Abstract
The cyclic starches α-, β-, and γ-cyclodextrins (CDs) readily form inclusion complexes (ICs) with a large variety of polymers. In polymer-CD-ICs, the CD hosts are threaded by the guest polymers, which must be highly extended, and stacks of polymer threaded host CDs pack closely together and crystallize. When guest polymers are coalesced from their CD-IC crystals, by washing with a solvent good, bad for CD, polymer, or treatment with an amylase enzyme, the guest polymers coalesce into bulk samples whose structures, morphologies, and even conformations are distinct from bulk samples made from their solutions and melts. We generally observe (i) crystallizable homopolymers coalesced from their CD-ICs to evidence increased levels of crystallinity, unusual polymorphs, and higher melting, crystallization, and decomposition temperatures, while coalesced amorphous homopolymers exhibit higher glass-transition temperatures, than samples consolidated from their disordered solutions and melts; (ii) molecularly mixed, intimate blends of two or more polymers that are normally believed to be immiscible can be achieved by coalescence from their common CD-IC crystals, (iii) the phase segregation of incompatible blocks can be controlled (suppressed or increased) when block copolymers are coalesced from their CD-IC crystals, and (iv) the thermal and temporal stabilities of the coalesced and well-mixed homopolymer blends and block copolymers appear to be substantial, thereby suggesting retention of as-coalesced structures and morphologies under normal thermal processing conditions. Furthermore, CDs may be covalently incorporated in polymers both during and after their syntheses, thereby providing a broad range of new functionalities for delivery of additives or to act as sensors or filters. Alternatively, additive-CD-ICs or additives rotaxanated with CDs may be effectively delivered to polymers. As an example, TiO2—filled polypropylene fibers may be readily dyed in aqueous solution using water soluble CD-rotaxanated azo-dyes.
Similar content being viewed by others
References
Bullions, T.A., Wei, M., Porbeni, F.E., Gerber, M.J., Peet, J., Balik, C.M., White, J.L., Tonelli, A.E.: Reorganization of the structures and morphologies of bulk polymers via coalescence from their polymer-cyclodextrin inclusion compounds. J. Polym. Sci. Polym. Phys. Ed. 40, 992–1012 (2002)
Wei, M., Bullions, T.A., Rusa, C.C., Wang, X., Tonelli, A.E.: Unique morphological and thermal behaviors of reorganized poly(ethylene terephthalates) J. Polym. Sci. Part B: Polym. Phys. Ed. 42, 386–394 (2003)
Tonelli, A.E.: Can polymers containing rings in their backbones form inclusion compounds with small-molecule, host clathrates? Comput. Theor. Polym. Sci. 2, 80–83 (1992)
Shuai, X., Porbeni, F.E., Wei, M., Bullions, T.A., Tonelli, A.E.: Inclusion complex formation between α,γ-cyclodextrins and a triblock copolymer and the cyclodextrin type-dependent microphase structures of their coalesced samples. Macromolecules 35, 2401–2405 (2002)
Lu, J., Mirau, P.A., Tonelli, A.E.: The dynamics of isolated polycaprolactone chains in their inclusion complexes with cyclodextrins. Macromolecules 34, 3276–3284 (2001)
Rusa, C.C., Wei, M., Shuai, X., Bullions, T.A., Wang, X., Rusa, M., Uyar, T., Tonelli, A.E.: Molecular mixing of incompatible polymers through formation of and coalescence from their common crystalline cyclodextrin inclusion compounds. J. Polym. Sci. Part B: Polym. Phys. Ed. 42, 4207–4224 (2004)
Wei, M., Shuai, X., Tonelli, A.E.: Melting and crystallization behaviors of biodegradable polymers enzymatically coalesced from their cyclodextrin inclusion complexes. Biomacromolecules 4, 783–792 (2003)
Rusa, C.C., Tonelli, A.E.: Polymer/polymer inclusion compounds as a novel approach to obtaining a PLLA/PCL intimately compatible blend. Macromolecules 33, 5321–5324 (2000)
Yang, J.M., Chen, H.L., You, Y.W., Hwang, L.C.: Miscibility and crystallization of poly(l-lactide)/poly(ethylene glycol) and poly(l-lactide)/poly(ɛ-caprolactone) blends. Polym. J. 29, 657–662 (1997)
Jia, X., Wang, X., Tonelli, A.E., White, J.L.: Two-dimensional spin diffusion NMR reveals differential mixing in biodegradable polymer blends. Macromolecules 38, 2775–2780 (2005)
Shuai, X., Wei, M., Porbeni, F.E., Bullions, T.A., Tonelli, A.E.: Formation of and coalescence from the inclusion complex of a biodegradable block copolymer and α-cyclodextrin - 2. Biomacromolecules 3, 201–207 (2002)
Huang, L., Taylor, H., Gerber, M., Orndorff, P., Horton, J., Tonelli, A.E.: Formation of antibiotic, biodegradable/bioabsorbable polymers by processing with neomycin sulfate and its inclusion compound with β-cyclodextrin. J. Appl. Polym. Sci. 74, 937–947 (1999)
Huang, L., Gerber, M., Lu, J., Tonelli, A. E.: Formation of a flame retardant-cyclodextrin inclusion compound and its application as a flame retardant for poly(ethylene terephthalate). Polym. Degrad. Stabil. 71, 279–284 (2001)
Lu, J., Hill, M., Hood, M., Greeson Jr D.F., Horton, R., Orndorff, P.E., Herndon, S.A., Tonelli, A.E.: Formation of antibiotic, biodegradable polymers by processing with Irgasan DP300R (Trichlosan) and its inclusion compound with β-cyclodextrin. J. Appl. Polym. Sci. 82, 300–309 (2001)
Nam, D., Tonelli, A.E.: unpublished observations
Park, J.S., Tonelli, A.E., Srinivasarao M.: Aqueous dyeing of polypropylene fibers with an azo-dye rotaxanated with cyclodextrin. Adv. Mater. Submitted (2007)
Haque, S.A., Park, J.S., Srinivasarao, M., Durrant, J.R.: Molecular-level insulation:an approach to controlling interfacial charge transfer. Adv. Mater. 16(14), 1177–1181 (2004)
Etherton, B.P., McFaddin, D.C.: Method for preparing cyclodextrin-polyolefin blends and products therefrom, US Patent Application (20050043482), Feb. 2005
Romi, R., Lo Nostro, P., Bocci, E., Ridi, F., Baglioni, P.: Bioengineering of a cellulosic fabric for insecticide delivery via grafted cyclodextrin. Biotech. Prog. 21(6), 1724–1730 (2005)
Odian, G.: Principles of Polymerization, 4th edn., pp. 316–325. John Wiley, New York, (2004)
Acknowledgements
I thank my collaborators C. C. Rusa, M. Wei, L. Huang, J. Lu, M. Rusa, X. Shuai, X. Wang, B. Busche, J. S. Park, F. E. Porbeni, I. D. Shin, C. M. Balik, M. Srinivasarao, J. L. White, and I am appreciative of the funding provided by The National Textile Center (US Commerce Dept.), NSF, and NC-State University.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Tonelli, A.E. Cyclodextrins as a means to nanostructure and functionalize polymers. J Incl Phenom Macrocycl Chem 60, 197–202 (2008). https://doi.org/10.1007/s10847-007-9372-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-007-9372-6