Highly orthogonal functionalization of ADMET polymers via photo-induced Diels-Alder reactions

Winkler, M., Mueller, J. O., Oehlenschlaeger, K. K., Montero De Espinosa, L., Meier, M. A. R., & Barner-Kowollik, C. (2012) Highly orthogonal functionalization of ADMET polymers via photo-induced Diels-Alder reactions. Macromolecules, 45(12).

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Within the current contribution, we introduce two strategies for the catalyst-free, modular, ambient temperature synthesis of ABC triblock copolymers via photoinduced Diels-Alder reactions. On the one hand, the 2-formyl-3-methylphenoxy (FMP) moiety (a second generation photoenol precursor) was employed for orthogonal polymer-polymer conjugations using terminal acrylates of diblock copolymers synthesized via acyclic-diene-metathesis (ADMET) polymerizations to directly prepare triblock copolymers. On the other hand, the disparate reactivity of 2,5-dimethylbenzophenone (first generation photoenol) and the FMP moiety was exploited to selectively synthesize complex triblock copolymers (6.5 kDa≥ M n ≥11.5 kDa, 1.16≥ PDI ≥ 1.30) via a sequential one pot approach utilizing the extraordinary orthogonality of the photoinduced Diels-Alder reaction. Polymers functionalized with a photoenol (second generation) moiety were employed for conjugation reactions with polymers featuring an acrylate terminus, while polymers having a photoenol (first generation) end group were employed for selective conjugations of maleimide functional polymers. In this context, the selective head-to-tail ADMET polymerization was employed as a straightforward methodology for the preparation of bifunctional polymers having a terminal acrylate and a photoenol end-group. © 2012 American Chemical Society.

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40 citations in Web of Science®
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ID Code: 99331
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :33
Export Date: 5 September 2016
Correspondence Address: Meier, M.A.R.; Laboratory of Applied Chemistry, Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany; email: m.a.r.meier@kit.edu
References: Liu, F., Urban, M.W., (2010) Prog. Polym. Sci., 35 (1-2), pp. 3-23; Roy, D., Cambre, J.N., Sumerlin, B.S., (2010) Prog. Polym. Sci., 35 (1-2), pp. 278-301; Katz, J.S., Zhong, S., Ricart, B.G., Pochan, D.J., Hammer, D.A., Burdick, J.A., (2010) J. Am. Chem. Soc., 132 (11), pp. 3654-3655; Kim, J.K., Yang, S.Y., Lee, Y., Kim, Y., (2010) Prog. Polym. Sci., 35 (11), pp. 1325-1349; Gohy, J.-F., Abetz, V., (2005) Adv. Polym. Sci., 190, pp. 65-136. , Block Copolymers II, Ed. Springer: Berlin and Heidelberg, Germany, Vol; Frechet, J., (1994) Science, 263 (5154), pp. 1710-1715; Sumerlin, B.S., Vogt, A.P., (2009) Macromolecules, 43 (1), pp. 1-13; Barner-Kowollik, C., Inglis, A.J., (2009) Macromol. Chem. Phys., 210 (12), pp. 987-992; Chmielewski, M.K., (2009) Org. Lett., 11 (16), pp. 3742-3745; 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 (1), pp. 60-62; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40 (11), pp. 2004-2021; Tasdelen, M.A., (2011) Polym. Chem., 2 (10), pp. 2133-2145; Gruendling, T., Oehlenschlaeger, K.K., Frick, E., Glassner, M., Schmid, C., Barner-Kowollik, C., (2011) Macromol. Rapid Commun., 32 (11), pp. 807-812; Meador, M.A.B., Meador, M.A., Williams, L.L., Scheiman, D.A., (1996) Macromolecules, 29 (27), pp. 8983-8986; Tyson, D.S., Ilhan, F., Meador, M.A.B., Smith, D.D., Scheiman, D.A., Meador, M.A., (2005) Macromolecules, 38 (9), pp. 3638-3646; Pauloehrl, T., Delaittre, G., Winkler, V., Welle, A., Bruns, M., Börner, H.G., Greiner, A.M., Barner-Kowollik, C., (2012) Angew. Chem., Int. Ed., 51 (4), pp. 1071-1074; Winkler, M., Montero De Espinosa, L., Barner-Kowollik, C., Meier, M.A.R., (2012) Chem. Sci., , 10.1039/C2SC20402A; Jeffery, T., (1984) J. Chem. Soc., Chem. Commun., 19, pp. 1287-1289; Montero De Espinosa, L., Meier, M.A.R., (2011) Chem. Commun., 47 (6), pp. 1908-1910; Glassner, M., Oehlenschlaeger, K.K., Gruendling, T., Barner-Kowollik, C., (2011) Macromolecules, 44 (12), pp. 4681-4689; Mutlu, H., De Espinosa, L.M., Meier, M.A.R., (2011) Chem. Soc. Rev., 40 (3), pp. 1404-1445; Alston, P.V., Ottenbrite, R.M., Cohen, T., (1978) J. Org. Chem., 43 (10), pp. 1864-1867
Keywords: ABC triblock copolymers, Bifunctional, Catalyst-free, Diels-Alder reaction, End groups, Functionalizations, Functionalized, Maleimides, One pot, Orthogonality, Photo-induced, Photoenol, Second generation, Temperature synthesis, Functional polymers, Olefins, Polymerization, Block copolymers
DOI: 10.1021/ma3007043
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: 30 Sep 2016 03:08

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