Abstract
By increasing the hydrophobicity of end group, the complexation rate between α-cyclodextrin (α-CD) and poly(ethylene glycol) (PEG) derivative speeds up greatly. Based on such a huge difference of complexation kinetics, the PEG derivative with palmityloxy terminal (PEG-C16) can be successfully separated from a carboxylic acid end-functionalized analogue (PEG-COOH) by once supramolecular purification. Adding α-CD into the aqueous solution of PEG-C16/PEG-COOH mixture, PEG-C16 is encapsulated into α-CD cavity to form the crystalline inclusion complex in a very short time, while almost all of PEG-COOH molecules are still reserved in the aqueous solution. After dichloromethane extraction, the pure PEG-C16 is obtained. Moreover, the host CD can be recycled. Thus, it is an efficient green way to separate and purify the linear polymers with different terminal functionality.
Similar content being viewed by others
References
Mengerinka, Y., Petersa, R., van der Wala, S.J., Claessensb, H.A., Cramersb, C.A.: Endgroup-based separation and quantitation of polyamide-6,6 by means of critical chromatography. J. Chromatogr. A 949, 337–349 (2002)
Jiang, X.-L., Lima, V., Schoenmakers, P.J.: Robust isocratic liquid chromatographic separation of functional poly(methyl methacrylate). J. Chromatogr. A 1018, 19–27 (2003)
Jiang, X.-L., Schoenmakers, P.J., van Dongen, J.L.J., Lou, X.W., Lima, V., Brokken-Zijp, J.: Mass spectrometric characterization of functional poly(methyl methacrylate) in combination with critical liquid chromatography. Anal. Chem. 75, 5517–5524 (2003)
Jiang, X.-L., Schoenmakersa, P.J., Lou, X.W., Lima, V., van Dongenc, J.L.J., Brokken-Zijp, J.: Separation and characterization of functional poly(n-butyl acrylate) by critical liquid chromatography. J. Chromatogr. A 1055, 123–133 (2004)
Pasch H., Trathnigg B.: HPLC of Polymers. Springer-Verlag, Berlin (1998)
Park, S., Park, I., Chang, T., Ryu, C.Y.: Interaction-controlled HPLC for block copolymer analysis and separation. J. Am. Chem. Soc. 126, 8906–8907 (2004)
Chang, T.: Recent advances in liquid chromatography analysis of synthetic polymers. Adv. Polym. Sci. 163, 1–60 (2003)
Jiang, X.-L.: Separation and characterization of functional polymers. PhD thesis, University of Amsterdam (2004)
Ray, S.K., Sawant, S.B., Joshi, J.B., Pangarkar, V.G.: Development of new synthetic membranes for separation of benzene-cyclohexane mixtures by pervaporation: a solubility parameter approach. Ind. Eng. Chem. Res. 36, 5265–5276 (1997)
Bakos, D., Bleha, T., Ozima, A., Berek, D.: Contribution of adsorption and partition to the separation mechanism in gel chromatography on inorganic carriers. J. Appl. Polym. Sci. 23, 2233–2244 (1979)
Wu, R., Zou, H., Ye, M., Lei, Z., Ni, J.: Capillary electrochromatography for separation of peptides driven with electrophoretic mobility on monolithic column. Anal. Chem. 73, 4918–4923 (2001)
Gorbunov, A., Trathnigg, B.: Theory of liquid chromatography of mono- and difunctional macromolecules I. studies in the critical interaction mode. J. Chromatogr. A 955, 9–17 (2002)
Philipsen, H.J.A.: Determination of chemical composition distributions in synthetic polymers. J. Chromatogr. A 1037, 329–350 (2004)
Barth, H.G., Boyes, B.E., Jackson, C.: Size exclusion chromatography and related separation techniques. Anal. Chem. 70, 251R–278R (1998)
Berek, D.: Coupled liquid chromatographic techniques for the separation of complex polymers. Prog. Polym. Sci. 25, 873–908 (2000)
Entelis, S.G., Evreinov, V.V., Gorshkov, A.V.: Functionality and molecular weight distribution of telechelic polymers. Adv. Polym. Sci. 76, 129–175 (1986)
Xue, J., Jia, Z.F., Jiang, X.-L., Wang, Y.P., Chen, L., Zhou, L., He, P., Zhu, X.Y., Yan, D.Y.: Kinetic separation of polymers with different terminals through inclusion complexation with cyclodextrin. Macromolecules 39, 8905–8907 (2006)
Harada, A., Li, J., Suzuki, S., Kamachi, M.: Complex formation between polyisobutylene and cyclodextrins: inversion of chain-length selectivity between β-cyclodextrin and γ-cyclodextrin. Macromolecules 26, 5267–5268 (1993)
Rusa, C.C., Tonelli, A.E.: Separation of polymers by molecular weight through inclusion compound formation with urea and α-cyclodextrin hosts. Macromolecules 33, 1813–1818 (2000)
Okumura, H., Okada, M., Kawaguchi, Y., Harada, A.: Complex formation between poly(dimethylsiloxane) and cyclodextrins: new pseudo-polyrotaxanes containing inorganic polymers. Macromolecules 33, 4297–4298 (2000)
Harada, A., Li, J., Kamachi, M.: The molecular necklace: a rotaxane containing many threaded α-cyclodextrins. Nature 356, 325–327 (1992)
Harada, A., Li, J., Kamachi, M.: Preparation and properties of inclusion complexes of polyethylene glycol with α-cyclodextrin. Macromolecules 26, 5698–5703 (1993)
Ceccato, M., Lo Nostro, P., Baglioni, P.: α-Cyclodextrin/polyethylene glycol polyrotaxane: a study of the threading process. Langmuir 13, 2436–2439 (1997)
Singla, S., Zhao, T., Beckham, H.W.: Purification of cyclic polymers prepared from linear precursors by inclusion complexation of linear byproducts with cyclodextrins. Macromolecules 36, 6945–6948 (2003)
Harada, A., Kamachi, M.: Complex formation between poly(ethylene glycol) and α-cyclodextrin. Macromolecules 23, 2821–2823 (1990)
Rusa, C.C., Luca, C., Tonelli, A.E.: Polymer-cyclodextrin inclusion compounds: toward new aspects of their inclusion mechanism. Macromolecules 34, 1318–1322 (2001)
Li, J., Ni, X., Zhou, Z., Leong, K.: Preparation and characterization of polypseudorotaxanes based on block-selected inclusion complexation between poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide) triblock copolymers and α-cyclodextrin. J. Am. Chem. Soc. 125, 1788–1795 (2003)
Chen, L., Zhu, X.Y., Yan, D.Y., Chen, Y., Chen, Q., Yao, Y.F.: Controlling polymer architecture through host-guest interactions. Angew. Chem. Int. Ed. 45, 87–90 (2006)
Wenz, G., Han, B.-H., Müller, A.: Cyclodextrin rotaxanes and polyrotaxanes. Chem. Rev. 106, 782–817 (2006)
Allcock, H.R., Sunderland, N.J.: Separation of polymers and small molecules by crystalline host systems. Macromolecules 34, 3069–3076 (2001)
Fang, Y.P., Zhu, X.Y., Yan, D.Y., Lu, Q.H., Zhu, P.F.: Investigations on poly(ethylene oxide)-p-bromotoluene intercalate by in situ heating Fourier transform IR spectroscopy. Colloid Polym. Sci. 280, 59–64 (2002)
Takahashi, Y., Tadokoro, H.: Structural studies of polyethers, (–(CH2)m–O–)n. X. crystal structure of poly(ethylene oxide). Macromolecules 6, 672–675 (1973)
Tadokoro, H., Chatani, Y., Yoshihara, T., Tahara, S.: Structural studies on polyethers, [–(CH2)m–O–]n. II. molecular structure of poly(ethylene oxide). Makromol. Chem. 73, 109–127 (1964)
Ritter, H., Tabatabai, M.: Cyclodextrin in polymer synthesis: a green way to polymers. Prog. Polym. Sci. 27, 1713–1720 (2002)
Szejtli, J.: Introduction and general overview of cyclodextrin chemistry. Chem. Rev. 98, 1743–1753 (1998)
Uekama, K., Hirayama, F., Irie, T.: Cyclodextrin drug carrier systems. Chem. Rev. 98, 2045–2076 (1998)
Li, Y.G., Shi, P.J., Pan, C.Y.: Synthesis, characterization, and thermal behavior of H-shaped copolymers prepared by atom transfer radical polymerization. Macromolecule 37, 5190–5195 (2004)
Xue, J., Chen, L., Zhou, L., Jia, Z.F., Wang, Y.P., Zhu, X.Y., Yan, D.Y.: Effect of end groups on complexation kinetics between cyclodextrins and guest polymers. J. Polym. Sci., Part B: Polym. Phys. 44, 2050–2057 (2006)
Ooya, T., Ito, A., Yui, N.: Preparation of α-cyclodextrin-terminated poly-rotaxane consisting of β-cyclodextrins and pluronic as a building block of a biodegradable network. Macromol. Biosci. 5, 379–383 (2005)
Acknowledgements
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (20574044, 20744002 and 50633010). This work was also partially sponsored by NCET, Shanghai Rising-Star Program (06QA14029).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Xue, J., Zhou, L., He, P. et al. Supramolecular end-group separation of linear polymers with different terminals through host–guest interaction. J Incl Phenom Macrocycl Chem 61, 83–88 (2008). https://doi.org/10.1007/s10847-007-9397-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-007-9397-x