Postpolymerization modification of hydroxyl-functionalized polymers with isocyanates

Biedermann, F., Appel, E. A., Del Barrio, J., Gruendling, T., Barner-Kowollik, C., & Scherman, O. A. (2011) Postpolymerization modification of hydroxyl-functionalized polymers with isocyanates. Macromolecules, 44(12).

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The postpolymerization functionalization of hydroxyl-group terminated polymers (Mn in the range of 1000-6000 g mol-1) such as poly(ethylene glycol) (PEG), poly(N-isopropylacrylamide) (PNIPAM), poly(N,N-dimethylacrylamide) (PDMAM), and poly(tert-butyl acrylate) (PtBA) with a wide range of functional isocyanate derivatives such as azobenzene, viologen, and anthracene has been investigated. It was shown by 1H and 13C NMR, GPC, Fourier transform infrared spectroscopy (FTIR), and electrospray ionization mass spectrometry (ESI-MS) that a high degree of end-group conversion, typically >98%, with little or no formation of side products can be achieved at ambient temperature. PNIPAM, PDMAM, PtBA, and PHEAM polymers have been obtained by reversible addition-fragmentation chain transfer (RAFT) radical polymerization from a hydroxyl-group containing chain transfer agent (CTA). The formation of the carbamate has been shown to be compatible with the trithiocarbonate end-group of the RAFT polymers. Additionally, this approach allows for the direct functionalization of RAFT polymers without the need of additional steps such as deprotection or aminolysis of the CTA. This route was subsequently used for the preparation of a variety of side-chain functional polymers from poly(N-hydroxyethyl acrylamide) (PHEAM). Three different high yielding methods have been employed to prepare the isocyanates (R-NCO). Either amino or carboxylic acid precursors have been converted into the desired R-NCO or hydroxyl group moieties have been reacted with an excess of 1,6-hexamethylene diisocyanate (HDI) to statistically form the monofunctional product. © 2011 American Chemical Society.

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ID Code: 99266
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :36
Export Date: 5 September 2016
Correspondence Address: Scherman, O. A.; Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, United Kingdom; email:
References: Hawker, C.J., Wooley, K.L., (2005) Science, 309, pp. 1200-1205; Haag, R., Kratz, F., (2006) Angew. Chem., Int. Ed., 45, pp. 1198-1215; Droumaguet, B.L., Nicolas, J., (2010) Polym. Chem., 1, pp. 563-598; Börner, H.G., Kühnle, H., Hentschel, J., (2010) J. Polym. Sci., Part A: Polym. Chem., 48, pp. 1-14; Matyjaszewski, K., (2005) Prog. Polym. Sci., 30, pp. 858-875; Hawker, C.J., Bosman, A.W., Harth, E., (2001) Chem. Rev., 101, pp. 3661-3688; Barner-Kowollik, C., Barner, L., Perrier, S., (2008) Polymers with Well-Defined End Groups Via RAFT-Synthesis, Applications and Postmodifications, , Handbook of RAFT Polymerization; Wiley-VCH Verlag: Weinheim, Germany; Barner, L., Davis, T.P., Stenzel, M.H., Barner-Kowollik, C., (2007) Macromol. Rapid Commun., 28, pp. 539-559; Kamber, N.E., Jeong, W., Waymouth, R.M., Pratt, R.C., Lohmeijer, B.G.G., Hedrick, J.L., (2007) Chem. Rev., 107, pp. 5813-5840; Pitet, L.M., Chamberlain, B.M., Hauser, A.W., Hillmyer, M.A., (2010) Macromolecules, 43, pp. 8018-8025; Hilf, S., Kilbinger, A.F.M., (2007) Macromol. Rapid Commun., 28, pp. 1225-1230; Scherman, O.A., Walker, R., Grubbs, R.H., (2005) Macromolecules, 38, pp. 9009-9014; Barner-Kowollik, C., Du Prez, F.E., Espeel, P., Hawker, C.J., Junkers, T., Schlaad, H., Camp, W.V., (2011) Angew. Chem., Int. Ed., 50, pp. 60-62; Kolb, H.C., Finn, M.G., Sharpless, K.B., (2001) Angew. Chem., Int. Ed., 40, pp. 2004-2021; Laurent, B.A., Grayson, S.M., (2006) J. Am. Chem. Soc., 128, pp. 4238-4239; Johnson, J.A., Finn, M.G., Koberstein, J.T., Turro, N.J., (2007) Macromolecules, 40, pp. 3589-3598; Vogt, A.P., Sumerlin, B.S., (2006) Macromolecules, 39, pp. 5286-5292; Geng, J., Mantovani, G., Tao, L., Nicolas, J., Chen, G., Wallis, R., Mitchell, D.A., Haddleton, D.M., (2007) J. Am. Chem. Soc., 129, pp. 15156-15163; Opsteen, J.A., Van Hest, J.C.M., (2005) Chem. Commun., pp. 57-59; Jia, Z., Bell, C.A., Monteiro, M.J., (2011) Macromolecules, 44, pp. 1747-1751; Kulis, J., Bell, C.A., Micallef, A.S., Jia, Z., Monteiro, M.J., (2009) Macromolecules, 42, pp. 8218-8227; Quemener, D., Davis, T.P., Barner-Kowollik, C., Stenzel, M.H., (2006) Chem. Commun., pp. 5051-5053; Sinnwell, S., Synatschke, C.V., Junkers, T., Stenzel, M.H., Barner-Kowollik, C., (2008) Macromolecules, 41, pp. 7904-7912; Inglis, A., Sinnwell, S., Stenzel, M., Barner-Kowollik, C., (2009) Angew. Chem., Int. Ed., 48, pp. 2411-2414; Gruendling, T., Oehlenschlaeger, K.K., Frick, E., Glassner, M., Schmid, C., Barner- Kowollik, C., (2011) Macromol. Rapid Commun., 32. , (DOI: 10.1002/marc.201100159); Lowe, A.B., (2010) Polym. Chem., 1, pp. 17-36; Scales, C.W., Convertine, A.J., McCormick, C.L., (2006) Biomacromolecules, 7, pp. 1389-1392; Qiu, X.-P., Winnik, F.M., (2006) Macromol. Rapid Commun., 27, pp. 1648-1653; Becer, C., Hoogenboom, R., Schubert, U., (2009) Angew. Chem., Int. Ed., 48, pp. 4900-4908; Sumerlin, B.S., Vogt, A.P., (2009) Macromolecules, 43, pp. 1-13; Binder, W.H., Sachsenhofer, R., (2007) Macromol. Rapid Commun., 28, pp. 15-54; Ladmiral, V., Legge, T.M., Zhao, Y., Perrier, S., (2008) Macromolecules, 41, pp. 6728-6732; Gruendling, T., Pickford, R., Guilhaus, M., Barner-Kowollik, C., (2008) J. Polym. Sci., Part A: Polym. Chem., 46, pp. 7447-7461; Xu, J., He, J., Fan, D., Wang, X., Yang, Y., (2006) Macromolecules, 39, pp. 8616-8624; Zhao, X., Milton Harris, J., (1998) J. Pharm. Sci., 87, pp. 1450-1458; Mongondry, P., Bonnans-Plaisance, C., Jean, M., Tassin, J.F., (2003) Macromol. Rapid Commun., 24, pp. 681-685; Harris, J.M., Struck, E.C., Case, M.G., Paley, M.S., Yalpani, M., Van Alstine, J.M., Brooks, D.E., (1984) J. Polym. Sci., Part A, 22, pp. 341-352; Li, H., Yu, B., Matsushima, H., Hoyle, C.E., Lowe, A.B., (2009) Macromolecules, 42, pp. 6537-6542; Li, Q., Zhou, H., Wicks, D.A., Hoyle, C.E., Magers, D.H., McAlexander, H.R., (2009) Macromolecules, 42, pp. 1824-1833; Tarbell, D.S., Mallatt, R.C., Wilson, J.W., (1942) J. Am. Chem. Soc., 64, pp. 2229-2230; Lligadas, G., Ronda, J.C., Galia, M., Cadiz, V., (2010) Biomacromolecules, 11, pp. 2825-2835; Voit, B.I., Lederer, A., (2009) Chem. Rev., 109, pp. 5924-5973; Brandl, F., Hammer, N., Blunk, T., Tessmar, J., Goepferich, A., (2010) Biomacromolecules, 11, pp. 496-504; Goodson, S.H., Novak, B.M., (2001) Macromolecules, 34, pp. 3849-3855; Flores, J.D., Shin, J., Hoyle, C.E., McCormick, C.L., (2010) Polym. Chem., 1, pp. 213-220; Shioiri, T., Ninomiya, K., Yamada, S., (1972) J. Am. Chem. Soc., 94, pp. 6203-6205; Cotarca, L., Delogu, P., Nardelli, A., Sunjic, V., (1996) Synthesis, 1996, pp. 553-576; Del Barrio, J., Oriol, L., Sanchez, C., Serrano, J.L., Di Cicco, A., Keller, P., Li, M.-H., (2010) J. Am. Chem. Soc., 132, pp. 3762-3769; Mabrouk, E., Cuvelier, D., Brochard-Wyart, F., Nassoy, P., Li, M.-H., (2009) Proc. Natl. Acad. Sci. U.S.A., 106, pp. 7294-7298; Gittins, D.I., Bethell, D., Schiffrin, D.J., Nichols, R.J., (2000) Nature, 408, pp. 67-69; Biedermann, F., Rauwald, U., Zayed, J.M., Scherman, O.A., (2011) Chem. Sci., 2, pp. 279-286; Wu, J., Isaacs, L., (2009) Chem.-Eur. J., 15, pp. 11675-11680; Jeon, W.S., Kim, E., Ko, Y.H., Hwang, I., Lee, J.W., Kim, S.-Y., Kim, H.-J., Kim, K., (2005) Angew. Chem., Int. Ed., 44, pp. 87-91; Moon, K., Grindstaff, J., Sobransingh, D., Kaifer, A.E., (2004) Angew. Chem., Int. Ed., 43, pp. 5496-5499; Biedermann, F., Rauwald, U., Cziferszky, M., Williams, K.A., Gann, L.D., Guo, B.Y., Urbach, A.R., Scherman, O.A., (2010) Chem.-Eur. J., 16, pp. 13716-13722; Moad, G., Rizzardo, E., Thang, S.H., (2008) Polymer, 49, pp. 1079-1131; Celiz, A.D., Scherman, O.A., (2010) J. Polym. Sci., Part A: Polym. Chem., 48, pp. 5833-5841
Keywords: 1 ,6-hexamethylene diisocyanate, Acrylamides, Aminolysis, Chain transfer agents, Deprotection, Electrospray ionization mass spectrometry, End groups, FTIR, Functionalizations, Hydroxyl groups, Monofunctional, NO formation, Poly(N ,N-dimethylacrylamide), Poly(N-isopropyl acrylamide) (pNIPAM), Poly(tert-butyl acrylate) (PtBA), Post-polymerization, Post-polymerization functionalization, Reversible addition-fragmentation chain transfer, Side products, Side-chains, Trithiocarbonate, Viologens, Acrylic monomers, Amides, Amination, Carboxylic acids, Electrospray ionization, Ethylene, Fourier transform infrared spectroscopy, Free radical polymerization, Glycols, Hydrogels, Mass spectrometry, Polyethylene glycols, Functional polymers
DOI: 10.1021/ma2008018
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 01:38

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