Abstract
To introduce a phosphorylcholine (PC) moiety into segmented polyurethane, which has been widely used as an elastic material, the synthesis of a novel diol monomer containing a PC unit was performed. PC-containing polyurethanes were then prepared by polyaddition of the diol monomer and poly(carbonate diol) with 4,4′-diphenylmethane diisocyanate. The obtained polyurethanes were soluble in aprotic polar solvents, such as N,N-dimethylacetamide, N,N-dimethylformamide (DMF) and dimethyl sulfoxide, but were insoluble in water and alcohol. According to thermal analysis and the stress–strain measurements, the polyurethane films exhibited thermal stability up to 250 °C and elastic properties with high tensile strength. In addition, it was confirmed from the results of the protein adsorption experiments that the PC-containing polyurethane films efficiently reduced protein adsorption to the surface.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Lelah, M. D. & Cooper, S. L. Polyurethanes in Medicine, (CRC Press, Boca Raton, 1986).
Eisenbach, C. D., Fischer, K., Hayen, H., Nefzger, H., Ribbe, A. & Stadler, E. Polymeric Materials Encyclopedia Vol. 9, pp 6957–6968 (CRC Press, Boca Raton, 1996).
Zhao, Q., Topham, N., Anderson, J. M., Hiltner, A., London, G. M. & Payet, C. R. Foreign-body giant cells and polyurethane biostability: In vivo correlation of cell adhesion and surface cracking. J. Biomed. Mater. Res. 25, 177–183 (1991).
Wu, Y., Zhao, Q., Anderson, J. M., Hiltner, A., London, G. M. & Payet, C. R. Effect of some additives on the biostability of a poly(ether urethane) elastomer. J. Biomed. Mater. Res. 25, 725–798 (1991).
Zhao, Q. H., McNally, A. K., Rubin, K. R., Renier, M. & Wu, Y. V. Human plasma α2-macroglobulin promotes in vitro oxidative stress cracking of pellethane 2363-80A: In vivo and in vitro correlations. J. Biomed. Mater. Res. 27, 379–388 (1993).
Stokes, K., McVenes, R. & Anderson, J. M. Polyurethane Elastomer Biostability. J. Biomater. Appl. 9, 321–354 (1995).
Kang, I. K., Kwon, O. H., Kim, M. K., Lee, Y. M. & Sung, Y. K. In vitro blood compatibility of functional group-grafted and heparin-immobilized polyurethanes prepared by plasma glow discharge. Biomaterials 18, 1099–1107 (1997).
Mathur, A. B., Collier, T. O., Kao, W. J., Wiggins, M., Schubert, M. A., Hiltner, A. & Anderson, J. M. In vivo biocompatibility and biostability of modified polyurethanes. J. Biomed. Mater. Res. 36, 246–257 (1997).
Flemming, R. G., Proctor, R. A. & Cooper, S. L. Bacterial adhesion to functionalized polyurethanes. J. Biomater. Sci. Polym. Ed. 10, 679–697 (1999).
Roh, H. W., Song, M. J., Han, D. K., Lee, D. S., Ahn, J. H. & Kim, S. C. Effect of cross-link density and hydrophilicity of PU on blood compatibility of hydrophobic PS/hydrophilic PU IPNs. J. Biomater. Sci. Polym. Ed. 10, 123–143 (1999).
Lee, J. H., Ju, Y. M. & Kim, D. M. Platelet adhesion onto segmented polyurethane film surfaces modified by addition and crosslinking of PEO-containing block copolymers. Biomaterials 21, 683–691 (2000).
Khan, I., Smith, N., Jones, E., Finch, D. S. & Cameron, R. E. Analysis and evaluation of a biomedical polycarbonate urethane tested in an in vitro study and an ovine arthroplasty model. Part I: materials selection and evaluation. Biomaterials 26, 621–631 (2005).
Khan, I., Smith, N., Jones, E., Finch, D. S. & Cameron, R. E. Analysis and evaluation of a biomedical polycarbonate urethane tested in an in vitro study and an ovine arthroplasty model. Part II: in vivo investigation. Biomaterials 26, 633–643 (2005).
Ishihara, K., Ueda, T. & Nakabayashi, N. Preparation of phospholipid polymers and their properties as polymer hydrogel membranes. Polym. J. 22, 355–360 (1990).
Ueda, T., Oshida, H., Kurita, K., Ishihara, K. & Nakabayashi, N. Preparation of 2-methacryloxyethyl phosphorylcholine copolymers with alkyl methacrylates and their blood compatibility. Polym. J. 24, 1259–1269 (1992).
Ishihara, K., Hanyuda, H. & Nakabayashi, N. Synthesis of phospholipid polymers having a urethane bond in the side chain as coating material on segmented polyurethane and their platelet adhesion-resistant properties. Biomaterials 16, 873–879 (1995).
Ishihara, K., Tanaka, S., Furukawa, N., Kurita, K. & Nakabayashi, N. Improved blood compatibility of segmented polyurethanes by polymeric additives having phospholipid polar groups I. Molecular design of polymeric additives and their functions. J. Biomed. Mater. Res. 32, 391–399 (1996).
Ishihara, K., Shibata, N., Tanaka, S., Iwasaki, Y., Kurosaki, T. & Nakabayashi, N. Improved blood compatibility of segmented polyurethane by polymeric additives having phospholipid polar group II. Dispersion state of the polymeric additive and protein adsorption on the surface. J. Biomed. Mater. Res. 32, 401–408 (1996).
Iwasaki, Y., Aiba, Y., Morimoto, N., Nakabayashi, N. & Ishihara, K. Semi-interpenetrating polymer networks composed of biocompatible phospholipid polymer and segmented polyurethane. J. Biomed. Mater. Res. 52, 701–708 (2000).
Ishihara, K. & Iwasaki, Y. Biocompatible elastomers composed of segmented polyurethane and 2-methacryloyloxyethyl phosphorylcholine polymer. Polym. Adv. Technol. 11, 626–634 (2000).
Morimoto, N., Iwasaki, Y., Nakabayashi, N. & Ishihara, K. Physical properties and blood compatibility of surface-modified segmented polyurethane by semi-interpenetrating polymer networks with a phospholipid polymer. Biomaterials 23, 4881–4887 (2002).
Nagase, Y., Oku, M., Iwasaki, Y. & Ishihara, Y. Preparations of aromatic diamine monomers and copolyamides containing phosphorylcholine moiety and the biocompatibility of copolyamides. Polym. J. 39, 712–721 (2007).
Horiguchi, K., Shimoyamada, N., Nagawa, D., Nagase, Y., Iwasaki, Y. & Ishihara, K. Syntheses of a novel diamine monomer and aromatic polyamides containing phosphorylcholine group. Trans. Mater. Res. Soc. Jpn 33, 1261–1264 (2008).
Nagase, Y., Nakajima, S., Oku, M., Iwasaki, Y. & Ishihara, K. Synthesis and properties of segmented poly(urethane-urea)s containing phosphorylcholine moiety in the side-chain. Polym. J. 40, 1149–1156 (2008).
Nagase, Y. & Horiguchi, K. Biocompatible Polyamides And Polyurethanes Containing Phospholipid Moiety pp 217–232 (Biomedical Engineering—Frontiers and Challenges, InTech, Croatia, 2011).
Yung, L. L. & Cooper, S. L. Neutrophil adhesion on phosphorylcholine-containing polyurethane. Biomaterials 19, 31–40 (1998).
Edmundson, R. S. Oxidation of cyclic phosphorochloridites. Chem. Ind. 1828–1829 (1962).
Tanaka, H. & Kunimura, M. Mechanical properties of thermoplastic polyurethanes containing aliphatic polycarbonate soft segments with different chemical structures. Polym. Eng. Sci. 42, 1333–1349 (2002).
Eceiza, A., Martin, M. D., Caba, K., de la, Kortaberria, G., Gabilondo, N., Corcuera, M. A. & Mondragon, I. Thermoplastic polyurethane elastomers based on polycarbonate diols with different soft segment molecular weight and chemical structure: mechanical and thermal properties. Polym. Eng. Sci. 48, 297–306 (2008).
Kojio, K., Furukawa, M., Motokucho, S., Shimada, M. & Sakai, M. Structure-mechanical property relationships for poly(carbonate urethane) elastomers with novel soft segments. Macromolecules 42, 8322–8327 (2009).
Chung, Y. C., Choi, J. W., Shin, S. J. & Chun, B. C. Laterally crosslinked polyurethane copolymers with polycarbonate as a soft segment. Fiber Polym 13, 815–822 (2012).
Acknowledgements
We express our sincere gratitude to Professor Kazuhiko Ishihara and Professor Yasuhiko Iwasaki, who are from the School of Engineering, University of Tokyo and from the Faculty of Chemistry, Materials and Bioengineering, Kansai University, respectively, for their scientific and technical support. We also thank Professor Takashi Asaka from the Department of Applied Chemistry, Tokai University, for his help in conducting the stress–strain measurements. This work was partially supported by a Grant-in-Aid for Research from the Tokai University Support Association Union.
Author information
Authors and Affiliations
Corresponding author
Additional information
Supplementary Information accompanies the paper on Polymer Journal website
Supplementary information
Rights and permissions
About this article
Cite this article
Sakagami, Y., Horiguchi, K., Narita, Y. et al. Syntheses of a novel diol monomer and polyurethane elastomers containing phospholipid moieties. Polym J 45, 1159–1166 (2013). https://doi.org/10.1038/pj.2013.48
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2013.48
