The ester base oil of dioctyl adipate (DOA) was oxidized in an oven at 200 degrees C for 30 h, and variations in the physicochemical and tribological properties were studied. To investigate the thermal-oxidation mecha...The ester base oil of dioctyl adipate (DOA) was oxidized in an oven at 200 degrees C for 30 h, and variations in the physicochemical and tribological properties were studied. To investigate the thermal-oxidation mechanism, the thermal-oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS), and the thermal-oxidation process was simulated using visual reactive force field molecular dynamics (ReaxFF MD). The results indicated that the total acid number (TAN) increased significantly because of the presence of 14% carboxylic acids and low molecular weight monoesters. The tribological properties were improved by the formation of the strongly polar carboxylic acids. Additionally, the increase in kinematic viscosity was limited due to the formation of high molecular weight polymerization products and low molecular weight degradation products. Thermal-oxidative degradation and polymerization mechanisms were proposed by combining ReaxFF MD simulations and GC-MS results.展开更多
Phthalates and adipate ester in water have been extracted with n-hexane and analyzed by gas chromatography-mass spectrometry(GC-MS).The mean recoveries ranged from 69% to 109% with their RSD range of 1.96%-10.2%.The r...Phthalates and adipate ester in water have been extracted with n-hexane and analyzed by gas chromatography-mass spectrometry(GC-MS).The mean recoveries ranged from 69% to 109% with their RSD range of 1.96%-10.2%.The research results also showed that the method presented simplicity-operating,excellent linearity and reproducibility.展开更多
Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization beha...Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.展开更多
The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends we...The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.展开更多
The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differen...The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge- on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the （00l） PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.展开更多
The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy ...The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy （IR） and scanning electron microscopy （SEM）. The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within theγ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.展开更多
An aliphatic polyester, poly(hexalene adipate) (PHA) and an aliphatic copolyester, poly (hexalene adipate succinate) (PHAS) were synthesized by direct condensation of corresponding binary acid and binary alcohol in th...An aliphatic polyester, poly(hexalene adipate) (PHA) and an aliphatic copolyester, poly (hexalene adipate succinate) (PHAS) were synthesized by direct condensation of corresponding binary acid and binary alcohol in the presence of a catalyst, p-toluene sulfonic acid. The biodegradation of these polyesters were studied in the laboratory by enzyme attack and outdoor soil burial. The results show that these polyesters have good biodegradability and the copolyester PHAS, even displayed a better biodegradability than the polyester PHA. In the presence of Penicillium chrysogenum the weight loss reached 18.3% for the PHAS (film thickness 1.0 mm) and 9.1% for the PHA (film thickness 1.0 mm) after 28 days. Outdoor soil burial tests indicate that these polyesters also have good biodegradability in natural conditions. The weight loss reached 14.2% for PHAS (film thickness 0.1 mm) and 6.7% for PHA (film thickness 0.1 mm) after burying in soil for 36 days.展开更多
Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal cryst...Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal crystallization. It was found that both the Teflon surface structure and the PBA polymorphic structure are the determining factors to induce epitaxial crystallization. The oriented Teflon film was able to induce epitaxial crystallization of PBA α crystal, while the non-oriented Teflon did not induce any epitaxial crystallization of PBA. Epitaxial crystallization did not occurred for PBA β crystals between neither the oriented nor the non-oriented Teflon films. The enzymatic degradation rate of PBA films was not determined by the epitaxial crystallization, in fact it was still dependent on the polymorphic crystal structure of PBA. The morphological changes of PBA films after enzymatic degradation confirmed again that the epitaxial crystallization only occurred for the PBA film with α crystal structure which was produced by being sandwiched between oriented Teflon films, and it happened only on the surface of PBA films.展开更多
The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, opti...The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, optical microscopy（OM） and scanning electron microscopy（SEM）. A depression of the equilibrium melting point of PVDF was observed. From the melting point data of PVDF, a negative but quite small value of the interaction parameter ？PVDF-PEA is derived using the Flory-Huggins equation, implying that PVDF shows miscibility with PEA to some extent. Nonisothermal and isothermal crystallization kinetics suggest that the crystallization rate of PVDF decreases with increasing the amount of PEA, and a contrary trend was found when PEA crystallizes with the increase of the amount of PVDF. It was further disclosed that the blend ratio and crystallization temperature affect the texture of PVDF spherulites greatly, which determines the subsequent crystallization of PEA. At high temperatures, e.g. 150 ℃, the band spacing of PVDF spherulites increases with the addition of PEA content and the spherulitic structure becomes more open. In this case, spherulitic crystallization of PEA is not observed for all blend compositions. At low temperatures, e.g. 130 ℃, for the PEA-rich blends, the interpenetrated structures are eventually formed by the penetration of the spherulites of PEA growing within the pre-existing PVDF spherulites.展开更多
基金The authors are grateful for the financial support from the National Basic Research Program of China，the National Natural Science Foundation of China
文摘The ester base oil of dioctyl adipate (DOA) was oxidized in an oven at 200 degrees C for 30 h, and variations in the physicochemical and tribological properties were studied. To investigate the thermal-oxidation mechanism, the thermal-oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS), and the thermal-oxidation process was simulated using visual reactive force field molecular dynamics (ReaxFF MD). The results indicated that the total acid number (TAN) increased significantly because of the presence of 14% carboxylic acids and low molecular weight monoesters. The tribological properties were improved by the formation of the strongly polar carboxylic acids. Additionally, the increase in kinematic viscosity was limited due to the formation of high molecular weight polymerization products and low molecular weight degradation products. Thermal-oxidative degradation and polymerization mechanisms were proposed by combining ReaxFF MD simulations and GC-MS results.
文摘Phthalates and adipate ester in water have been extracted with n-hexane and analyzed by gas chromatography-mass spectrometry(GC-MS).The mean recoveries ranged from 69% to 109% with their RSD range of 1.96%-10.2%.The research results also showed that the method presented simplicity-operating,excellent linearity and reproducibility.
基金financially supported by the National Natural Science Foundation of China(No.21304070)Natural Science Foundation of Tianjin City(No.15JCYBJC47300)+1 种基金Major Program of National Natural Science Foundation of China(No.11432016)the Municipal Key Program of Natural Science Foundation of Tianjin(No.14JCZDJC40700)
文摘Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045 and 21276151)Natural Science Basic Research Plan in Shaanxi Province of China(No.2011JQ2004)Key Scientific Research Group of Shaanxi Province(No.2013KCT-08)
文摘The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.
基金financially supported by the National Natural Science Foundation of China(Nos.50833006,21274009,21204018,51221002and50973008)
文摘The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge- on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the （00l） PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045 and 21276151)Key Scientific Research Group of Shanxi Province(No.2013KCT-08)Scientific Research Group of Shanxi University of Science and Technology(No.TD12-04)
文摘The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy （IR） and scanning electron microscopy （SEM）. The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within theγ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.
文摘An aliphatic polyester, poly(hexalene adipate) (PHA) and an aliphatic copolyester, poly (hexalene adipate succinate) (PHAS) were synthesized by direct condensation of corresponding binary acid and binary alcohol in the presence of a catalyst, p-toluene sulfonic acid. The biodegradation of these polyesters were studied in the laboratory by enzyme attack and outdoor soil burial. The results show that these polyesters have good biodegradability and the copolyester PHAS, even displayed a better biodegradability than the polyester PHA. In the presence of Penicillium chrysogenum the weight loss reached 18.3% for the PHAS (film thickness 1.0 mm) and 9.1% for the PHA (film thickness 1.0 mm) after 28 days. Outdoor soil burial tests indicate that these polyesters also have good biodegradability in natural conditions. The weight loss reached 14.2% for PHAS (film thickness 0.1 mm) and 6.7% for PHA (film thickness 0.1 mm) after burying in soil for 36 days.
基金financially supported by the National Natural Science Foundation of China(No.51025314)the Oticon Foundation in Denmark
文摘Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal crystallization. It was found that both the Teflon surface structure and the PBA polymorphic structure are the determining factors to induce epitaxial crystallization. The oriented Teflon film was able to induce epitaxial crystallization of PBA α crystal, while the non-oriented Teflon did not induce any epitaxial crystallization of PBA. Epitaxial crystallization did not occurred for PBA β crystals between neither the oriented nor the non-oriented Teflon films. The enzymatic degradation rate of PBA films was not determined by the epitaxial crystallization, in fact it was still dependent on the polymorphic crystal structure of PBA. The morphological changes of PBA films after enzymatic degradation confirmed again that the epitaxial crystallization only occurred for the PBA film with α crystal structure which was produced by being sandwiched between oriented Teflon films, and it happened only on the surface of PBA films.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045,21276151)Key Scientific Research Group of Shanxi Province(No.2013KCT-08)Scientific Research Group of Shanxi University of Science and Technology(No.TD12-04)
文摘The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, optical microscopy（OM） and scanning electron microscopy（SEM）. A depression of the equilibrium melting point of PVDF was observed. From the melting point data of PVDF, a negative but quite small value of the interaction parameter ？PVDF-PEA is derived using the Flory-Huggins equation, implying that PVDF shows miscibility with PEA to some extent. Nonisothermal and isothermal crystallization kinetics suggest that the crystallization rate of PVDF decreases with increasing the amount of PEA, and a contrary trend was found when PEA crystallizes with the increase of the amount of PVDF. It was further disclosed that the blend ratio and crystallization temperature affect the texture of PVDF spherulites greatly, which determines the subsequent crystallization of PEA. At high temperatures, e.g. 150 ℃, the band spacing of PVDF spherulites increases with the addition of PEA content and the spherulitic structure becomes more open. In this case, spherulitic crystallization of PEA is not observed for all blend compositions. At low temperatures, e.g. 130 ℃, for the PEA-rich blends, the interpenetrated structures are eventually formed by the penetration of the spherulites of PEA growing within the pre-existing PVDF spherulites.
