Facile Access to Chain Length Dependent Termination Rate Coefficients via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization: Influence of the RAFT Agent Structure

Feldermann, A., Stenzel, M. H., Davis, T. P., Vana, P., & Barner-Kowollik, C. (2004) Facile Access to Chain Length Dependent Termination Rate Coefficients via Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization: Influence of the RAFT Agent Structure. Macromolecules, 37(7).

View at publisher


A recently developed methodology for determining chain length dependent termination rate coefficients, 〈kt i,i〉, via reversible addition-fragmentation chain transfer (RAFT) polymerizations has been extended and validated for 1-phenylethyl phenyldithioacetate (PEPDA) and 3-benzylsulfanylthiocarbo-nylsulfanylpropionic acid (BSPA) mediated styrene (bulk) free radical polymerizations at 80°C. While the use of cumyl phenyldithioacetate (CPDA) enables a highly precise mapping of the chain length dependence of the termination rate coefficient, employment of PEPDA and BSPA leads to considerable information loss for short chain lengths (i < 10). Careful simulations demonstrate that such behavior is caused by a substantial decrease in the initial transfer effectiveness of the RAFT agents when going from CPDA to BSPA, leading to hybrid behavior between conventional and living free radical polymerization. The observed hybrid behavior is quantifiable via (overall) transfer rate coefficients for the individual RAFT agents in the preequilibrium step [CPDA (ktr,R = 5.0 × 105 L mol-1 s-1), PEPDA (ktr,R = 2.0 × 10 5 L mol-1 s-1), and BSPA (ktr,R = 1.0 × 104 L mol-1 s-1) at 80°C]. The underlying structural cause is the change from a tertiary (CPDA), via a secondary (PEPDA), to a primary (BSPA) leaving group in the initial RAFT agent. Further, the presented simulations open an efficient pathway for approximating overall preequilibrium transfer rate coefficients for the employed RAFT agents.

Impact and interest:

49 citations in Scopus
46 citations in Web of Science®
Search Google Scholar™

Citation counts are sourced monthly from Scopus and Web of Science® 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 the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

ID Code: 99086
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :48
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng./Indust. Chemistry, University of New South Wales, Sydney, NSW 2033, Australia
References: Matyjaszewski, K., (2000) Controlled/Living Radical Polymerization-progress in ATRP, NMP and RAFT, 768. , American Chemical Society: Washington, DC; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev., 101, pp. 3661-3688; Wang, J.S., Matyjaszewski, K., (1995) J. Am. Chem. Soc., 117, pp. 5614-5615; Haddleton, D.M., Crossman, M.C., Dana, B.H., Duncalf, D.J., Heming, A.M., Kukulj, D., Shooter, A.J., (1999) Macromolecules, 32, pp. 2110-2119; Mayadunne, R.T.A., Rizzardo, E., Chiefari, J., Chong, Y.K., Moad, G., Thang, S.H., (1999) Macromolecules, 32, pp. 6977-6980; Moad, G., Chiefari, J., Chong, Y.K., Krstina, J., Mayadunne, R.T.A., Postma, A., Rizzardo, E., Thang, S.H., (2000) Polym. Int., 49, pp. 993-1001; Chong, Y.K., Le, T.P.T., Moad, G., Rizzardo, E., Thang, S.H., (1999) Macromolecules, 32, pp. 2071-2074; Fischer, H., (2001) Chem. Rev., 101, pp. 3581-3610; notePrescott, S.W., (2003) Macromolecules, 36, pp. 9608-9621; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Rapid Commun., 23, pp. 952-956; Müller, A.H.E., Yan, D., Litvinenko, G., Zhuang, R., Dong, H., (1995) Macromolecules, 28, pp. 7335-7338; Müller, A.H.E., Zhuang, R., Yan, D., Litvinenko, G., (1995) Macromolecules, 28, pp. 4326-4333; Litvinenko, G., Müller, A.H.E., (1997) Macromolecules, 30, pp. 1253-1266; Moad, G., Rizzardo, E., Solomon, D.H., Johns, S.R., Willing, R.I., (1984) Makromol. Chem., Rapid Commun., 5, pp. 793-798; Buback, M., Huckestein, B., Kuchta, F.-D., Russell, G.T., Schmid, E., (1994) Macromol Chem. Phys., 195, pp. 2117-2140; Fischer, H., Radom, L., (2001) Angew. Chem., Int. Ed., 40, pp. 1340-1371; Olaj, O.F., Vana, P., Zoder, M., Kornherr, A., Zifferer, G., (2000) Macromol. Rapid Commun., 21, pp. 913-920; Heuts, J.P.A., Gilbert, R.G., Radom, L., (1995) Macromolecules, 28, pp. 8771-8781. , and literature cited therein; Beuermann, S., (2002) Macromolecules, 35, pp. 9300-9305; Willemse, R.X.E., Staal, B.B.P., Van Herk, A.M., Pierik, S.C.J., Klumperman, B., (2003) Macromolecules, 36, pp. 9797-9803; Barner-Kowollik, C., Quinn, J.F., Morsley, D.R., Davis, T.P., (2001) J. Polym. Sci., Polym. Chem., 39, pp. 1353-1365; Barner-Kowollik, C., Quinn, J.F., Nguyen, T.L.U., Heuts, J.P.A., Davis, T.P., (2001) Macromolecules, 34, pp. 7849-7857; Vana, P., Davis, T.P., Barner-Kowollik, C., (2002) Macromol. Theory Simul., 11, pp. 823-835; Perrier, S., Barner-Kowollik, C., Quinn, J.F., Vana, P., Davis, T.P., (2002) Macromolecules, 35, pp. 8300-8306; Zhang, M., Ray, W.H., (2001) Ind. Eng. Chem. Res., 40, pp. 4336-4352; Monteiro, M.J., De Brouwer, H., (2001) Macromolecules, 34, pp. 349-352; Kwak, Y., Goto, A., Tsujii, Y., Murata, Y., Komatsu, K., Fukuda, T., (2002) Macromolecules, 35, pp. 3026-3029; Calitz, F.M., McLeary, J.B., McKenzie, J.M., Tonge, M.P., Klumperman, B., Sanderson, R.D., (2003) Macromolecules, 36, pp. 9687-9690; Ah Toy, A., Vana, P., Davis, T.P., Barner-Kowollik, C., (2004) Macromolecules, 37, pp. 744-751; Coote, M.L., Radom, L., (2003) J. Am. Chem. Soc., 125, pp. 1490-1491; Barner-Kowollik, C., Coote, M.L., Davis, T.P., Radom, L., Vana, P., (2003) J. Polym. Sci., Polym. Chem., 41, pp. 2828-2832; Wang, A.R., Zhu, S., Kwak, Y., Goto, A., Fukuda, T., Monteiro, M.S., (2003) J. Polym. Sci., Polym. Chem., 41, pp. 2833-2839; Vana, P., Quinn, J.F., Davis, T.P., Barner-Kowollik, C., (2002) Aust. J. Chem., 55, pp. 425-431; Monteiro, M.J., Bussels, R., Beuermann, S., Buback, M., (2002) Aust. J. Chem., 55, pp. 433-437; Quinn, J.F., Rizzardo, E., Davis, T.P., (2001) Chem. Commun., pp. 1044-1046; Jesberger, M., Barner, L., Stenzel, M.H., Malmström, E., Davis, T.P., Barner-Kowollik, C., (2003) J. Polym. Sci., Polym. Chem., 41, pp. 3847-3861; Bywater, S., Worsfold, D.J., (1962) J. Polym. Sci., 58, pp. 571-579; Buback, M., Gilbert, R.G., Hutchinson, R.A., Klumperman, B., Kuchta, F.-D., Mandera, B.G., O'Driscoll, K.F., Schweer, J., (1995) Macromol. Chem. Phys., 196, pp. 3267-3280; Breitenbach, J.W., Schindler, A., (1937) Monatsh. Chem., 88, pp. 810-821; Buback, M., Kuchta, F.-D., (1997) Macromol. Chem. Phys., 198, pp. 1455-1480; Barner-Kowollik, C., Vana, P., Davis, T.P., (2002) Handbook of Radical Polymerization, 1st Ed., p. 187. , Davis, T. P., Matyjaszewski, K., Eds.; Wiley-Interscience: New York; Wulkow, M., Busch, M., Davis, T.P., Barner-Kowollik, C., (2004) J. Polym. Sci., Polym. Chem., 42, pp. 1441-1448; Beckwith, A.J.L., Griller, D., Lorand, J.P., (1984) Landolt-börnstein, Numerical Data and Functional Relationships in Science and Technology, New Series, 13 (PART A). , Fischer, H., Ed.; Springer-Verlag: Berlin, Chapter 1; Olaj, O.F., Vana, P., (2000) J. Polym. Sci., Polym. Chem., 38, pp. 697-705; Buback, M., Busch, M., Kowollik, C., (2000) Macromol. Theory Simul., 9, pp. 442-452; noteLansalot, M., Davis, T.P., Heuts, J.P.A., (2002) Macromolecules, 35, pp. 7582-7591; Stenzel, M.H., Davis, T.P., (2002) J. Polym. Sci., Polym. Chem., 40, pp. 4498-4512; Chong, Y.K., Krstina, J., Le, T.P.T., Moad, G., Postma, A., Rizzardo, E., Thang, S.H., (2003) Macromolecules, 36, pp. 2256-2272
Keywords: Approximation theory, Computer simulation, Fourier transform infrared spectroscopy, Molecular structure, Monte Carlo methods, Reaction kinetics, Rate coefficients, Reversible addition fragmentation chain transfer (RAFT, Free radical polymerization
DOI: 10.1021/ma0358428
ISSN: 00249297
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

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page