Journal of Polymer Science Part A: Polymer Chemistry, Vol.46, No.15, 5036-5052, 2008
beta-cyclodextrin polymer brushes based on hyperbranched polycarbosilane: Synthesis and characterization
In this article, our main goal is to combine hyperbranched polymer with beta-cyclodextrin (beta-CD) to establish a novel functional polymer species with core-shell structure and supramolecular system for further application in inclusion technologies and the complex drugs delivery system. Therefore, two beta-CD polymer brushes based on hyperbranched polycarbosilane (HBP) as a hydrophobic core and poly(N,N-dimethylaminoethyl methacrylate) (PDMA) carrying beta-CD units as a hydrophilic shell were synthesized. Hyperbranched polycarbosilane macroinitiator carrying -Cl groups (HBP-Cl) was also prepared by using 1,1,3,3-tetrmethyldisiloxane, allyl alcohol, and chloroacetyl chloride as reagents. The molecular structures of HBP-Cl macroinitiator and beta-CD polymer brushes were characterized by Fourier transform infrared spectroscopy (FTIR), H-1 nuclear magnetic resonance (H-1 NMR), C-13 nuclear magnetic resonance (C-13 NMR) spectroscopies, size exclusion chromatography/multi-angle laser light scattering (SEC/MALLS) and laser particle size analyzer. The results indicate that the grafted chain length of two beta-CD polymer brushes can be controlled by changing the feed ratio. Differential scanning calorimetry (DSC) results show that two beta-CD polymer brushes have two glass transition temperatures (T(g)s) from a hydrophobic core part and a hydrophilic shell part, respectively, and the T, from PDMA is higher than that of HBP-g-PDMA. Thermalgravimetric analyzer (TGA) analysis indicates that the thermostability of two beta-CD polymer brushes is higher than that of HBP, but is lower than that of HBP-g-PDMA. Using phenolphthalein (PP) as a guest molecule, molecular inclusion behaviors for two beta-CD polymer brushes were studied. It reveals that two beta-CD polymer brushes possess molecular inclusion capability in PP buffer solution with a fixed concentration. (C) 2008 Wiley Periodicals, Inc.
Keywords:atom transfer radical polymerization;core-shell structure;beta-cyclodextrin;polymer brushes;hyperbranched polymer;synthesis