Using kinetics and thermodynamics in the controlled synthesis of low molecular weight polymers in free-radical polymerization
Barner-Kowollik, C. & Davis, T. P. (2001) Using kinetics and thermodynamics in the controlled synthesis of low molecular weight polymers in free-radical polymerization. Macromolecular Theory and Simulations, 10(4).
A simple way of controlling molecular weights in the free-radical copolymerization of styrene and a α-methylstyrene (AMS) is presented and investigated by simulation via the program package PREDICI®. It is shown that the molecular weight of the product copolymers may be varied in a wide range (from ̄w = 500 to 2 · 106) by variation of the comonomer feed ratio and the reaction temperature. The reasons for this simple molecular weight control are associated with the AMS comonomer and are threefold: (i) AMS has a low propagation rate coefficient , due to the increased steric requirements of the monomer, (ii) AMS has a transfer to monomer constant (CM) in comparison with styrene and (iii) AMS has a low ceiling temperature, so that the effective propagation rate coefficient decreases with increasing temperature. In addition to the styrene/AMS system, other comonomer systems showing similar kinetic and thermodynamic features (e. g. the styrene/methyl ethacrylate (MEA) system) may also be used to generate a wide range of molecular weights. The possibilities for controlling molecular weight and end group functionalities by replacing the slowly propagating monomer by a functional monomer are discussed.
Impact and interest:
Citation counts are sourced monthly from and citation databases.
These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.
Citations counts from theindexing service can be viewed at the linked Google Scholar™ search.
|Item Type:||Journal Article|
|Additional Information:||Cited By :14
Export Date: 5 September 2016
Correspondence Address: Davis, T.P.; Ctr. for Adv. Macromolecular Design, Sch. of Chemical Engg./Indust. Chem., University of New South Wales, Sydney, NSW 2052, Australia
References: Brandrup, J., Immergut, E.H., (1989) "Polymer Handbook", 3rd edition, , Wiley-Interscience, New York; Karmilova, V.L., Ponomarev, G.V., Smirnov, B.R., Belgovskii, I.M., (1984) Russ. Chem. Rev., 53, p. 132; Davis, T.P., Kukulj, D., Haddleton, D.M., Maloney, D.R., (1995) Trends Polym. Sci., 3, p. 365; Heuts, J.P.A., Forster, D.J., Davis, T.P., Yamada, B., Yamazoe, H., Azukizawa, M., (1999) Macromolecules, 32, p. 2511; Chiefari, J., Chong, Y.K., Ercole, E., Krstina, J., Jeffery, J., Le, T.P.T., Roshan, R.T.A., Thang, S.H., (1998) Macromolecules, 16, p. 31; Kotani, Y., Kamigaito, M., Sawamoto, M., (1999) Macromolecules, 32, p. 6877; Haddleton, D.M., Jasieczek, C.B., Hannon, M.J., Shooter, A.J., (1997) Macromolecules, 30, p. 2190; Xia, J., Zhang, X., Matyjaszewski, K., (1999) Macromolecules, 32, p. 4482; Kukulj, D., Davis, T.P., (1998) Macromolecules, 31, p. 5668; Buback, M., Gilbert, R.G., Hutchinson, R.A., Klumperman, B., Kuchta, F.-D., Manders, B.G., O'Driscoll, K.F., Schweer, J., (1995) Macromol. Chem. Phys., 196, p. 3267; Kukulj, D., Davis, T.P., Gilbert, R.G., (1998) Macromolecules, 31, p. 994; Wulkow, M., (1996) Macromol. Theory Simul., 5, p. 393; Moad, G., Rizzardo, E., Solomon, D.H., Johns, S.R., Willing, R.I., (1984) Makromol. Chem., Rapid Commun., 5, p. 793; Buback, M., Huckestein, B., Kuchta, F.-D., Russell, G.T., Schmid, E., (1994) Macromol. Chem. Phys., 195, p. 2117; Fischer, J.P., (1972) Makromol. Chem., 177, p. 997; Tefera, N., Weickert, G., Bloodworth, R., Schweer, J., (1994) Macromol. Chem. Phys., 195, p. 3067; Buback, M., Kowollik, C., (1999) Macromolecules, 32, p. 1445; Buback, M., Kuchta, F.-D., (1997) Macromol. Chem. Phys., 198, p. 1455; Kapfenstein-Doak, H., Barner-Kowollik, C., Schweer, J., Davis, T.P., (2001) Macromolecules, , in press; Kowollik, C., Davis, T.P., (2000) J. Polym. Sci. Chem., 38, p. 3303; Morris, L.M., Chaplin, R.P., Davis, T.P., Macromol. Chem. Phys., , submitted
|Keywords:||alpha methylstyrene, copolymer, free radical, polymer, styrene, styrene derivative, unclassified drug, article, chemical reaction, chemical reaction kinetics, computer simulation, molecular model, molecular weight, polymerization, synthesis, thermodynamics|
|Divisions:||Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
|Deposited On:||22 Sep 2016 04:50|
|Last Modified:||22 Sep 2016 04:50|
Repository Staff Only: item control page