Block copolymers via macromercaptan initiated ring opening polymerization

Lefay, C., Glé, D., Rollet, M., Mazzolini, J., Bertin, D., Viel, S., Schmid, C., Boisson, C., D'Agosto, F., Gigmes, D., & Barner-Kowollik, C. (2011) Block copolymers via macromercaptan initiated ring opening polymerization. Journal of Polymer Science, Part A: Polymer Chemistry, 49(3).

View at publisher


Poly(styrene) macromercaptanes (Mn = 1900, 3600, and 6100 g mol-1, PDI ≈ 1.2) derived from thiocarbonyl thio capped polymers prepared via reversible addition fragmentation chain transfer polymerization were employed to initiate the ring opening polymerization (ROP) of D,L-lactide under conditions of organo-catalyis employing 4,4-dimethylaminopyridine. Poly(styrene)-block-poly(lactide) polymers of number average molecular weights up to 25,000 g mol-1 (PDI ≈ 1.2 to 1.6) were obtained and characterized via multiple detection size exclusion chromatography (SEC) using refractive index as well as UV detection. In addition, diffusion ordered nuclear magnetic resonance and liquid chromatography at critical conditions (of both polystyrene as well as poly(lactide) were employed to assess the copolymers' structure. Furthermore, it was demonstrated that polyethylenes capped with a thiol moiety can also be readily chain extended in a ROP employing D,L-lactide, evidenced via NMR and high temperature SEC. This study indicates that the direct use of macromercaptantes is indeed a methodology to switch from a radical to a ROP process. © 2010 Wiley Periodicals, Inc.

Impact and interest:

15 citations in Scopus
Search Google Scholar™
13 citations in Web of Science®

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: 99277
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :15
Export Date: 5 September 2016
Correspondence Address: Lefay, C.; UMR 6264, Laboratoire Chimie Provence, Université de Provence, Avenue Escadrille Normandie-Niémen, Case 542, Marseille 13397 Cedex 20, France; email:
References: Dechy-Cabaret, O., Martin-Vaca, B., Bourissou, D., (2004) Chem. Rev., 104, pp. 6147-6176; Uhrich, K.E., Cannizzaro, S.M., Langer, R.S., Shakesheff, K.M., (1999) Chem Rev, 99, pp. 3181-3198; Puppi, D., Chiellini, F., Piras, A.M., Chiellini, E., (2010) Prog Polym Sci, 35, pp. 403-440; Nair, L.S., Laurencin, C.T., (2007) Prog Polym Sci, 32, pp. 762-798; Gupta, A.P., Kumar, V., (2007) Eur Polym J, 43, pp. 4053-4074; Anderson, K.S., Schreck, K.M., Hillmyer, M.A., (2008) Polym Rev, 48, pp. 85-108; Rasal, R.M., Janorkar, A.V., Hirta, D.E., (2010) Prog Polym Sci, 35, pp. 338-356; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem Rev, 101, pp. 3661-3688; Kamigaito, M., Ando, T., Sawamoto, M., (2001) Chem Rev, 101, pp. 3689-3745; Matyjaszewski, K., Xia, J.H., (2001) Chem Rev, 101, pp. 2921-2990; Chiefari, J., Chong, Y.K., Ercole, F., Krstina, J., Le, T.P.T., Mayadunne, R.T.A., Meijs, G.F., Thang, S.H., (1998) Macromolecules, 31, pp. 5559-5562; Favier, A., Charreyre, M.T., (2006) Macromol Rapid Commun, 27, pp. 653-692; Moad, G., Rizzardo, E., Thang, S.H., (2005) Aust J Chem, 58, pp. 379-410; Perrier, S., Takolpuckdee, P., (2005) J Polym Sci Polym Chem, 43, pp. 5347-5393; Barner-Kowollik, C., Perrier, S., (2008) J Polym Sci Polym Chem, 46, pp. 5715-5723; Barner, L., Perrier, S., (2008) Handbook of RAFT Polymerization, p. 467. , Barner-Kowollik, C., Ed.; Wiley-VCH: Weinheim; Saeed, A.O., Dey, S., Howdle, S.M., Thurecht, K.J., Alexander, C., (2009) J Mater Chem, 19, pp. 4529-4535; Pratt, R.C., Lohmeijer, B.G.G., Long, D.A., Lundberg, P.N.P., Dove, A.P., Li, H., Wade, C.G., Hedrick, J.L., (2006) Macromolecules, 39, pp. 7863-7871; You, Y., Hong, C., Wang, W., Lu, W., Pan, C.Y., (2004) Macromolecules, 37, pp. 9761-9767; Li, J., Ren, J., Cao, Y., Yuan, W., (2010) Polymer, 51, pp. 1301-1310; Kakwere, H., Perrier, S.J., (2009) J Polym Sci Polym Chem, 47, pp. 6396-6408; Le Hellaye, M., Lefay, C., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2008) J Polym Sci Polym Chem, 46, pp. 3058-3067; Dietrich, M., Glassner, M., Gruendling, T., Schmid, C., Falkenhagen, J., Barner-Kowollik, C., (2010) Polym Chem, 1, pp. 634-644; Gruendling, T., Dietrich, M., Barner-Kowollik, C., (2009) Aust J Chem, 62, pp. 806-812; Schmid, C., Falkenhagen, J., Barner-Kowollik, C., (2011) J Polym Sci Polym Chem, 49, pp. 1-10; Zhang, X., Oddon, M., Giani, O., Monge, S., Robin, J.J., (2010) Macromolecules, 43, pp. 2654-2656; Chiefari, J., Mayadunne, R.T.A., Moad, C.L., Moad, G., Rizzardo, E., Postma, A., Skidmore, M.A., Thang, S.H., (2003) Macromolecules, 36, pp. 2273-2283; Leung, M.K., Hsieh, D.T., Lee, K.H., Liou, J.C., (1995) J Chem Res Synop, 11, pp. 478-479; Chernikova, E.V., Terpugova, P.S., Garina, E.S., Golubev, V.B., (2007) Polym Sci ser A, 49, pp. 108-119; Briquel, R., Mazzolini, J., Bris, T.L., Boyron, O., Boisson, F., Delolme, F., D'Agosto, F., Spitz, R., (2008) Angew Chem Int Ed Engl, 47, p. 9311; Petit, C., Luneau, B., Beaudoin, E., Gigmes, D., Bertin, D., (2007) J Chrom A, 1163, pp. 128-137; Viel, S., Mazarin, M., Giordanengo, R., Phan, T.N.T., Charles, L., Caldarelli, S., Bertin, D., (2009) Anal Chim Acta, 654, pp. 45-48; Moad, G., Chong, Y.K., Postma, A., Rizzardo, E., Thang, S.H., (2005) Polymer, 46, pp. 8458-8468; Xu, J., He, J., Fan, D., Wang, X., Yang, Y., (2006) Macromolecules, 39, pp. 8616-8624; Guillaneuf, Y., Dufils, P.E., Autissier, L., Rollet, M., Gigmes, D., Bertin, D., (2010) Macromolecules, 43, pp. 91-100; MacKo, T., Hunkeler, D., Berek, D., (2002) Macromolecules, 35, pp. 1797-1804; Chang, T., (2005) J Polym Sci Polym Phys, 43, pp. 1591-1607; Srbek, J., Coufal, P., Bosîkovî, Z., Tesarova, E., (2005) J Sep Sci, 28, pp. 1263-1270; Price, W.S., (2009) NMR Studies of Translational Motion: Principles and Applications, , Cambridge University Press: New York; Morris, K.F., Johnson Jr., C.S., (1992) J Am Chem Soc, 114, pp. 3139-3141; Johnson Jr., C.S., (1999) Prog Nucl Magn Reson Spectrosc, 34, pp. 203-256; Chen, A., Wu, D., Johnson Jr., C.S., (1995) J Am Chem Soc, 117, pp. 7965-7970; Jerschow, A., Müller, N., (1998) Macromolecules, 31, pp. 6573-6578; D'Agosto, F., Boisson, C., (2010) Aust J Chem, 63, pp. 1155-1158; Mazzolini, J., Mokthari, I., Briquel, R., Boyron, O., Delolme, F., Monteil, V., Gigmes, D., Boisson, C., (2010) Macromolecules, 43, pp. 7495-7503
Keywords: diblock copolymers, DOSY-NMR, LCCC, polyethylene-block-poly(lactide), polystyrene-block-poly(lactide), reversible addition fragmentation chain transfer (RAFT) polymerization, ring-opening polymerization, thiol initiated ring opening polymerization (ROP), Diblock copolymer, Reversible addition-fragmentation chain transfer polymerization, Block copolymers, Copolymerization, Free radical polymerization, Liquid chromatography, Nuclear magnetic resonance, Organic polymers, Polyethylenes, Polymers, Polystyrenes, Refractive index, Resonance, Size exclusion chromatography, Styrene, Ring opening polymerization
DOI: 10.1002/pola.24496
ISSN: 0887624X
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: 05 Oct 2016 03:56

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page