HYDROXYL-FUNCTIONALIZED HYPERBRANCHED ALIPHATIC POLYESTERS BASED ON 1,1,1-TRIS(HYDROXYMETHYL)PROPANE (TMP) AS A CORE MOLECULE: SYNTHESIS AND CHARACTERIZATION

The aim of this study is to synthesize and characterize the new hydroxyl-functionalized hyperbranched aliphatic polyesters with various generations for potential use in cancer therapy as targeted drug delivery system. For this purpose, a series of novel hydroxyl-functionalized hyperbranched aliphatic polyesters (HBPs) based on 2,2-bis(hydroxymethyl)butyric acid (Bis-HBA) as AB2-type monomer and 1,1,1-tris(hydroxymethyl)propane (TMP) as B3 core molecule were synthesized via acid catalyzed polyesterification reaction in three different generations and named as HBP-2G, HBP-4G and HBP-5G. The synthesis route was a simple pseudo-one-step reaction where AB2-type monomer and B3 core molecule are polycondensed in the presence of an acid catalyst. The chemical structures of the synthesized HBPs were confirmed by FTIR, 13C NMR and 1H NMR analysis. The degree of branching (DB) of the HBPs as calculated from 1H NMR results were between 0.87 and 0.92. These results showed that all synthesized HBPs had a high degree of branching. TGA measurements exhibited that all of HBPs had similar and good thermal stability. Glass transition temperatures (Tg) of samples were identified using DSC analysis and were found to be between 66.2 °C and 69.1 °C. Low generation HBPs have considerably higher solubility in organic solvents than high generation HBPs. All synthesized HBPs displayed extremely low water solubility but extremely high solubility in dimethyl sulfoxide. It was concluded that new HBPs which were synthesized in this study have reasonable characteristics for hyperbranched polymers applications.

___

  • [1] Yan D., Gao C., Frey H., (2011) Hyperbranched polymers: synthesis, properties, and applications. John Wiley & Sons: Hoboken, New Jersey.
  • [2] Johansson M., Glauser T., Jansson A., Hult A., Malmström E., Claesson H., (2003) Design of coating resins by changing the macromolecular architecture: solid and liquid coating systems, Prog. Org. Coat. 48(2), 194-200.
  • [3] Johansson M., Glauser T., Rospo G., Hult A. J., (2000) Radiation curing of hyperbranched polyester resins, Appl. Polym. Sci. 75(5), 612-618.
  • [4] Johansson K., Bergman T., Johansson M., (2008) Hyperbranched aliphatic polyesters and reactive diluents in thermally cured coil coatings, ACS Appl. Mater. Inter. 1(1), 211-217.
  • [5] Haxton K. J., Burt H. M., (2008) Hyperbranched polymers for controlled release of cisplatin, Dalton Trans. 43, 5872-5875.
  • [6] Kolhe P., Misra E., Kannan R. M., Kannan S., Lieh-Lai M., (2003) Drug complexation, in vitro release and cellular entry of dendrimers and hyperbranched polymers, Int. J. Pharm. 259(1), 143-160.
  • [7] Gao C., Yan D., (2004) Hyperbranched polymers: from synthesis to applications, Prog. Polym. Sci. 29(3), 183–275.
  • [8] Seiler M., (2006) Hyperbranched polymers: Phase behavior and new applications in the field of chemical engineering, Fluid Phase Equilibr. 241(1), 155-174.
  • [9] Tomalia D. A., Fréchet J. M., (2002) Discovery of dendrimers and dendritic polymers: a brief historical perspective, J. Polym. Sci. A2. 40(16), 2719-2728.
  • [10] Bosman A. W., Janssen H. M., Meijer E. W., (1999) About dendrimers: structure, physical properties, and applications, Chem. Rev. 99(7), 1665-1688.
  • [11] Ihre H., Hult A., Söderlind E. J., (1996) Synthesis, characterization, and 1H NMR self-diffusion studies of dendritic aliphatic polyesters based on 2, 2-bis (hydroxymethyl) propionic acid and 1, 1, 1-tris (hydroxyphenyl) ethane, Am. Chem. Soc. 118(27), 6388-6395.
  • [12] Freemantle M., (1999) Blossoming of dendrimers, Chem. Eng. News. 77(44), 27-35.
  • [13] Zagar E., Zigon M., (2011) Aliphatic hyperbranched polyesters based on 2, 2-bis (methylol) propionic acid—Determination of structure, solution and bulk properties, Prog. Polym. Sci. 36(1), 53–88.
  • [14] Schmaljohann D., Komber H., Voit B. I., (1999) Conversion dependence of the structural units and the degree of branching of a hyperbranched polyester based on 4, 4-bis-(4′-hydroxyphenyl) pentanoic acid determined by NMR spectroscopy, Acta Polym. 50(5-6), 196–204.
  • [15] Scholl M., Nguyen T. Q., Bruchmann B., Klok H. A., (2007) Controlling polymer architecture in the thermal hyperbranched polymerization of L-Lysine, Macromolecules 40(16), 5726-5734.
  • [16] Kou Y., Wan A., Tong S., Wang L., Tang J., (2007) Preparation, characterization and modification of hyperbranched polyester-amide with core molecules, React. Funct. Polym. 67(10), 955–965.
  • [17] Soccio M., Finelli L., Lotti N., Marchese P., Siracusa V., Munari A., (2007) A novel hyperbranched polyester based on 2, 2-bis (hydro xylmethyl) butyric acid: synthesis and characterization, e-Polymers 7(1), 564-577.
  • [18] Müller A. H., Yan D., Wulkow M., (1997) Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization, Macromolecules 30(23), 7015-7023.
  • [19] Yan D., Müller A. H., Matyjaszewski K., (1997) Molecular parameters of hyperbranched polymers made by self-condensing vinyl polymerization. 2. Degree of branching, Macromolecules 30(23), 7024-7033.
  • [20] Boye S., Komber H., Friedel P., Lederer A., (2010) Solution properties of selectively modified hyperbranched polyesters, Polymer 51(18), 4110-4120.
  • [21] Zhu Z., Kai L., Wang Y., (2006) Synthesis and applications of hyperbranched polyesters—preparation and characterization of crystalline silver nanoparticles, Mater. Chem. Phys. 96(2), 447-453.
  • [22] Komber H., Ziemer A., Voit B., (2002) Etherification as side reaction in the hyperbranched polycondensation of 2, 2-bis (hydroxymethyl) propionic acid, Macromolecules 35(9), 3514-3519.
  • [23] Magnusson H., Malmstrom E., Hult A., (2000) Structure buildup in hyperbranched polymers from 2, 2-bis (hydroxymethyl) propionic acid, Macromolecules 33(8), 3099-3104.
  • [24] Sunder A., Hanselmann R., Frey H., Mulhaupt R., (1999) Controlled synthesis of hyperbranched polyglycerols by ring-opening multibranching polymerization, Macromolecules 32(13), 4240-4246.
  • [25] Hanselmann R., Holter D., Frey H., (1998) Hyperbranched polymers prepared via the core-dilution/slow addition technique: computer simulation of molecular weight distribution and degree of branching, Macromolecules 31(12), 3790-3801.
  • [26] Magnusson H., Malmström E., Hult, A., Johansson M., (2002) The effect of degree of branching on the rheological and thermal properties of hyperbranched aliphatic polyethers, Polymer 43(2), 301-306.
  • [27] Holter D., Burgath A., Frey H., (1997) Degree of branching in hyperbranched polymers, Acta Polym. 48(1-2), 30-35.
  • [28] Hawker C. J., Lee R., Frechet J. M. J., (1991) One-step synthesis of hyperbranched dendritic polyesters, J. Am. Chem. Soc. 113(12), 4583–4588.
  • [29] Murillo E. A., Vallejo P. P., López B. L., (2011) Effect of tall oil fatty acids content on the properties of novel hyperbranched alkyd resins, J. Appl. Polym. Sci. 120(6), 3151-3158.
  • [30] Malmstrtjm E., Johansson M., Hult A., (1995) Hyperbranched aliphatic polyesters, Macromolecules 28(5), 1698-1703.
  • [31] Socrates G., (2001) Infrared and Raman Characteristic Group Frequencies: Tables and Charts, John Wiley and Sons Inc., England.
  • [32] Jiang G., Wang L., Chen T., Yu H., Dong X., Chen C., (2005) Synthesis and self-assembly of hyperbranched polyester peripherally modified by touluene-4-sulfonyl groups, Polymer 46(22), 9501-9507.
  • [33] Zagar E., Zigon M., Podzimek S., (2006) Characterization of commercial aliphatic hyperbranched polyesters, Polymer 47(1), 166–175.
  • [34] Ishida Y., Sun A. C. F., Jikei M., Kakimoto M. A., (2000) Synthesis of hyperbranched aromatic polyamides starting from dendrons as AB x monomers: effect of monomer multiplicity on the degree of branching, Macromolecules 33(8), 2832–2838.
  • [35] Jena K. K., Raju K. V. S. N., Prathab B., Aminabhavi T. M., (2007) Hyperbranched polyesters: synthesis, characterization, and molecular simulations, J. Phys. Chem. B. 111(30), 8801-8811.
  • [36] Goswami A., Singh A. K., (2004) Hyperbranched polyester having nitrogen core: synthesis and applications as metal ion extractant, React. Funct. Polym. 61(2), 255–263.
  • [37] Chikh L., Tessier M., Fradet A., (2008) Polydispersity of Hyperbranched Polyesters Based on 2, 2-Bis (hydroxymethyl) propanoic Acid: SEC/MALDI− TOF MS and 13C NMR/Kinetic-Recursive Probability Analysis, Macromolecules 41(23), 9044-9050.
  • [38] Lee S. S., Ma Y. T., Rhee H. W., Kim J., (2005) Exfoliation of layered silicate facilitated by ring-opening reaction of cyclic oligomers in PET–clay nanocomposites, Polymer 46(7), 2201-2210.
  • [39] Malmström E., Hult A., (1997) Hyperbranched polymers, Journal of Macromolecular Science Part C: Polymer Reviews 37(3), 555-579.
  • [40] Kim Y. H., Webster O. W., (1992) Hyperbranched polyphenylenes, Macromolecules 25(21), 5561-5572.
  • [41] Hawker C. J., Chu F., (1996) Hyperbranched poly (ether ketones): manipulation of structure and physical properties, Macromolecules 29(12), 4370-4380.
  • [42] Li X., Li Y., Tong Y., Shi L., Liu X., (2003) Synthesis and Characterization of Hyperbranched Aromatic Poly (ether imide)s, Macromolecules 36(15), 5537-5544.