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2007 Volume 25 Issue 4
2007, 25(4): 331-339
Abstract:
Conducting polymer, polyaniline (PANI), has been studied as a novel electroactive and electrically conductive material for tissue engineering applications. The biocompatibility of the conductive polymer can be improved by (i) covalently grafting various adhesive peptides onto the surface of prefabricated conducting polymer films or into the polymer structures during the synthesis, (ii) co-electrospinning or blending with natural proteins to form conducting nanofibers or films, and (iii) preparing conducting polymers using biopolymers, such as collagen, as templates. In this paper, we mainly describe and review the approaches of covalently attaching oligopeptides to PANI and electrospinning PANI-gelatin blend nanofibers. The employment of such modified conducting polymers as substrates for enhanced cell attachment, proliferation and differentiation has been investigated with neuronal PC-12 cells and H9c2 cardiac myoblasts. For the electrospun PANI-gelatin fibers, depending on the concentrations of PANI, H9c2 cells initially displayed different morphologies on the fibrous substrates, but after one week all cultures reached confluence of similar densities and morphologies. Furthermore, we observed, that conductive PANI, when maintained in an aqueous physiologic environment, retained a significant level of electrical conductivity for at least 100 h, even though this conductivity was decreasing over time. Preliminary data show that the application of micro-current stimulates the differentiation of PC-12 cells. All the results demonstrate the potential for using PANI as an electroactive polymer in the culture of excitable cells and open the possibility of using this material as an electroactive scaffold for cardiac and/or neuronal tissue engineering applications that require biocompatibility of conductive polymers.
Conducting polymer, polyaniline (PANI), has been studied as a novel electroactive and electrically conductive material for tissue engineering applications. The biocompatibility of the conductive polymer can be improved by (i) covalently grafting various adhesive peptides onto the surface of prefabricated conducting polymer films or into the polymer structures during the synthesis, (ii) co-electrospinning or blending with natural proteins to form conducting nanofibers or films, and (iii) preparing conducting polymers using biopolymers, such as collagen, as templates. In this paper, we mainly describe and review the approaches of covalently attaching oligopeptides to PANI and electrospinning PANI-gelatin blend nanofibers. The employment of such modified conducting polymers as substrates for enhanced cell attachment, proliferation and differentiation has been investigated with neuronal PC-12 cells and H9c2 cardiac myoblasts. For the electrospun PANI-gelatin fibers, depending on the concentrations of PANI, H9c2 cells initially displayed different morphologies on the fibrous substrates, but after one week all cultures reached confluence of similar densities and morphologies. Furthermore, we observed, that conductive PANI, when maintained in an aqueous physiologic environment, retained a significant level of electrical conductivity for at least 100 h, even though this conductivity was decreasing over time. Preliminary data show that the application of micro-current stimulates the differentiation of PC-12 cells. All the results demonstrate the potential for using PANI as an electroactive polymer in the culture of excitable cells and open the possibility of using this material as an electroactive scaffold for cardiac and/or neuronal tissue engineering applications that require biocompatibility of conductive polymers.
2007, 25(4): 341-345
Abstract:
Biosynthesis and thermal properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with different HV (hydrovalerate) content produced by a Bacillus cereus strain were investigated. A large variety of HV contents (up to about 90 mol%) of PHBV could be produced by this strain. Combined nitrogen sources containing both yeast extract and ammonium sulphate were better for cell growth and polyhydroxyalkanoates (PHA) production than either yeast extract or ammonium sulphate alone. Propionic acid is more favorable for the production of HV content than that of valeric acid. Finally, thermal properties of PHBV produced by this strain are found close to the results of other groups.
Biosynthesis and thermal properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with different HV (hydrovalerate) content produced by a Bacillus cereus strain were investigated. A large variety of HV contents (up to about 90 mol%) of PHBV could be produced by this strain. Combined nitrogen sources containing both yeast extract and ammonium sulphate were better for cell growth and polyhydroxyalkanoates (PHA) production than either yeast extract or ammonium sulphate alone. Propionic acid is more favorable for the production of HV content than that of valeric acid. Finally, thermal properties of PHBV produced by this strain are found close to the results of other groups.
2007, 25(4): 347-355
Abstract:
Electrorheological (ER) properties of polyaniline (PAni), pumice and polyaniline/pumice composites (PAPC) were investigated. Polyaniline and PAni/pumice composite were prepared by oxidative polymerization. PAni/pumice particles-based ER suspensions were prepared in silicone oil (SO), and their ER behavior was investigated as a function of shear rate, electric field strength, concentration and temperature. Sedimentation stabilities of suspensions were determined. It has been found that ER activity of all the suspensions increases with increasing electric field strength, concentration and decreasing shear rate. It has shown that the suspensions have a typical shear thinning non-Newtonian viscoelastic behavior. Yield stress of composite suspensions increased linearly with increasing applied electric field strength and with concentrations of the particles. The effect of high temperature on ER activity of pumice/silicone oil systems was also investigated.
Electrorheological (ER) properties of polyaniline (PAni), pumice and polyaniline/pumice composites (PAPC) were investigated. Polyaniline and PAni/pumice composite were prepared by oxidative polymerization. PAni/pumice particles-based ER suspensions were prepared in silicone oil (SO), and their ER behavior was investigated as a function of shear rate, electric field strength, concentration and temperature. Sedimentation stabilities of suspensions were determined. It has been found that ER activity of all the suspensions increases with increasing electric field strength, concentration and decreasing shear rate. It has shown that the suspensions have a typical shear thinning non-Newtonian viscoelastic behavior. Yield stress of composite suspensions increased linearly with increasing applied electric field strength and with concentrations of the particles. The effect of high temperature on ER activity of pumice/silicone oil systems was also investigated.
2007, 25(4): 357-364
Abstract:
Metallocene-catalyzed linear low-density polyethylene/polypropylene (mLLDPE/PP) blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by on-line measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends.
Metallocene-catalyzed linear low-density polyethylene/polypropylene (mLLDPE/PP) blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by on-line measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends.
2007, 25(4): 365-377
Abstract:
The estimation of the amount of reactive impurities in a loop reactor is of strategic importance to the propylene polymerization industry. It is essential to investigate the level of impurities in order to develop reliable monitoring and control strategies. This paper described one approach based on generation function technique with the following two steps. First, a new mechanism for propylene polymerization was proposed by considering the effects of the reactive impurities in the material on the propylene polymerization. Second, a series of equations of population balance for the propylene polymerization in loop reactors were established based on the proposed mechanism. Accordingly, the equations were transformed into the mathematic matrix through the generation function technique to investigate the effects of the reactive impurities on the propylene polymerization. Significant effects of the reactive impurities were analyzed through computational simulation. The results show that the concentration of active centre on catalysts and the polymerization conversion both decrease with the increase of the initial concentration of any reactive impurity; hydrogen concentration decreases with the increase of the initial concentration of ethylene or butylenes, whereas, it increases with the increase of the initial concentration of propadiene; the simulated weight average molecular weight and the molecular weight distribution index of polymer resins both increase with the increase of the initial concentration of ethylene or butylenes. They decrease with the increase of the initial concentration of propadiene.
The estimation of the amount of reactive impurities in a loop reactor is of strategic importance to the propylene polymerization industry. It is essential to investigate the level of impurities in order to develop reliable monitoring and control strategies. This paper described one approach based on generation function technique with the following two steps. First, a new mechanism for propylene polymerization was proposed by considering the effects of the reactive impurities in the material on the propylene polymerization. Second, a series of equations of population balance for the propylene polymerization in loop reactors were established based on the proposed mechanism. Accordingly, the equations were transformed into the mathematic matrix through the generation function technique to investigate the effects of the reactive impurities on the propylene polymerization. Significant effects of the reactive impurities were analyzed through computational simulation. The results show that the concentration of active centre on catalysts and the polymerization conversion both decrease with the increase of the initial concentration of any reactive impurity; hydrogen concentration decreases with the increase of the initial concentration of ethylene or butylenes, whereas, it increases with the increase of the initial concentration of propadiene; the simulated weight average molecular weight and the molecular weight distribution index of polymer resins both increase with the increase of the initial concentration of ethylene or butylenes. They decrease with the increase of the initial concentration of propadiene.
2007, 25(4): 379-386
Abstract:
Microporous ethylene-vinyl alcohol copolymer (EVOH) flat membranes and hollow-fiber membranes with 38 mol% ethylene content were prepared via thermally induced phase separation (TIPS) using the mixture of 1,4-butanediol and poly(ethylene glycol)(PEG400) as diluents. Effects of the ratio of 1,4-butanediol to PEG400 on the phase diagrams, phase separation mechanism and membrane morphology were studied by small angle light scattering (SALS) measurements, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). It was found that by varying the composition of the binary solvent, the phase diagrams and membrane morphology can be controlled successfully. Moreover, the phase diagrams showed that broader regions of Liquid-Liquid (L-L) phase separation were obtained, as well as closer distances between L-L phase separation lines and Solid-Liquid (S-L) phase separation lines. Interconnected structures observed both in the flat membrane and hollow fiber membrane consist with the above results.
Microporous ethylene-vinyl alcohol copolymer (EVOH) flat membranes and hollow-fiber membranes with 38 mol% ethylene content were prepared via thermally induced phase separation (TIPS) using the mixture of 1,4-butanediol and poly(ethylene glycol)(PEG400) as diluents. Effects of the ratio of 1,4-butanediol to PEG400 on the phase diagrams, phase separation mechanism and membrane morphology were studied by small angle light scattering (SALS) measurements, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). It was found that by varying the composition of the binary solvent, the phase diagrams and membrane morphology can be controlled successfully. Moreover, the phase diagrams showed that broader regions of Liquid-Liquid (L-L) phase separation were obtained, as well as closer distances between L-L phase separation lines and Solid-Liquid (S-L) phase separation lines. Interconnected structures observed both in the flat membrane and hollow fiber membrane consist with the above results.
2007, 25(4): 387-392
Abstract:
A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume (V) against longitudinal variation (l) showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.
A method to quantify crazing deformations by tensile tests for polystyrene (PS) and polyolefin elastomer (POE) blends was investigated. The toughness of PS/POE blends, reflected by the Charpy impact strength, increased with the content of POE. SEM micrographs showed the poor compatibility between PS and POE. In simple tensile tests, it is very easy to achieve the ratio of crazing deformation, i.e. K by measuring the size changes of samples. The K values decreased with increasing the content of POE, and the deformations of PS/POE blends were dominated by crazing. The plots of the change of volume (V) against longitudinal variation (l) showed a linear relationship, and the slope of lines decreased with the content of POE. Measuring samples at the tensile velocities of 5 mm/min, 50 mm/min, and 500 mm/min respectively, the K values kept unchanged for each PS/POE blends.
2007, 25(4): 393-397
Abstract:
One of the suitable methods for removing heavy metals from water is by using surface adsorption process. In this paper, the preparation of polypyrrole and its composites as adsorbents are discussed and the capability of separating mercury from water is investigated. The results indicated that the polypyrrole and its composites are able to remove mercury from aqueous media. Furthermore the adsorption percentage is related to the surface morphology, type of additives and its concentration.
One of the suitable methods for removing heavy metals from water is by using surface adsorption process. In this paper, the preparation of polypyrrole and its composites as adsorbents are discussed and the capability of separating mercury from water is investigated. The results indicated that the polypyrrole and its composites are able to remove mercury from aqueous media. Furthermore the adsorption percentage is related to the surface morphology, type of additives and its concentration.
2007, 25(4): 399-407
Abstract:
New Schiff base polymers poly[4,4′-methylenebis(cinnamaldehyde)ethylenediimine] (PMBCen), poly[4,4′-methylenebis(cinnamaldehyde)1,2-propylenediimine] (PMBCPn), poly[4,4′-methylenebis(cinnamaldehyde)1,3-propylenedi-imine] (PMBCPR), poly[4,4′-methylenebis(cinnamaldehyde)1,2-phenylenediimine] (PMBCPh), poly[4,4′-methylene-bis(cinnamaldehyde)meso-stilbenediimine] (PMBCS), poly[4,4′-methylenebis(cinnamaldehyde)urea] (PMBCUR), poly[4,4′-methylenebis(cinnamaldehyde)semicarbazone] (PMBCSc), poly[4,4′-methylenebis(cinnamaldehyde)thiosemicarbazone] (PMBCTSc) and poly[4,4′-methylenebis(cinnamaldehyde)hydrazone] (PMBCH) were formed by polycondensation of 4,4′-methylenebis(cinnamaldehyde) with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and 1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.
New Schiff base polymers poly[4,4′-methylenebis(cinnamaldehyde)ethylenediimine] (PMBCen), poly[4,4′-methylenebis(cinnamaldehyde)1,2-propylenediimine] (PMBCPn), poly[4,4′-methylenebis(cinnamaldehyde)1,3-propylenedi-imine] (PMBCPR), poly[4,4′-methylenebis(cinnamaldehyde)1,2-phenylenediimine] (PMBCPh), poly[4,4′-methylene-bis(cinnamaldehyde)meso-stilbenediimine] (PMBCS), poly[4,4′-methylenebis(cinnamaldehyde)urea] (PMBCUR), poly[4,4′-methylenebis(cinnamaldehyde)semicarbazone] (PMBCSc), poly[4,4′-methylenebis(cinnamaldehyde)thiosemicarbazone] (PMBCTSc) and poly[4,4′-methylenebis(cinnamaldehyde)hydrazone] (PMBCH) were formed by polycondensation of 4,4′-methylenebis(cinnamaldehyde) with ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2-phenylenediamine, meso-stilbenediamine, urea, semicarbazide, thiosemicarbazide and hydrazine, respectively. The dialdehyde and polymers have been characterized through elemental micro-analysis, IR, UV-Vis and 1H-NMR spectroscopic techniques. Thermoanalytical studies and viscous flow of dilute solutions of dialdehyde and its polymers have been examined and compared.
SYNTHESIS AND CHARACTERIZATION OF ORGANSOLUBLE POLYIMIDE AND COPOLYIMIDES FROM ALICYCLIC DIANHYDRIDE
2007, 25(4): 409-417
Abstract:
A kind of highly organsoluble polyimide and copolyimides were successfully synthesized from bicyclo(2.2.2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA), the commercial diamine 4,4-methylenedianiline (MDA) and the designed diamine 4,4-methylenebis-(2-tert-butylaniline) (MBTBA). The polyimide from BCDA and MBTBA is highly soluble in conventional low boiling point solvents (such as chloroform, tetrahydrofuran) at room temperature. But the solubility of the copolyimides in conventional solvents decreased with the molar ratio of MBTBA and MDA decreased. When the molar ratio of MBTBA and MDA was larger than 7/3, the copolyimides can be soluble in low boiling point solvents at room temperature to form a transparent, flexible, tough film by solution casting. When the molar ratio of MBTBA and MDA was between 7/3 and 1/9, they can only be soluble in hot dipolar aprotic solvents (such as DMF, NMP etc.) and form films too. The copolyimide was only soluble in m-cresol when the molar ratio of MBTBA and MDA was lower than 1/9. The number-average molecular weights of the soluble copolyimides were larger than 5.8 × 104 g/mol by GPC and their polydispersity indices were higher than 1.4. Only one glass transition temperature of these copolyimides was detected around 400°C by DMA. The copolyimides did not show appreciable decomposition up to 430°C in N2.
A kind of highly organsoluble polyimide and copolyimides were successfully synthesized from bicyclo(2.2.2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA), the commercial diamine 4,4-methylenedianiline (MDA) and the designed diamine 4,4-methylenebis-(2-tert-butylaniline) (MBTBA). The polyimide from BCDA and MBTBA is highly soluble in conventional low boiling point solvents (such as chloroform, tetrahydrofuran) at room temperature. But the solubility of the copolyimides in conventional solvents decreased with the molar ratio of MBTBA and MDA decreased. When the molar ratio of MBTBA and MDA was larger than 7/3, the copolyimides can be soluble in low boiling point solvents at room temperature to form a transparent, flexible, tough film by solution casting. When the molar ratio of MBTBA and MDA was between 7/3 and 1/9, they can only be soluble in hot dipolar aprotic solvents (such as DMF, NMP etc.) and form films too. The copolyimide was only soluble in m-cresol when the molar ratio of MBTBA and MDA was lower than 1/9. The number-average molecular weights of the soluble copolyimides were larger than 5.8 × 104 g/mol by GPC and their polydispersity indices were higher than 1.4. Only one glass transition temperature of these copolyimides was detected around 400°C by DMA. The copolyimides did not show appreciable decomposition up to 430°C in N2.
2007, 25(4): 419-426
Abstract:
A novel sulfonated poly(arylene ether) containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by 1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton’s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nafion 117 under same conditions. The membrane electrode assembly (MEA) prepared with the as-made film (706 EW, 100 m dry thickness) shows better cell performance than Nafion 115-MEA in the whole current density range.
A novel sulfonated poly(arylene ether) containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by 1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton’s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nafion 117 under same conditions. The membrane electrode assembly (MEA) prepared with the as-made film (706 EW, 100 m dry thickness) shows better cell performance than Nafion 115-MEA in the whole current density range.
2007, 25(4): 427-430
Abstract:
The ring-opening polymerization of 1,4-dioxan-2-one (PDO) was carried out by lanthanum tris(2,6-di-tert-butyl-4-methylphenolate) (La(OAr)3) as novel single component initiator. The influences of polymerization reaction temperature and the molar ratio of monomer to initiator on the monomer conversion and molecular weight of poly(1,4-dioxan-2-one) (PPDO) were explored. PPDO with high viscosity average molecular weight of 1.95 × 105 can be prepared at 40oC when [PDO]/ [La(OAr)3] molar ratio was 800. Mechanism investigation shows that the polymerization proceeds through a “coordination-insertion” mechanism with selective rupture of acyl-oxygen bond of PDO.
The ring-opening polymerization of 1,4-dioxan-2-one (PDO) was carried out by lanthanum tris(2,6-di-tert-butyl-4-methylphenolate) (La(OAr)3) as novel single component initiator. The influences of polymerization reaction temperature and the molar ratio of monomer to initiator on the monomer conversion and molecular weight of poly(1,4-dioxan-2-one) (PPDO) were explored. PPDO with high viscosity average molecular weight of 1.95 × 105 can be prepared at 40oC when [PDO]/ [La(OAr)3] molar ratio was 800. Mechanism investigation shows that the polymerization proceeds through a “coordination-insertion” mechanism with selective rupture of acyl-oxygen bond of PDO.
