Isothermal crystallization kinetics and melting behavior of poly (beta-hydroxybutyrate) and maleated poly (beta-hydroxybutyrate)

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB) and maleated PHB with different graft degree were studied by using differential scanning calorimetry (DSC). The Avrami analysis indicates that the introduction of maleic anhydride results in the decrease in the overall crystallization rate of PHB, but does not affect its nucleation mechanism and geometry of crystal growth. The activation energy of the overall crystallization process increases with the increase in graft degree. The phenomenon of multiple melting endotherms is observed, which results from melting and recrystallization during the DSC heating run.

Mechanical properties of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

Tensile properties of poly (P-hydroxybutyrate)/poly (ethylene oxide) (PHB/PEO) blends were reported in this paper. It was found that the blends of PHB with different molecular-weight PEO exhibited different mechanical properties. The mechanical properties of the blends of PHB and PEO3 (M-w=0.3x10(6)) were very poor. However, the blends of PHB and PEO5 (M-w=5x10(6)) showed compatible in mechanical properties. Excellent synergism was observed not only in tensile stress and tensile elongation but also in modulus. Moreover, the ductility of the blends could be improved further under proper heat-treatment.

Study on the properties of poly(beta-hydroxybutyrate) grafted with maleic anhydride

The thermal stability, crystallization behavior and biodegradability of poly(beta -hydroxybutyrate) (PHB) grafted with maleic anhydride (MA) were studied by DSC,TGA, optical microscopy and WAXD. The results showed that thermal stability of maleated PHB was obviously improved, comparing with that of pure PHB. The temperature of decomposition was enhanced about 20 degreesC After grafting MA, the crystallization behavior of PHB changed evidently. The rate of spherulite growth decreased, the crystallization temperature from the melt state reduced, and the cold crystallization temperature from the glass state increased. With the increase in graft degree, the banding texture of spherulite became more distinct and orderly. Moreover, the introduction of MA groups promoted the biodegradation of PHB.

Miscibility and crystallization behavior of poly(beta-hydroxybutyrate)/poly(ethylene oxide) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB)/poly(ethylene oxide) (PEO) blends were studied by differential scanning calorimetry(DSC) and polarizing microscopy (POM). It is found that the miscibility is related to the composition of the blends. When the PEO content is over 20 percent, the miscible blends turn into partially miscible and the phase separation can be observed with POM. The addition of the PEO influences not only the morphology of PHB crystals and the radial growth rate of spherulites, but also the cold crystallization temperature.

Nonisothermal crystallization and melting behavior of poly(beta-hydroxybutyrate)-poly(vinyl-acetate) blends

Nonisothermal crystallization and melting behavior of poly(P-hydroxybutyrate) (PHB)-poly(vinyl acetate) (PVAc) blends from the melt were investigated by differential scanning calorimetry using various cooling rates. The results show that crystallization of PHB from the melt in the PHB-PVAc blends depends greatly upon cooling rates and blend compositions. For a given composition, the crystallization process begins at higher temperatures when slower scanning rates are used. At a given cooling rate, the presence of PVAc reduces the overall PHB crystallization rate. The Avrami analysis modified by Jeziorny and a new method were used to describe the nonisothermal crystallization process of PHB-PVAc blends very well. The double-melting phenomenon is found to be caused by crystallization during heating in DSC. (C) 1999 John Wiley & Sons, Inc.

Isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate)/poly(vinyl acetate) blends

The overall isothermal crystallization kinetics and melting behavior of poly(beta-hydroxybutyrate) (PHB)/poly(vinyl acetate) (PVAc) blends were studied by using differential scanning calorimetry(DSC). The Avrami analysis indicates that the addition of PVAc into PHB results in the decrease in the overall crystallization rate of the PHB phase, but does not affect PHB's nucleation mechanism and geometry of crystal growth. The activation energy of the overall process of crystallization increases with the increasing PVAc content in the blends. The phenomenon of multiple melting endotherms is observed, which is caused by melting and recrystallization during the DSC heating run. (C) 1998 Elsevier Science Ltd. All rights reserved.

Nonisothermal crystallization kinetics of poly(beta-hydroxybutyrate)

Kinetics of nonisothermal crystallization of poly( beta-hydroxybutyrate) from melt and glassy states were performed by differential scanning calorimetry under various heating and cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that both Avrami treatment and a new method developed by combining the Avrami equation and Ozawa equation could describe this system very well. However, Ozawa analysis failed. By using an evaluation method, proposed by Kissinger, activation energies have been evaluated to be 92.6 kJ/mol and 64.6 kJ/mol for crystallization from the glassy and melt state, respectively. (C) 1998 John Wiley & Sons, Inc.

Crystallization kinetics and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends

The crystallization behavior and morphology of poly(beta-hydroxybutyrate) and poly(vinyl acetate) blends have been studied with DSC, POM, SAXS and WAXD methods. The results indicate that the overall crystallization rate and spherulite growth rate are slower in the blends than that in the pure PHB. The addition of PVAc has no effect on the crystal structure of PHB, but affects its crystalline morphology. During crystallization of PHB, PVAc chains were being rejected into the region between the lamellae of crystalline PHB. (C) 1997 Elsevier Science Ltd.

Miscibility and crystallization of poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB) and poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry and optical microscopy (OM). The blends exhibit a single composition-dependent glass transition temperature, characteristic of miscible systems, A depression of the equilibrium melting temperature of PHB is observed. The interaction parameter values obtained from analysis of the melting point depression are of large negative values, which suggests that PHB and PVPh blends are thermodynamically miscible in the melt. Isothermal crystallization kinetics in the miscible blend system PHB/PVPh was examined by OM. The presence of the amorphous PVPh component results in a reduction in the rate of spherulite growth of PHB. The spherulite growth rate is analyzed using the Lauritzen-Hoffman model, The isothermally crystallized blends of PHB/PVPh were examined by wide-angle X-ray diffraction and smell-angle X-ray scattering (SAXS). The long period obtained from SAXS increases with the increase in PVPh component, which implies that the amorphous PVPh is squeezed into the interlamallar region of PHB.

Compatibility and specific interactions in poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and specific interactions in poly (beta-hydroxybutyrate) (PHB)/poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry(DSC) , fourier transform infrared(FTIR) spectrometer and high resolution solid state C-13 NMR, A single composition-dependent glass transition temperatures were obtained by DSC which indicate the blends of PHB/PVPh were miscible in the melt state, The experimental glass transition temperatures were fitted quite well with those obtained from Couchman-Karasz equation. The FTIR study shows that the strong intermolecular hydrogen bonding exists in blends of PHB with strong proton acceptor and PVPh with strong proton donor and is the origin of its compatibility. The CPMAS C-13 NMR spectra also show that the strong hydrogen bonding exists in PHB/PVPh blends. From the T-1 rho(H) relaxation time it follows that the blends of PHB/PVPh(40/60, 20/80) studied are completely homogeneous on the scale of about 3.2 nm.

Sugars-grafted aliphatic biodegradable poly(L-lactide-co-carbonate)s by click reaction and their specific interaction with lectin molecules

A novel biodegradable aliphatic poly(L-lactide-co-carbonate) bearing pendant acetylene groups was successfully prepared by ring-opening copolymerization of L-lactide (LA) with 5-methyl-5-propargyloxycarbonyl-1,3-dioxan-2-one (PC) in the presence of benzyl alcohol as initiator with ZnEt2 as catalyst in bulk at 100 degrees C and subsequently used for grafting 2-azidoethyl beta-D-glucopyranoside and 2-azidoethyl beta-lactoside by the typical "click reaction," that is Cu(I)-catalyzed cycloaddition of azide and alkyne. The density of acetylene groups in the copolymer can be tailored by the molar ratio of PC to LA during the copolymerization. The aliphatic copolymers grafted with sugars showed low cytotoxicity to L929 cells, improved hydrophilic properties and specific recognition and binding ability with lectins, that is Concanavalin A (Con A) and Ricinus communis agglutinin (RCA). Therefore, this kind of sugar-grafted copolymer could be a good candidate in variety of biomedical applications.

Synthesis and characterization of maleated poly(3-hydroxybutyrate)

Graft copolymerization of maleic anhydride (MA) onto poly(3-hydroxybutyrate) (PHB) was carried out by use of benzoyl peroxide as initiator. The effects of various polymerization conditions on graft degree were investigated, including solvents, monomer and initiator concentrations, reaction temperature, and time. The monomer and initiator concentrations played an important role in graft copolymerization, and graft degree could be controlled in the range from 0.2 to 0.85% by changing the reaction conditions. The crystallization behavior and the thermal stability of PHB and maleated PHB were studied by DSC, WAXD, optical microscopy, and TGA. The results showed that, after grafting MA, the crystallization behavior of PHB was obviously changed. The cold crystallization temperature from the glass state increased, the crystallization temperature from the melted state decreased, and the growth rate of spherulite decreased. With the increase in graft degree, the banding texture of spherulites became more distinct and orderly. Moreover, the thermal stability of maleated PHB was obviously improved, compared with that of pure PHB.

The kinetics of the thermal decomposition of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3-hydroxybutyrate) (PHB) was investigated by FTIR and H-1 NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six-membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating-up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E. as a kinetic parameter of thermal decomposition was estimated by the Flynn-Wall-Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods.

Macrocyclic polyamine-modified poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith for capillary electrochromatography

1,4,10,13,16-Pentaazatricycloheneicosane-9,17-dione (macrocyclic polyamine)-modified polymer-based monolithic column for CEC was prepared by ring opening reaction of epoxide groups from poly(glycidyl methacrylate-co-ethylene dimethacrylate) (GMA-co-EDMA) monolith with macrocyclic polyamine. Conditions such as reaction time and concentration of macrocyclic polyamine for the modification reaction were optimized to generate substantial EOF and enough chromatographic interactions. Anodic EOF was observed in the pH range of 2.0-8.0 studied due to the protonation of macrcyclic polyamine at the surface of the monolith. Morphology of the monolithic column was examined by SEM and the incorporation of macrocyclic polyamine to the poly(GMA-co-EDMA) monolith was characterized by infrared (IR) spectra. Successful separation of inorganic anions, isomeric benzenediols, and benzoic acid derivatives on the monolithic column was achieved for CEC. In addition to hydrophobic interaction, hydrogen bonding and electrostatic interaction played a significant role in the separation process.