Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero diels-alder (HDA) chemistry

Espinosa, E., Glassner, M., Boisson, C., Barner-Kowollik, C., & D'Agosto, F. (2011) Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero diels-alder (HDA) chemistry. Macromolecular Rapid Communications, 32(18).

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In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M̄=1 400 as well as 2 800 g a · mol -1, PDI=1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M̄=4 600 g a · mol -1, PDI=1.10) and poly(styrene) (M̄=6 300 g a · mol -1, PDI=1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments. Hetero Diels-Alder (HDA) chemistry was employed for the modular synthesis of block copolymers utilizing polyethylene end capped with a cyclopentadienyl moiety. Poly(isobornyl acrylate) and polystyrene obtained by RAFT polymerization with BPDF as chain transfer agent were used as dienophiles. The success of block copolymer formation was shown by high-temperature SEC and NMR spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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ID Code: 99268
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :15 Export Date: 5 September 2016 CODEN: MRCOE Correspondence Address: Boisson, C.; Laboratoire de Chimie Catalyse Polymères et Procédés (C2P2), Université de Lyon, Equipe LCPP Bat 308F, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France; email: Chemicals/CAS: polyethylene, 9002-88-4; Polyethylene, 9002-88-4; Polymers References: Kim, H.-C., Park, S.-M., Hinsberg, W.D., (2009) Chem. Rev., 110, p. 146; Kim, J.K., Yang, S.Y., Lee, Y., Kim, Y., (2010) Prog. Polym. Sci., 35, p. 1325; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, p. 2004; Iha, R.K., Wooley, K.L., Nyström, A.M., Burke, D.J., Kade, M.J., Hawker, C.J., (2009) Chem. Rev., 109, p. 5620; Inglis, A.J., Barner-Kowollik, C., (2010) Macromol. Rapid Commun., 31, p. 1247; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, T., Van Camp, W., (2011) Angew. Chem., Int. Ed., 50, p. 60; Binder, W.H., Sachsenhofer, R., (2008) Macromol. Rapid Commun., 29, p. 952; Sumerlin, B.S., Vogt, A.P., (2010) Macromolecules, 43, p. 1; Inglis, J., Sinnwell, S., Davis, T.P., Barner-Kowollik, C., Stenzel, M.H., (2008) Macromolecules, 41, p. 4120; Sinnwell, S., Inglis, A.J., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2008) Chem. Commun., 17, p. 2052; Inglis, A.J., Sinnwell, S., Stenzel, M.H., Barner-Kowollik, C., (2009) Angew. Chem., Int. Ed., 48, p. 2411; Inglis, A.J., Paulöhrl, T., Barner-Kowollik, C., (2009) Macromolecules, 43, p. 33; Chung, T.C., (2002) Prog. Polym. Sci., 27, p. 39; Kempe, R., (2007) Chem. Eur. J., 13, p. 2764; Sita, L.R., (2009) Angew. Chem., Int. Ed., 48, p. 2464; D'Agosto, F., Boisson, C., (2010) Aust. J. Chem., 63, p. 1; Mazzolini, J., Espinosa, E., D'Agosto, F., Boisson, C., (2010) Polym. Chem., 1, p. 793; Mazzolini, J., Mokthari, I., Briquel, R., Boyron, O., Delolme, F., Monteil, V., Bertin, D., Boisson, C., (2010) Macromolecules, 43, p. 7495; Briquel, R., Mazzolini, J., Le Bris, T., Boyron, O., Boisson, F., Delolme, F., D'Agosto, F., Spitz, R., (2008) Angew. Chem., Int. Ed., 47, p. 9311; Strazielle, C., Benoit, H., Vogl, O., (1978) Eur. Polym. J., 14, p. 331; Dervaux, B., Junkers, T., Schneider-Baumann, M., Du Prez, F.E., Barner-Kowollik, C., (2009) J. Polym. Sci., Part A: Polym. Chem., 47, p. 6641; MacLean, S., Haynes, P., (1965) Tetrahedron, 21, p. 2343; MacLean, S., Haynes, P., (1965) Tetrahedron, 21, p. 2329; MacLean, S., Haynes, P., (1965) Tetrahedron, 21, p. 2313; Inglis, A.J., Nebhani, L., Altintas, O., Schmidt, F.G., Barner-Kowollik, C., (2010) Macromolecules, 43, p. 5515; Paulöhrl, T., Inglis, A.J., Barner-Kowollik, C., (2010) Adv. Mater., 22, p. 2788; Glassner, M., Blinco, J.P., Barner-Kowollik, C., (2011) Polym. Chem., 2, p. 83; Dervaux, B., Van Camp, W., Van Renterghem, L., Du Prez, F.E., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, p. 1649
Keywords: cyclopentadienyl capped polymers, hetero Diels-Alder cycloaddition, poly(ethylene), reversible addition fragmentation chain transfer, Chain transfer agents, Current system, Cyclopentadienyls, Diels-Alder, Dienophiles, Electronwithdrawing, Elevated temperature, End groups, High temperature, Modular synthesis, RAft polymerization, Reaction temperature, Reversible addition-fragmentation chain transfer polymerization, Thiocarbonyl, Transfer agents, Block copolymers, Copolymerization, Cycloaddition, Directive antennas, Ethylene, Free radical polymerization, Gel permeation chromatography, Living polymerization, Nuclear magnetic resonance spectroscopy, Polyethylenes, Polymers, Polystyrenes, Resonance, Size exclusion chromatography, Styrene, Synthesis (chemical), Plastic products, polyethylene, polymer, article, chemical reaction, chemical structure, chemistry, polymerization, synthesis, Chemical Processes, Molecular Structure
DOI: 10.1002/marc.201100310
ISSN: 10221336
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 03:29

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