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2010 Volume 28 Issue 3
2010, 28(3): 291-297
Abstract:
Base on the principle of absolute quantification of size exclusion chromatography (SEC), a light scattering (LS) detector coupled with a concentration detector (refractive index detector) is utilized to determine the compositions of complicated binary mixtures. A theoretical analysis predicts that the response factors for both LS and RI detectors are linear functions with the composition of any specified polymer mixtures in the binary polymer mixtures. Two pairs of complicated binary mixtures were used to test the theory mentioned in the present paper, and the experimental results show an excellent accordance with the theory.
Base on the principle of absolute quantification of size exclusion chromatography (SEC), a light scattering (LS) detector coupled with a concentration detector (refractive index detector) is utilized to determine the compositions of complicated binary mixtures. A theoretical analysis predicts that the response factors for both LS and RI detectors are linear functions with the composition of any specified polymer mixtures in the binary polymer mixtures. Two pairs of complicated binary mixtures were used to test the theory mentioned in the present paper, and the experimental results show an excellent accordance with the theory.
2010, 28(3): 299-304
doi: 10.1007/s10118-010-0034-6
Abstract:
The discovery of highly active 2,6-bis(imino)pyridyl iron and cobalt complexes provided a milestone of late-transition metal catalysts for ethylene oligomerization and polymerization with being currently investigated for the scale-up process. The crucial problems are remaining in the catalytic systems: the catalytic systems targeting ethylene polymerization produce more oligomers at elevated reaction temperatures, however, there is a recognizable amount of high-molecular-weight polyethylene remained in the modified catalytic system for the oligomerization process. Beyond the modification of bis(imino)pyridyl metal complexes, several alternative procatalysts models have been developed in our group. This review highlighted the achievements in exploring new iron and cobalt complexes with tridentate NNN ligands as procatalysts for ethylene oligomerization and polymerization.
The discovery of highly active 2,6-bis(imino)pyridyl iron and cobalt complexes provided a milestone of late-transition metal catalysts for ethylene oligomerization and polymerization with being currently investigated for the scale-up process. The crucial problems are remaining in the catalytic systems: the catalytic systems targeting ethylene polymerization produce more oligomers at elevated reaction temperatures, however, there is a recognizable amount of high-molecular-weight polyethylene remained in the modified catalytic system for the oligomerization process. Beyond the modification of bis(imino)pyridyl metal complexes, several alternative procatalysts models have been developed in our group. This review highlighted the achievements in exploring new iron and cobalt complexes with tridentate NNN ligands as procatalysts for ethylene oligomerization and polymerization.
2010, 28(3): 305-310
doi: 10.1007/s10118-010-9007-z
Abstract:
Three Keggin-type heteropolyanions, namely H3PMo12O4013H2O, (NH4)3PMo12O404H2O and H3PW12O4013H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation (H+, NH4+) and the peripheral atoms (Mo, W) on the polymerization were investigated. It has been found that when the protons of H3PMo12O4013H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms (Mo) were replaced by their homologous (W), the polymerization rate increased twofold. As for the viscosity average molecular weight (Mv) of polymer products, it was found that the high molecular weight (7930) was obtained by using H3PW12O4013H2O. The molecular weight (Mv) obtained by H3PMo12O4013H2O and (NH4)3PMo12O404H2O was 6470 and 6810, respectively.
Three Keggin-type heteropolyanions, namely H3PMo12O4013H2O, (NH4)3PMo12O404H2O and H3PW12O4013H2O were prepared and tested in the ring-opening polymerization reaction of tetrahydrofuran. The effects of the counter-cation (H+, NH4+) and the peripheral atoms (Mo, W) on the polymerization were investigated. It has been found that when the protons of H3PMo12O4013H2O were replaced by the ammonium cations the polymerization rate decreased dramatically. Whereas, when the peripheral atoms (Mo) were replaced by their homologous (W), the polymerization rate increased twofold. As for the viscosity average molecular weight (Mv) of polymer products, it was found that the high molecular weight (7930) was obtained by using H3PW12O4013H2O. The molecular weight (Mv) obtained by H3PMo12O4013H2O and (NH4)3PMo12O404H2O was 6470 and 6810, respectively.
2010, 28(3): 311-322
doi: 10.1007/s10118-010-9006-0
Abstract:
Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths Nb, arm lengths Na and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The radius of gyration, the shape factors and bond length in different cases during elastic process are calculated, and it is found that the comb-like polymer molecules with longer backbone or shorter arm are more close to linear chains. But the arm density m affects the chain conformation non-monotonously. Some thermodynamic properties are also studied. Average Helmholtz free energy and elastic force f all increase with elongation ratio #61548; for all chains.
Three-dimensional Monte Carlo simulations of comb-like polymer chains with various backbone lengths Nb, arm lengths Na and arm densities m are carried out to study the elastic behavior of comb-like polymer chains. The radius of gyration, the shape factors and bond length in different cases during elastic process are calculated, and it is found that the comb-like polymer molecules with longer backbone or shorter arm are more close to linear chains. But the arm density m affects the chain conformation non-monotonously. Some thermodynamic properties are also studied. Average Helmholtz free energy and elastic force f all increase with elongation ratio #61548; for all chains.
2010, 28(3): 323-330
doi: 10.1007/s10118-010-9009-x
Abstract:
Synthesis and characterization of the copolymers (PAG) of -methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H-NMR) and thermogravimetery (TG). Based on the copolymer compositions determined by 1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 0.012 and 0.883 0.046 respectively by Kelen-Tds method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.
Synthesis and characterization of the copolymers (PAG) of -methyl styrene (AMS) and glycidyl methacrylate (GMA) are presented. The copolymers of PAG were characterized by gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H-NMR) and thermogravimetery (TG). Based on the copolymer compositions determined by 1H-NMR, the reactivity ratios of AMS and GMA were found to be 0.105 0.012 and 0.883 0.046 respectively by Kelen-Tds method. TG revealed that thermal stability of the copolymers decreased with increasing the AMS content in the copolymers, which indicated that the degradation was mainly caused by the chain scission of AMS-containing structures. Under heating, the copolymers depolymerize at their weak bonds and form chain radicals, which could further initiate other chemical reactions.
2010, 28(3): 331-336
doi: 10.1007/s10118-010-9014-0
Abstract:
The stability of full-conjugated self-assembled (SA) multilayer films based on partially doped polyaniline (PANI) as a polycation and poly(o-aminobenzoic acid) (PCAN), poly(aniline-2-sulfonic acid) (PSAN) as polyanions is investigated in alkali aqueous solutions. The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution, the PANI-PSAN films, however, maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN. The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.
The stability of full-conjugated self-assembled (SA) multilayer films based on partially doped polyaniline (PANI) as a polycation and poly(o-aminobenzoic acid) (PCAN), poly(aniline-2-sulfonic acid) (PSAN) as polyanions is investigated in alkali aqueous solutions. The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution, the PANI-PSAN films, however, maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN. The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.
2010, 28(3): 337-346
doi: 10.1007/s10118-010-9022-0
Abstract:
High density polyethylene (HDPE)/polyethylene-block-poly(ethylene glycol) (PE-b-PEG) blend porous membranes were prepared via thermally induced phase separation (TIPS) process using diphenyl ether (DPE) as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry (DSC). By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.
High density polyethylene (HDPE)/polyethylene-block-poly(ethylene glycol) (PE-b-PEG) blend porous membranes were prepared via thermally induced phase separation (TIPS) process using diphenyl ether (DPE) as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry (DSC). By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.
2010, 28(3): 347-355
doi: 10.1007/s10118-010-9025-x
Abstract:
A series of H-shaped (PS)2PEG(PS)2 block copolymers with different PS chain lengths were prepared. The influence of different confinements active on the crystallization and self-nucleation (SN) behavior of the PEG blocks was investigated by differential scanning calorimetry (DSC). When the content of the crystalline block was high, a classical SN behavior was obtained. The block copolymer with PEG content of 49% (by weight) showed a classical SN behavior with a narrow self-nucleation domain and had bimodal crystallization exotherms. When the PEG dispersed as separated microdomains in the block copolymer, the self-nucleation domain disappeared and only annealing was observed.
A series of H-shaped (PS)2PEG(PS)2 block copolymers with different PS chain lengths were prepared. The influence of different confinements active on the crystallization and self-nucleation (SN) behavior of the PEG blocks was investigated by differential scanning calorimetry (DSC). When the content of the crystalline block was high, a classical SN behavior was obtained. The block copolymer with PEG content of 49% (by weight) showed a classical SN behavior with a narrow self-nucleation domain and had bimodal crystallization exotherms. When the PEG dispersed as separated microdomains in the block copolymer, the self-nucleation domain disappeared and only annealing was observed.
NON-ISOTHERMAL CRYSTALLIZATION OF POLY(L-LACTIDE) (PLLA) UNDER QUIESCENT AND STEADY SHEAR CONDITIONS
2010, 28(3): 357-366
doi: 10.1007/s10118-010-9015-z
Abstract:
The non-isothermal crystallization of poly(L-lactide) (PLLA) under quiescent and steady shear flow conditions was in situ investigated by using polarizing optical microscopy (POM) with a hot shear stage and wide-angle X-ray diffraction (WAXD). The shear rate and the cooling rate both play a significant role in the final crystalline morphology and crystallinity. Under quiescent conditions, the morphology assumes different sized spherulites, and its crystallinity dramatically reduces with increasing the cooling rate. On the other hand, the shear flow increases the onset crystallization temperature, and enhances the final crystallinity. When the shear rate is above 5 s-1, cylindrite-like crystals are observed, furthermore, their content depends on the cooling rate.
The non-isothermal crystallization of poly(L-lactide) (PLLA) under quiescent and steady shear flow conditions was in situ investigated by using polarizing optical microscopy (POM) with a hot shear stage and wide-angle X-ray diffraction (WAXD). The shear rate and the cooling rate both play a significant role in the final crystalline morphology and crystallinity. Under quiescent conditions, the morphology assumes different sized spherulites, and its crystallinity dramatically reduces with increasing the cooling rate. On the other hand, the shear flow increases the onset crystallization temperature, and enhances the final crystallinity. When the shear rate is above 5 s-1, cylindrite-like crystals are observed, furthermore, their content depends on the cooling rate.
2010, 28(3): 367-376
doi: 10.1007/s10118-010-9026-9
Abstract:
Thermal properties of acrylonitrile (AN)-acrylamide (AM) copolymers for carbon fibers were studied by DSC and in situ FTIR techniques in nitrogen (N2) and air flows. The cyclization mechanism and stabilization behavior of polyacrylonitrile (PAN) were discussed. In N2 flow, it was found that AM had the ability to initiate and accelerate cyclization process, which was confirmed by the fact that the initiation of nitriles shifted to a lower temperature. Compared to AN homopolymer, the initiation temperature of cyclization was ahead 32 K by introducing 3.59 mol% AM into the copolymer. The exothermic reaction was relaxed due to the presence of two separated exothermic peaks. Accompanied by DSC, in situ FTIR and calculation of activation energy, the two peaks were proved to be caused by ionic cyclization and free radical cyclization, respectively, and the corresponding cyclization mechanism was proposed. With increasing in AM content, the ionic cyclization tends to be dominant and the total heat liberated first increases and then decreases. For AN homopolymer, the activation energy of cyclization is 179 kJ/mol. For AN-AM copolymer (containing 3.59 mol% AM), the activation energy of ionic cyclization is 96 kJ/mol and that of free radical cyclization is 338 kJ/mol. In air flow, similar cyclization routes occur and the difference is the contribution of oxidation. The oxygen in environment has no remarkable effect on cyclization of AN homopolymer but retards the cyclization of AN-AM copolymers. For AN-AM copolymer with 3.59 mol% AM, the cyclization temperature is postponed 10C in air.
Thermal properties of acrylonitrile (AN)-acrylamide (AM) copolymers for carbon fibers were studied by DSC and in situ FTIR techniques in nitrogen (N2) and air flows. The cyclization mechanism and stabilization behavior of polyacrylonitrile (PAN) were discussed. In N2 flow, it was found that AM had the ability to initiate and accelerate cyclization process, which was confirmed by the fact that the initiation of nitriles shifted to a lower temperature. Compared to AN homopolymer, the initiation temperature of cyclization was ahead 32 K by introducing 3.59 mol% AM into the copolymer. The exothermic reaction was relaxed due to the presence of two separated exothermic peaks. Accompanied by DSC, in situ FTIR and calculation of activation energy, the two peaks were proved to be caused by ionic cyclization and free radical cyclization, respectively, and the corresponding cyclization mechanism was proposed. With increasing in AM content, the ionic cyclization tends to be dominant and the total heat liberated first increases and then decreases. For AN homopolymer, the activation energy of cyclization is 179 kJ/mol. For AN-AM copolymer (containing 3.59 mol% AM), the activation energy of ionic cyclization is 96 kJ/mol and that of free radical cyclization is 338 kJ/mol. In air flow, similar cyclization routes occur and the difference is the contribution of oxidation. The oxygen in environment has no remarkable effect on cyclization of AN homopolymer but retards the cyclization of AN-AM copolymers. For AN-AM copolymer with 3.59 mol% AM, the cyclization temperature is postponed 10C in air.
2010, 28(3): 377-384
doi: 10.1007/s10118-010-9033-x
Abstract:
Syndiotactic polypropylene (sPP) as-spun fiber (sPP1) and drawn fiber (sPP2) were prepared by melt-spinning and melt-spinning/hot-drawing, respectively. The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD) and tensile testing. The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature (40C). With increasing the annealing temperature, the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension. Upon removing the tension, a small amount of mesophase and trans-planar conformation will be regained. The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.
Syndiotactic polypropylene (sPP) as-spun fiber (sPP1) and drawn fiber (sPP2) were prepared by melt-spinning and melt-spinning/hot-drawing, respectively. The structure transition of the two fibers induced by annealing at different temperatures and the corresponding mechanical properties were subsequently investigated by the combination of Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD) and tensile testing. The results indicate that the chain conformation and crystal forms of the two sPP fibers are not obviously changed at low annealing temperature (40C). With increasing the annealing temperature, the trans-planar conformation and mesophase in sPP1 and sPP2 fibers can be completely transformed to helical conformation and crystal form I under tension. Upon removing the tension, a small amount of mesophase and trans-planar conformation will be regained. The mechanical properties of the annealed fibers are manifestly dependent on their initial structure and the annealing temperature.
2010, 28(3): 385-393
doi: 10.1007/s10118-010-9034-9
Abstract:
FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe was utilized to study in situ the copolymerization of butadiene (Bd) and isoprene (Ip) with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm-1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration ([Bd]) in the range of 0.46-3.88 molL-1. The signal bands at 890 and 989 cm-1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration ([Ip]) in the range of 0.08-4.73 molL-1 at 890 cm-1 and 0.08-7.49 molL-1 at 989 cm-1, respectively. Thus the signal band at 1010 cm-1 was chosen to monitor Bd concentration and bands at 989 and 890 cm-1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The polymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJmol-1 and 57.7 kJmol-1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd (rBd) and 0.48 for IP (rIp) based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.
FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe was utilized to study in situ the copolymerization of butadiene (Bd) and isoprene (Ip) with neodymium-based catalyst in hexane. The relationship between the signal intensity of monomer and its concentration was investigated. The kinetic study of copolymerization of Bd and Ip was further conducted, and the monomer reactivity ratios were determined via in situ ATR FTIR. The signal band at 1010 cm-1 was assigned to wagging vibration of Bd and its intensity was proportional to Bd concentration ([Bd]) in the range of 0.46-3.88 molL-1. The signal bands at 890 and 989 cm-1 were assigned to wagging vibration of Ip and the signal intensity was also proportional to Ip concentration ([Ip]) in the range of 0.08-4.73 molL-1 at 890 cm-1 and 0.08-7.49 molL-1 at 989 cm-1, respectively. Thus the signal band at 1010 cm-1 was chosen to monitor Bd concentration and bands at 989 and 890 cm-1 to monitor Ip concentration during the copolymerization, respectively. It was demonstrated that the conversions of Bd and Ip calculated from FTIR data agreed very well with those obtained gravimetrically. The polymerization rates were first order with respect to both [Bd] and [Ip], respectively at different polymerization temperatures. The apparent propagation activation energy for Bd and Ip could be determined to be 54.4 kJmol-1 and 57.7 kJmol-1, respectively. The monomer reactivity ratios were calculated to be 1.08 for Bd (rBd) and 0.48 for IP (rIp) based on FTIR data. The Bd-Ip copolymer products with random sequence could be obtained with only one glass transition temperature.
2010, 28(3): 395-404
doi: 10.1007/s10118-010-9037-6
Abstract:
Three dendronized polymers from generation one to generation three have been prepared by complexing negatively charged Frchet-type dendrons with a polyanion, poly(diallydimethylammonium chloride) (PDADMAC). The grafting degree has been confirmed mainly by elemental analysis. In dilute solutions of tetrahydrofuran, static light scattering studies indicate that the first generation complex has a coil-like conformation, even more flexible than PDADMAC. The second and third generation complexes exhibit polyelectrolyte behavior. Dynamic light scattering experiments indicate that all the three complexes have almost the same hydrodynamic radius, indicating that they might own similar coil conformation. Atomic force microscopy shows the existence of disordered globules formed by one or a couple of complex coils. All these observations can be explained by the flowerlike coil conformation, which is formed by the intra-molecular association. This is totally different from the stretched chain conformation formed by covalently connected dendronized polymers. This result also explains why some ordered supramolecular structures, found in condensed state of the similar complexes, are not as perfect as those of conventional dendronized polymers.
Three dendronized polymers from generation one to generation three have been prepared by complexing negatively charged Frchet-type dendrons with a polyanion, poly(diallydimethylammonium chloride) (PDADMAC). The grafting degree has been confirmed mainly by elemental analysis. In dilute solutions of tetrahydrofuran, static light scattering studies indicate that the first generation complex has a coil-like conformation, even more flexible than PDADMAC. The second and third generation complexes exhibit polyelectrolyte behavior. Dynamic light scattering experiments indicate that all the three complexes have almost the same hydrodynamic radius, indicating that they might own similar coil conformation. Atomic force microscopy shows the existence of disordered globules formed by one or a couple of complex coils. All these observations can be explained by the flowerlike coil conformation, which is formed by the intra-molecular association. This is totally different from the stretched chain conformation formed by covalently connected dendronized polymers. This result also explains why some ordered supramolecular structures, found in condensed state of the similar complexes, are not as perfect as those of conventional dendronized polymers.
2010, 28(3): 405-415
doi: 10.1007/s10118-010-9032-y
Abstract:
Biodegradable aliphatic/aromatic copolyesters, poly(butylene terephthalate-co-lactate) (PBTL) were prepared via direct melt polycondensation of terephthalic acid (TPA), 1,4-butanediol (BDO) and poly(L-lactic acid) oligomer (OLLA). The effects of polymerization time and temperature, as well as aliphatic/aromatic moiety ratio on the physical and thermal properties were investigated. The largest molecular weight of the copolyesters was up to 64100 with molecular weight distribution index of 2.09 when the polycondensation was carried out at 230C for 6 h. DSC, XRD, DMA and TGA analysis clearly indicated that the degree of crystallinity, glass-transition temperature, melting point, decomposition temperature, tensile strength, elongation and Youngs modulus were influenced by the ratio between TPA and OLLA in the final copolyesters. Hydrolytic degradation results demonstrated that the incorporation of biodegradable lactate moieties into the aromatic polyester could efficiently improve hydrolytic degradability of the copolymer even though it still had many aromatic units in the main chains.
Biodegradable aliphatic/aromatic copolyesters, poly(butylene terephthalate-co-lactate) (PBTL) were prepared via direct melt polycondensation of terephthalic acid (TPA), 1,4-butanediol (BDO) and poly(L-lactic acid) oligomer (OLLA). The effects of polymerization time and temperature, as well as aliphatic/aromatic moiety ratio on the physical and thermal properties were investigated. The largest molecular weight of the copolyesters was up to 64100 with molecular weight distribution index of 2.09 when the polycondensation was carried out at 230C for 6 h. DSC, XRD, DMA and TGA analysis clearly indicated that the degree of crystallinity, glass-transition temperature, melting point, decomposition temperature, tensile strength, elongation and Youngs modulus were influenced by the ratio between TPA and OLLA in the final copolyesters. Hydrolytic degradation results demonstrated that the incorporation of biodegradable lactate moieties into the aromatic polyester could efficiently improve hydrolytic degradability of the copolymer even though it still had many aromatic units in the main chains.
2010, 28(3): 417-425
doi: 10.1007/s10118-010-9041-x
Abstract:
Poly(-hydroxy octanoic acid) was first used as an additive for the preparation of electrospun ultra-fine fibers of poly(ethylene glycol)-b-poly(L-lactide) (PEG-PLLA). Ibuprofen was loaded in the electrospun ultra-fine fibers. The results from environmental scanning electron microscopy (ESEM), wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) demonstrated that ibuprofen could be perfectly entrapped in the fibers electrospun from PEG-PLLA using -hydroxy octanoic acid or PEG-b-poly(-hydroxy octanoic acid) (PEG-PHOA) as additives. Compared with electrospun PEG-PLLA fibers which entrapped 20 wt% ibuprofen, the PEG-PLLA electrospun fibers containing PEG-PHOA exhibited integral and robust after 1 week incubated in 37C, pH 7.4 phosphate buffer solution with 10 g/mL proteinase K. Compared with electrospun fibers without PEG-PHOA, the concentration of proteinase K in release media had less effect on the release rate of ibuprofen. An unique release profile was found from PEG-PLLA fiber after the incorporation of PEG-PHOA. Enzyme degradation experiments demonstrated that PEG-PHOA but not -hydroxy octanoic acid monomer was the crucial factor for integrity maintenance of the electrospun fibers, which may be due to the enzyme degradation tolerance property of the PEG-PHOA polymer additive.
Poly(-hydroxy octanoic acid) was first used as an additive for the preparation of electrospun ultra-fine fibers of poly(ethylene glycol)-b-poly(L-lactide) (PEG-PLLA). Ibuprofen was loaded in the electrospun ultra-fine fibers. The results from environmental scanning electron microscopy (ESEM), wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) demonstrated that ibuprofen could be perfectly entrapped in the fibers electrospun from PEG-PLLA using -hydroxy octanoic acid or PEG-b-poly(-hydroxy octanoic acid) (PEG-PHOA) as additives. Compared with electrospun PEG-PLLA fibers which entrapped 20 wt% ibuprofen, the PEG-PLLA electrospun fibers containing PEG-PHOA exhibited integral and robust after 1 week incubated in 37C, pH 7.4 phosphate buffer solution with 10 g/mL proteinase K. Compared with electrospun fibers without PEG-PHOA, the concentration of proteinase K in release media had less effect on the release rate of ibuprofen. An unique release profile was found from PEG-PLLA fiber after the incorporation of PEG-PHOA. Enzyme degradation experiments demonstrated that PEG-PHOA but not -hydroxy octanoic acid monomer was the crucial factor for integrity maintenance of the electrospun fibers, which may be due to the enzyme degradation tolerance property of the PEG-PHOA polymer additive.
2010, 28(3): 427-435
doi: 10.1007/s10118-010-9050-9
Abstract:
Adsorption of humic, tannic and gallic acids by a macro weakly basic ion-exchange resin JN-01 was studied. The adsorption capacity of this resin for gallic and tannic acids is much higher than that for humic acid, which can be explained on the basis of both their molecular size and ionization degree. Furthermore, humic acid is separated into different components with molecular weight in the range from 2000 Da to 100000 Da by ultra-filter, and their adsorption isotherms on resin JN-01 indicate that humic acids molecular weight is an important factor which makes significant influence on adsorption. Finally, changes in the amount of Cu2+ and Pb2+ adsorbed on resin JN-01 as a function of the concentration of each of these three acids were studied. A large increase in the heavy metal ions uptake is observed in the presence of humic substance, such advantages are due to the interactions between the heavy metal ions and the unbound functional groups of the adsorbed organic acids.
Adsorption of humic, tannic and gallic acids by a macro weakly basic ion-exchange resin JN-01 was studied. The adsorption capacity of this resin for gallic and tannic acids is much higher than that for humic acid, which can be explained on the basis of both their molecular size and ionization degree. Furthermore, humic acid is separated into different components with molecular weight in the range from 2000 Da to 100000 Da by ultra-filter, and their adsorption isotherms on resin JN-01 indicate that humic acids molecular weight is an important factor which makes significant influence on adsorption. Finally, changes in the amount of Cu2+ and Pb2+ adsorbed on resin JN-01 as a function of the concentration of each of these three acids were studied. A large increase in the heavy metal ions uptake is observed in the presence of humic substance, such advantages are due to the interactions between the heavy metal ions and the unbound functional groups of the adsorbed organic acids.
2010, 28(3): 437-447
doi: 10.1007/s10118-010-9085-y
Abstract:
The effects of heating rate on the aggregate behavior of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions were investigated in detail by laser light scattering and TEM. By employing two separate heating protocols, step-by-step heating at 5 K/step and one-step jump, to heat the sample from 15oC to the selected temperature, we found that the heating rate only showed significant effect on the aggregates above the cloud point. The aggregate formed by step-by-step heating exhibited a much larger size and a broader size distribution than those formed by one-step jump heating. Moreover, neither of the aggregates were ideal micellar structures as indicated by the size and the Rg/Rh values. On the contrary, at temperatures below the cloud point where the block copolymer formed core-shelled micelles, the heating rate showed negligible effect on the size and size distribution of the micelles. Since the system underwent a phase separation above the cloud point, the heating rate effect could be reasonably explained by the phase separation mechanisms: the nucleation-and-growth mechanism in the metastable region and the spinodal decomposition mechanism in the unstable region.
The effects of heating rate on the aggregate behavior of poly(ethylene oxide)-b-poly(N-isopropylacrylamide) in aqueous solutions were investigated in detail by laser light scattering and TEM. By employing two separate heating protocols, step-by-step heating at 5 K/step and one-step jump, to heat the sample from 15oC to the selected temperature, we found that the heating rate only showed significant effect on the aggregates above the cloud point. The aggregate formed by step-by-step heating exhibited a much larger size and a broader size distribution than those formed by one-step jump heating. Moreover, neither of the aggregates were ideal micellar structures as indicated by the size and the Rg/Rh values. On the contrary, at temperatures below the cloud point where the block copolymer formed core-shelled micelles, the heating rate showed negligible effect on the size and size distribution of the micelles. Since the system underwent a phase separation above the cloud point, the heating rate effect could be reasonably explained by the phase separation mechanisms: the nucleation-and-growth mechanism in the metastable region and the spinodal decomposition mechanism in the unstable region.
2010, 28(3): 449-456
doi: 10.1007/s10118-010-9092-z
Abstract:
The copolymerization of 4-vinylbenzyl chloride (VBC) and vinyl acetate (VAC) was carried out in toluene at 75C via radical polymerization using 2,2-azo-bis-(isobutyronitrile) (AIBN) as an initiator. The random copolymers of poly(4-vinylbenzyl chloride-co-vinyl acetate) (P(VBC-co-VAC)) with number average molecular weight (Mn) from 2000 to 6900, relatively narrow molecular weight distribution (MWD, Mw/Mn ca. 2.0) and with different copolymer composition of 4-vinylbenzyl chloride (VBC) from 17 mol% to 62 mol% could be obtained. The P(VBC-co-VAC) copolymers with an average number of 7 to 13 initiating sites of benzyl chloride per macromolecule could be used for the cationic polymerization of isobutylene (IB). The cationic polymerizations of IB were further conducted by using P(VBC-co-VAC) copolymers as macroinitiators in conjunction with TiCl4 at-40C in CH2Cl2. The effects of VBC/TiCl4 (molar ratio) on monomer conversion, Mn and MWD of the resultant copolymers were investigated under 3 sets of conditions. It is found that P(VBC-co-VAC)-g-PIB copolymers with relatively narrow MWD (Mw/Mn ca. 2.0) and with terminal tert-chlorine functional groups in branched PIB chains could be successfully synthesized when VBC/TiCl4 (molar ratio) was set in the range from 0.10 to 1.12. The unimodal GPC curve of the P(VBC-co-VAC)-g-PIB copolymers by RI detector was almost in harmony with the GPC curve by UV detector. The TEM image of the P(VBC-co-VAC)-g-PIB copolymer stained by RuO indicated that the copolymer formed a two-phase morphology with P(VBC-co-VAC)-rich domains of 20-100 nm in size tethered by PIB branch segments.
The copolymerization of 4-vinylbenzyl chloride (VBC) and vinyl acetate (VAC) was carried out in toluene at 75C via radical polymerization using 2,2-azo-bis-(isobutyronitrile) (AIBN) as an initiator. The random copolymers of poly(4-vinylbenzyl chloride-co-vinyl acetate) (P(VBC-co-VAC)) with number average molecular weight (Mn) from 2000 to 6900, relatively narrow molecular weight distribution (MWD, Mw/Mn ca. 2.0) and with different copolymer composition of 4-vinylbenzyl chloride (VBC) from 17 mol% to 62 mol% could be obtained. The P(VBC-co-VAC) copolymers with an average number of 7 to 13 initiating sites of benzyl chloride per macromolecule could be used for the cationic polymerization of isobutylene (IB). The cationic polymerizations of IB were further conducted by using P(VBC-co-VAC) copolymers as macroinitiators in conjunction with TiCl4 at-40C in CH2Cl2. The effects of VBC/TiCl4 (molar ratio) on monomer conversion, Mn and MWD of the resultant copolymers were investigated under 3 sets of conditions. It is found that P(VBC-co-VAC)-g-PIB copolymers with relatively narrow MWD (Mw/Mn ca. 2.0) and with terminal tert-chlorine functional groups in branched PIB chains could be successfully synthesized when VBC/TiCl4 (molar ratio) was set in the range from 0.10 to 1.12. The unimodal GPC curve of the P(VBC-co-VAC)-g-PIB copolymers by RI detector was almost in harmony with the GPC curve by UV detector. The TEM image of the P(VBC-co-VAC)-g-PIB copolymer stained by RuO indicated that the copolymer formed a two-phase morphology with P(VBC-co-VAC)-rich domains of 20-100 nm in size tethered by PIB branch segments.
