In-depth LCCC-(GELC)-SEC characterization of ABA block copolymers generated by a mechanistic switch from RAFT to ROP

Schmid, C., Weidner, S., Falkenhagen, J., & Barner-Kowollik, C. (2012) In-depth LCCC-(GELC)-SEC characterization of ABA block copolymers generated by a mechanistic switch from RAFT to ROP. Macromolecules, 45(1).

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A recently introduced procedure involving a mechanistic switch from reversible addition-fragmentation chain transfer (RAFT) polymerization to ring-opening polymerization (ROP) to form diblock copolymers is applied to synthesize ABA (star) block copolymers. The synthetic steps include the polymerization of styrene with R-group designed RAFT agents, the transformation of the thiocarbonyl thio end groups into OH functionalities, and their subsequent chain extension by ROP. The obtained linear ABA poly(ε- caprolactone)-block-poly(styrene)-block-poly(ε-caprolactone) (pCL-b-pS-b-pCL) (12 500 g mol -1 ≤ M n ≤ 33 000 g mol -1) and the star-shaped poly(styrene)-block-poly(ε- caprolactone) (M n = 36 000 g mol -1) copolymers were analyzed by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, and matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. The focus of the current study is on the detailed characterization of the ABA (star) block polymers via multidimensional chromatographic techniques specifically high performance liquid chromatography coupled to size exclusion chromatography (HPLC-SEC). In particular, we demonstrate the first time separation of poly(ε- caprolactone) (pCL) homopolymer and additionally poly(styrene) (pS) from the ABA poly(ε-caprolactone)-b-poly(styrene)-b-poly(ε-caprolactone) and star-shaped poly(styrene)-b-poly(ε-caprolactone) block copolymer utilizing critical conditions (CC) for pCL with concomitant gradient elution liquid chromatography (GELC). © 2011 American Chemical Society.

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ID Code: 99321
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :22 Export Date: 5 September 2016 CODEN: MAMOB Correspondence Address: Falkenhagen, J.; BAM, Federal Institute for Materials Research and Testing, Richard-Willstaetter-Strasse 11, 12489 Berlin, Germany; email: References: Barner-Kowollik, C., (2008) Handbook of RAFT Polymerization, , Wiley-VCH: Weinheim, Germany; Solomon, D.H., Rizzardo, E., Cacioli, P., (1986), US4581429, (Chem. Abstr. 1985, 102, 221335q)Chiefari, J., Chong, Y.K., Ercole, F., Krstina, J., Jeffery, J., Le, T.P.T., Mayadunne, R.T.A., Thang, S.H., (1998) Macromolecules, 31, pp. 5559-5562; Le, T.P., Moad, G., Rizzardo, E., Thang, S.H., (1998), WO9801478, (Chem. Abstr. 1998, 128, 115390f)Wang, J.-S., Matyjaszewski, K., (1995) Macromolecules, 28 (23), pp. 7901-7910; Kataoka, K., Harada, A., Nagasaki, Y., (2001) Adv. Drug Delivery Rev, 47, p. 113; De Lambert, B., Charreyre, M.-T., Chaix, C., Pichot, C., (2007) Polymer, 48, p. 437; Hales, M., Barner-Kowollik, C., Davis, T.P., Stenzel, M.H., (2004) Langmuir, 20 (25), pp. 10809-10817; You, Y., Hong, C., Wang, W., Lu, W., Pan, C., (2004) Macromolecules, 37 (26), pp. 9761-9767; Tao, L., Luan, B., Pan, C., (2003) Polymer, 44, pp. 1013-1020; Liu, R., Shi, Y., Fu, Z., (2006) Adv. Mater. Res., 1112, pp. 749-752; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 113, p. 2056; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, p. 2004; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, H., Van Camp, W., (2011) Angew. Chem., Int. Ed., 50, pp. 60-62; Gruendling, T., Oehlenschlaeger, K.K., Frick, E., Glassner, M., Schmid, C., Barner-Kowollik, C., (2011) Macromol. Rapid Commun., 32, pp. 807-812; Altintas, O., Hizal, G., Tunca, U., (2008) J. Polym. Sci., Polym. Chem., 46, p. 1218; Quemener, D., Davis, T.P., Barner-Kowollik, C., Stenzel, M.H., (2006) Chem. Commun., pp. 5051-5053; Lefay, C., Glé, D., Rollet, M., Mazzolini, J., Bertin, D., Viel, S., Schmid, C., Barner-Kowollik, C., (2011) J. Polym. Sci., Polym. Chem., 49 (3), pp. 803-813; Gruendling, T., Pickford, R., Guilhaus, M., Barner-Kowollik, C., (2008) J. Polym. Sci., Polym. Chem., 46 (22), pp. 7447-7461; Gründling, T., Dietrich, M., Barner-Kowollik, C., (2009) Aust. J. Chem., 62, pp. 806-812; Dietrich, M., Glassner, M., Gruendling, T., Schmid, C., Falkenhagen, J., Barner-Kowollik, C., (2010) Polym. Chem., 1, pp. 634-644; Schmid, C., Falkenhagen, J., Barner-Kowollik, C., (2011) J. Polym. Sci., Polym. Chem., 49, pp. 1-10; Barner-Kowollik, C., Davis, T.P., Stenzel, M.H.C., (2006) Aust. J. Chem., 59 (10), pp. 719-727; Mishra, A.K., Patel, V.K., Vishwakarma, N.K., Biswas, C.S., Raula, M., Misra, A., Mandal, T.K., Ray, B., (2011) Macromolecules, 44 (8), pp. 2465-2473; Kipping, M., Krahl, F., Döring, A., Adler, H.-J., Kuckling, D., (2010) Eur. Polym. J., 46, pp. 313-323; Wolf, F.F., Friedemann, N., Frey, H., (2009) Macromolecules, 42, pp. 5622-5628; Belenky, B.G., Gankina, E.S., Tennikov, M.B., Vilenchik, L.Z., (1978) J. Chromatogr., 147, p. 99; Entelis, S.G., Evreinov, V.V., Gorshkov, A.V., (1986) Adv. Polym. Sci., 76, p. 129; Pasch, H., Trathnigg, B., (1997) HPLC of Polymers, , Springer: Heidelberg, Germany; MacKo, T., Hunkeler, D., (2003) Liquid Chromatography under Critical and Limiting Conditions: A Survey of Experimental Systems for Synthetic Polymers, 163, pp. 161-216. , Springer: Berlin; Falkenhagen, J., Much, H., Stauf, W., Mueller, A.H.E., (2000) Macromolecules, 33 (10), pp. 3687-3693; Berek, D., (2010) Anal. Bioanal. Chem., 396, pp. 421-441; Berek, D., (2000) Prog. Polym. Sci., 25, pp. 873-908; Pasch, H., Gallot, Y., Trathnigg, B., (1993) Polymer, 34, pp. 4986-4989; Striegel, A.M., Yau, W.W., Kirkland, J.J., Bly, D.D., (2009) Modern Size-Exclusion Liquid Chromatography, , 2 nd ed. Wiley: Hoboken, NJ; Dugo, P., Cacciola, F., Kumm, T., Dugo, G., Mondello, L., (2008) J. Chromatogr., A, 1184, pp. 353-368; Gloeckner, G., Stickler, M., Wunderlich, W., (1988) Fresenius' Z. Anal. Chem., 330, pp. 46-49; Gloeckner, G., Vandenberg, J.H.M., (1991) J. Chromatogr., 550, pp. 629-638; Kilz, P., Kruger, R.P., Much, H., Schulz, G., (1995) Chromatogr. Charact. Polym., 247, pp. 223-241; Van Der Horst, A., Schoenmakers, P.J., (2003) J. Chromatogr., A, 1000, pp. 693-709; Knecht, D., Rittig, F., Lange, R.F.M., Pasch, H., (2006) J. Chromatogr. A, 1130 (1), pp. 43-53; Ahmed, H., Trathnigg, B., Kappe, C.O., Saf, R., (2009) Eur. Polym. J., 45 (8), pp. 2338-2347; Falkenhagen, J., Weidner, S., (2009) Anal. Chem., 81, pp. 282-287; Chaffey-Millar, H., Stenzel, M.H., Davis, T.P., Coote, C., Barner-Kowollik, C., (2006) Macromolecules, 39, p. 6406; Schindler, A., Hibionada, Y.M., Pitt, C.G., (1982) J. Polym. Sci., Polym. Chem., 20, p. 319; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, pp. 331-334; Gruendling, T., Guilhaus, M., Barner-Kowollik, C., (2008) Anal. Chem., 80, pp. 6915-6927; Lohmeijer, B.G.G., Pratt, R.C., Leibfarth, F., Logan, J.W., Long, D.A., Dove, A.P., Nederberg, F., Hedrick, J.L., (2006) Macromolecules, 39, p. 8574; Pratt, R.C., Lohmeijer, B.G.G., Long, D.A., Waymouth, R.M., Hedrick, J.L., (2006) J. Am. Chem. Soc., 128, p. 4556; Ahmed, H., Trathnigg, B., Kappe, C.O., Saf, R., (2010) Eur. Polym. J., 46, p. 494; Ahmed, H., Trathnigg, B., (2009) J. Sep. Sci., 32, p. 1390; Chagneux, N., Trimaille, T., Rollet, M., Beaudoin, E., Gérard, P., Bertin, D., Gigmes, D., (2009) Macromolecules, 42, p. 9435; Jiang, X., Van Der Horst, A., Schoenmakers, P.J., (2002) J. Chromatogr., A, 982, pp. 55-68; Zhang, Y., Liu, H., Dong, H., Li, C., Liu, S., (2009) J. Polym. Sci., Polym. Chem., 47, p. 1636; Liang, C.Y., Krimm, S., (1958) J. Polym. Sci., 27, p. 241; Hesse, M., Meier, H., Zeeh, B., (2005) Spektroskopische Methoden in der Organischen Chemie, , Thieme: Stuttgart
Keywords: ABA block copolymers, Caprolactone, Chain extension, Concomitant gradients, Critical condition, End groups, HPLC-SEC, Matrix-assisted laser desorption/ionization mass spectrometry, Multidimensional chromatographic techniques, RAFT agents, Reversible addition-fragmentation chain transfer polymerization, Thiocarbonyl, Time separation, Block copolymers, Desorption, Free radical polymerization, Functional polymers, High performance liquid chromatography, Liquids, Mass spectrometry, Nuclear magnetic resonance, Nuclear magnetic resonance spectroscopy, Ring opening polymerization, Stars, Styrene, Size exclusion chromatography
DOI: 10.1021/ma2022452
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: 05 Oct 2016 00:12

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