ed. Engl., Vol. 41, (2002), pp. 3589–3590. http://dx.doi.org/10.1002/1521-3773(20021004)41:19<3589::AID-ANIE3589>3.0.CO;2-Q[Crossref]
• [8] K.D. Raner, C.R. Strauss, F. Vyskoc and L. Mokbel: “A Comparison of Reaction Kinetics Observed under Microwave Irradiation and Conventional Heating”, J. Org. Chem., Vol. 58, (1993), pp 950–953. http://dx.doi.org/10.1021/jo00056a031[Crossref]
• [9] D.R. Hofstadter: “Can inspiration be mechanised?”, Scientific American, Vol. 247(3), (1982), pp. 18–31. http://dx.doi.org/10.1038/scientificamerican0982-18[Crossref]
• [10] J.R. Ebdon: “Rate of copolymerisation in strongly alternating systems: the evidence for the involvement of monomer complexes”, Makromol. Chem., Macromol. Symp., Vol. 10/11, (1987), pp. 441–459. [Crossref]
• [11] N.-T. Ha and K. Fujimori: “Theoretical Study of the copolymerization of styrene and maleic anhydride prepared in CCl4 and DMF”, Acta Polym., Vol. 49, (1998), pp. 404–410. http://dx.doi.org/10.1002/(SICI)1521-4044(199808)49:8<404::AID-APOL404>3.0.CO;2-5
• [12] C.M. Fellows and E. Senogles: “Reactivity of Maleic Anhydride toward the 1-Phenylethyl Radical”, Eur. Polym. J., Vol. 34, (1998), pp. 1249–1254. http://dx.doi.org/10.1016/S0014-3057(97)00262-0[Crossref]
• [13] M. Hirooka: “Complexed Radical Mechanism of Alternating Copolymerisation of Vinyl Compounds”, J. Polym. Sci., Polym. Lett. Edn., Vol. 10, (1972), pp. 171–176. http://dx.doi.org/10.1002/pol.1972.110100303[Crossref]
• [14] M.G. Mikhael, A.B. Padias and H.K.J. Hall: “Competition between Diels-Alder cycloaddition and spontaneous copolymerization of 1-methoxy-1,2-butadiene with electrophilic olefins”, Macromolecules, Vol. 26, (1993), pp. 4100–4104. http://dx.doi.org/10.1021/ma00068a005[Crossref]
• [15] Z. Cheng, X. Zhu, G. Chen, W. Xu and L. Lu: “Reverse atom transfer radical solution polymerization of methyl methacrylate under pulsed microwave irradiation”, J. Polym. Sci. A: Polym. Chem., Vol. 40, (2002), pp. 3823–3834. http://dx.doi.org/10.1002/pola.10479[Crossref]
• [16] S.P. Sitaram and J.O. Stoffer: “Microwave initiated free radical catalyzed polymerizations: polystyrene”, Polym. Mat. Sci. Eng., Vol. 69, (1993), pp. 382–383.
• [17] J. Li, J. Zhao and J. Shen: “Microwave-initiated bulk polymerization of methyl methacrylate”, China Synth. Rubb. Ind., Vol. 20, (1997), pp. 53–59.
• [18] H.L. Chia, J. Jacob and F.Y.C. Boey: “The microwave radiation effect on the polymerization of styrene”, J. Polym. Sci. A: Polym. Chem., Vol. 34, (1996), pp. 2087–2094. http://dx.doi.org/10.1002/(SICI)1099-0518(199608)34:11<2087::AID-POLA1>3.0.CO;2-X[Crossref]
• [19] G. Chen, X. Zhu, Z. Cheng and J. Lu: “Controlled/‘living’ radical polymerization of methyl methacrylate with p_TsCl/CuBr/BPY initiating system under microwave irradiation”, Polymer International, Vol. 53, pp. 357–363.
• [20] K.F. O’Driscoll: “The Temperature Dependence of Copolymerisation Reactivity Ratios”, J. Macromol. Sci.-Chem., Vol. A3, (1969), pp. 307–309. [Crossref]
• [21] K.-M. Lee, S.-B. Lee and I.-K. Hong: “Microwave energy effect in styrene/acrylonitrile copolymerization”, J. Korean Ind. Eng. Chem., Vol. 12, (2001), pp. 569–575.
• [22] D.J.T. Hill, J.H. O’Donnell and P.W. O’Sullivan: “Analysis of the Mechanism of copolymerisation of styrene and acrylonitrile”, Macromolecules, Vol. 18, (1982), pp. 960–966. http://dx.doi.org/10.1021/ma00232a004[Crossref]
• [23] D.J.T. Hill, J.H. O’Donnell and P.W. O’Sullivan: “Methyl methacrylate-chloroprene copolymerization: an evaluation of copolymerization models”, Polymer, Vol. 25, (1984), pp. 569–573. http://dx.doi.org/10.1016/0032-3861(84)90221-0[Crossref]
• [24] J. Brandrup, E.H. Immergut and E.A. Grulke (Eds.): Polymer Handbook, 4th Ed., John Wiley and Sons, New York, 1999.
• [25] D. Ghesquiere, R. Arnaud and R.C. Caze: “Conformational and Nuclear Magnetic Resonance studies of the Charge Transfer Complex between Vinyl Acetate and Maleic Anhydride. Reactivity of this Complex in Radical Alternating Copolymerization”, J. Phys. Chem., Vol. 83, (1979), pp. 2029–2034. http://dx.doi.org/10.1021/j100478a021[Crossref]

Identifiers

DOI

10.2478/BF02476236