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Macromolecules, Vol.28, No.14, 4785-4794, 1995
Synthesis, Characterization, and in-Vitro Degradation of a Novel Thermotropic Ternary Copolyester Based on P-Hydroxybenzoic Acid, Glycolic Acid, and P-Hydroxycinnamic Acid
The direct copolycondensation of aromatic hydroxy acid with aliphatic alpha-hydroxy acid was achieved by using certain amounts of a third comonomer with or without a catalyst. High molecular weight main-chain thermotropic liquid crystalline terpolyesters with a potentially biodegradable property based on p-hydroxybenzoic acid (PHBA), glycolic acid (GA), and the bridge comonomer trans-p-hydroxycinnamic acid (PHCA) were synthesized via a one-step melt copolycondensation process. Solution viscosity, Fourier transform infrared spectrometer (FTIR), and nuclear magnetic resonance (H-1 NMR, C-13 NMR) measurements were used to identify the formation and structure of this terpolymer; a random sequence distribution of the comonomeric units along the polymeric chains was concluded. A single glass transition temperature at about 82 degrees C and a broad endothermic transition with a maximum at 150 degrees C were discerned in the DSC profiles of the as-prepared polymers. Wide-angle X-ray diffraction (WAXD) analysis indicated the occurrence of a nematic structure in the as-injected fiber of the terpolymer. This nematic liquid crystallinity was further confirmed from the characteristic textures under optical polarizing microscopy (POM) : a Schlieren-type texture for low molecular weight copolymers or banded textures for high molecular weight ones over a wide temperature range. The anisotropic-isotropic transition was not clearly detectable until the polymer decomposition. The in vitro degradation of the thermotropic liquid crystalline ternary copolyester was evaluated by water absorption, inherent viscosity, morphology, and thermal properties after treatment in buffer media in the absence of enzyme. It is clearly shown that the hydrophilicity was greatly improved due to the incorporation of GA segments. The copolymer degraded via a simple hydrolysis of the ester bonds of GA-rich segments, and the aromatic counterpart could also be involved in the hydrolysis. These degradations occurred predominantly in the amorphous or less aligned
Keywords:STRUCTURE PROPERTY RELATIONSHIPS;PEO/PLA BLOCK COPOLYMERS;BIODEGRADABLE POLYMERS;AQUEOUS-MEDIA;POLYESTERS;SURGERY