This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure...This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.展开更多
Titanium silicalite-1(TS-1) was synthesized by a hydrothermal synthesis method with different amounts of tetrapropyl ammonium hydroxide(TPAOH) as template.The as-prepared TS-1 was characterized by scanning electron mi...Titanium silicalite-1(TS-1) was synthesized by a hydrothermal synthesis method with different amounts of tetrapropyl ammonium hydroxide(TPAOH) as template.The as-prepared TS-1 was characterized by scanning electron microscopy,X-ray powder diffraction,Fourier-transform infrared resonance spectroscopy,ultravioletvisible diffuse reflectance spectroscopy and nitrogen physical adsorption and desorption,and studied in the propylene epoxidation with hydrogen peroxide in a fixed bed reactor.The results showed that the amount of TPAOH had a strong influence on the grain morphology,the amount of framework Ti,and the average particle sizes of TS-1.With the increase of TPAOH amount in the synthesis(the molar ratio of TPAOH/SiO_2 increasing from 0.25 to 0.45),the morphology changed gradually from ellipsoids to cubes,the particle sizes of TS-1 decreased slightly,the amount of the framework Ti increased appreciably,and the catalytic stability in the propylene epoxidation increased markedly.Moreover,all the catalysts had the same selectivity to propylene epoxide.However,when the molar ratio of TPAOH/SiO_2 was further increased to 0.55,the particles became large hexagons with the size distribution in a wide range,and the catalytic stability decreased sharply although the amount of the framework Ti increased further,which can be attributed to the long diffusion paths of the reactants in the zeolite.展开更多
Bipolar membrane electrodialysis(BMED) has already been described for the preparation of quaternary ammonium hydroxide. However, compared to quaternary ammonium hydroxide, di-quaternary ammonium hydroxide has raised g...Bipolar membrane electrodialysis(BMED) has already been described for the preparation of quaternary ammonium hydroxide. However, compared to quaternary ammonium hydroxide, di-quaternary ammonium hydroxide has raised great interest due to its high thermal stability and good oriented performance.In order to synthesize N,N-hexamethylenebis(trimethyl ammonium hydroxide)(HM(OH)_2) by EDBM,experiments designed by response surface methodology were carried out on the basis of single-factor experiments. The factors include current density, feed concentration and flow ratio of each compartment(feed compartment: base compartment: acid compartment: buffer compartment). The relationship between current efficiency and the above-mentioned three factors was quantitatively described by a multivariate regression model. According to the results, the feed concentration was the most significant factor and the optimum conditions were as follows: the current efficiency was up to 76.2%(the hydroxide conversion was over 98.6%), with a current density of 13.15 m A·cm^(-2), a feed concentration of 0.27 mol·L^(-1) and a flow ratio of 20 L·h^(-1):26 L·h^(-1):20 L·h^(-1):20 L·h^(-1) for feed compartment, base compartment, acid compartment, and intermediate compartment, respectively. This study demonstrates the optimized parameters of manufacturing HM(OH)_2 by direct splitting its halide for industrial application.展开更多
The flame-retardant properties of polyurethane(PU)containing ammonium polyphosphate(APP)and aluminum hydroxide(ATH)were investigated.Moreover,the flame retardant performance was investigated through thermogravimetric ...The flame-retardant properties of polyurethane(PU)containing ammonium polyphosphate(APP)and aluminum hydroxide(ATH)were investigated.Moreover,the flame retardant performance was investigated through thermogravimetric analysis,limiting oxygen index(LOI),vertical combustion(UL 94),and cone calorimeter.When 15 wt%APP and 5 wt%ATH were added together,the PU/15%APP/5%ATH sample shows better thermal stability and flame-retardant properties.When 15 wt%APP and 5 wt%ATH were added together,the LOI value of the PU/15%APP/5%ATH sample was 30.5%,and UL 94 V-0 rating was attained.Compared with PU,the peak heat release rate(PHRR),total heat release(THR),and average effective heat combustion(av-EHC)of the PU/15%APP/5%ATH sample decreased by 43.1%,21.0%,and 29.4%,respectively.In addition,the flame-retardant mechanism was investigated through cone calorimeter.The APP/ATH addition simultaneously exerted condensed phase and gas phase flame retardant effects.APP and ATH have synergistic flame retardant properties.展开更多
The precursor of ammonium aluminum carbonate hydroxide was synthesized by using aluminum sulfate（Al2（SO4）3） and ammonium carbonate（（NH4）2CO3）. The effects of α-Al2O3 seeds and mixture composed of α-Al2O3 and...The precursor of ammonium aluminum carbonate hydroxide was synthesized by using aluminum sulfate（Al2（SO4）3） and ammonium carbonate（（NH4）2CO3）. The effects of α-Al2O3 seeds and mixture composed of α-Al2O3 and ammonium nitrate, as well as multiplex catalysts （AT） on phase transformation of alumina in sintering process were investigated respectively. The results show that the α-Al2O3 seeds and the mixture of α-Al2O3 and ammonium nitrate can lower the phase transformation temperature of α-Al2O3 to different extents while the particles obtained agglomerate heavily. AT has great potential synergistic effects on the phase transformation of alumina and reduces the phase transformation temperature of α-Al2O3 and the trends of necking-formation between particles. Therefore the dispersion of powder particles is improved significantly.展开更多
An optimal concentration of the etching solution for deep etching of silicon, including 3% tetramethyl ammonium hydroxide and 0.3% (NH4)2S208, was achieved in this paper. For this etching solution, the etching rates o...An optimal concentration of the etching solution for deep etching of silicon, including 3% tetramethyl ammonium hydroxide and 0.3% (NH4)2S208, was achieved in this paper. For this etching solution, the etching rates of silicon and silicon dioxide were about 1.1μm.min^-1 and 0.5 nm.min^-1, respectively. The etching ratio between (100) and (111) planes was about 34:1, and the etched surface was very smooth.展开更多
Under the conditions of tetramethyl ammonia chloride (TMAC) used as starting material, Ti-based Dimensionally Stable Anode (DSA), stainless steel used as cathode and Nafion 900 cation membrane as cell diaphragm, this ...Under the conditions of tetramethyl ammonia chloride (TMAC) used as starting material, Ti-based Dimensionally Stable Anode (DSA), stainless steel used as cathode and Nafion 900 cation membrane as cell diaphragm, this paper studies the synthesis of tetramethyl ammonium hydroxide (TMAH) by cell diaphragm electrolytic method, examining not only the effects of current density, concentration of starting material and cell temperature, on the product purity and current efficiency, but also the effects of electrolyte circulation rate on the service life of Ti-based DSA. The experiment puts forward an optimum processing condition, and experimental findings show that preparing TMAH by using this technique can obtain a current efficiency 74.7% and get product with a purity greater than 99.9%.展开更多
A series of long-chain quaternary ammonium hydroxides were synthesized from tertiary amines and confirmed by ~1H NMR and FTIR.Surface properties and pH of these surfactants were investigated.The critical micelle conce...A series of long-chain quaternary ammonium hydroxides were synthesized from tertiary amines and confirmed by ~1H NMR and FTIR.Surface properties and pH of these surfactants were investigated.The critical micelle concentrations（CMC） of the synthesized quaternary ammonium hydroxides are lower than the conventional quaternary ammonium surfactants.The micelles shapes of these long-chain quaternary ammonium hydroxides in aqueous solution are spherical at a concentration of 0.1 mol/L.The pH values of the synthesized quaternary ammonium hydroxides are 12.25-12.51.展开更多
A simple and versatile strategy is designed to successfully fabricate ultrafine TiO2 nano-cages based on the rapid decomposition reaction between amphoteric hydroxide and ammonia solution by pulsed laser ablation of T...A simple and versatile strategy is designed to successfully fabricate ultrafine TiO2 nano-cages based on the rapid decomposition reaction between amphoteric hydroxide and ammonia solution by pulsed laser ablation of Ti/Al alloy in liquid. With the ammonia concentration （ V ammonia ：V water, where V is volume） increasing from 1 ： 10 to 1：4, the diameter and shell thickness of quasi-spherical TiO2 nano-cages substantially decrease from 300 and 60 nm to 9.2 and 2.8 nm, respectively. The obtained results have significant implications for obtaining insight into the properties of the TiO2 porous nano-cages, offering the basis for further fabrication of other nano-cages.展开更多
Ammonium aluminum sulfate hydroxide[NH4Al（SO4）2·12H2O], the precursor of Al2O3, was prepared with the method of sintering, leaching and adjusting the pH value by using fly ash and ammonium sulfate as raw materi...Ammonium aluminum sulfate hydroxide[NH4Al（SO4）2·12H2O], the precursor of Al2O3, was prepared with the method of sintering, leaching and adjusting the pH value by using fly ash and ammonium sulfate as raw materials.High-purity alumina was prepared by calcining NH4Al（SO4）2·12H2O.The effects of the temperature and time of sintering, molar ratio of（NH4）2SO4 vs the Al2O3 in fly ash and the grain size of fly ash on the extraction efficiency of Al2O3 from fly ash were studied.The efficiency of Al2O3 extraction could reach 95.6 percent under the optimum conditions.The purity of the Al2O3 from calcining NH4Al（SO4）2·12H2O that was refined by recrystallization was higher than 99.9 percent.展开更多
针对聚磷酸铵(APP)有一定的水溶解性和阻燃效率不高等问题,提出了采用氢氧化铝(ATH)包覆改性APP的方法。X射线荧光光谱(XRF)和扫描电镜(SEM)分析结果显示,在APP颗粒表面实现了ATH的包覆改性。测试表明,ATH包覆改性后的APP溶解度明显下降...针对聚磷酸铵(APP)有一定的水溶解性和阻燃效率不高等问题,提出了采用氢氧化铝(ATH)包覆改性APP的方法。X射线荧光光谱(XRF)和扫描电镜(SEM)分析结果显示,在APP颗粒表面实现了ATH的包覆改性。测试表明,ATH包覆改性后的APP溶解度明显下降,比表面大幅增加。将改性后的APP与双季戊四醇(DPER)复配,作为膨胀阻燃剂添加到PP中,阻燃PP的燃烧性能测试结果表明:阻燃剂总添加量为25%时,包覆ATH的APP使阻燃PP 3.2 mm样条的垂直燃烧级别从V-1提高到V-0,氧指数(LOI)从26.6%增加到31.8%,热释放速率峰值(PHRR)从475 k W/m2下降至308 k W/m2,下降了约35%。对阻燃PP的燃烧残炭研究说明,APP经ATH包覆改性后,促进了阻燃PP在燃烧时形成更加完整均匀的炭层,因而改善了阻燃性能。展开更多
基金the financial support by the National Natural Science Foundation of China (No. 20973022 and No. 11472048)
文摘This article presents a detailed structural study of a new spherical Mg Cl2-supported Ti Cl4 Ziegler-Natta catalyst for isotactic propylene polymerization, and researches on the relationship between catalyst structure and polymer properties. The spherical support with the chemical composition of CH3CH2 OMg OCH(CH2Cl)2 has been synthesized from a new dispersion system and is used as the supporting material to prepare Ziegler-Natta catalyst. The XRD analysis indicates that the catalyst is fully activated with δ-Mg Cl2 in the active catalyst. The far-IR spectrometric results confirm again the presence of δ-Mg Cl2 in the active catalyst. Textural property of the active catalyst exhibits high surface area coupled with high porosity. The high activity in propylene polymerization is mainly ascribed to the full activation and the porous structure of the catalyst. Scanning electron microscopy/energy dispersive spectrometer mapping results indicate a uniform titanium distribution throughout the catalyst particles. Particle size analysis shows that the catalyst has a narrow particle size distribution. The perfect spherical shape, uniform titanium distribution and narrow particle size distribution of the catalyst confirm the advantage of polymer particles production with less fines. The solid state 13 C NMR and mid-IR spectroscopic analyses indicate that there exists strong complexation between diisobutyl phthalate and Mg Cl2, which leads to the high isotacticity of polypropylene.
基金Supported by the National Natural Science Foundation of China(No.21276183)
文摘Titanium silicalite-1(TS-1) was synthesized by a hydrothermal synthesis method with different amounts of tetrapropyl ammonium hydroxide(TPAOH) as template.The as-prepared TS-1 was characterized by scanning electron microscopy,X-ray powder diffraction,Fourier-transform infrared resonance spectroscopy,ultravioletvisible diffuse reflectance spectroscopy and nitrogen physical adsorption and desorption,and studied in the propylene epoxidation with hydrogen peroxide in a fixed bed reactor.The results showed that the amount of TPAOH had a strong influence on the grain morphology,the amount of framework Ti,and the average particle sizes of TS-1.With the increase of TPAOH amount in the synthesis(the molar ratio of TPAOH/SiO_2 increasing from 0.25 to 0.45),the morphology changed gradually from ellipsoids to cubes,the particle sizes of TS-1 decreased slightly,the amount of the framework Ti increased appreciably,and the catalytic stability in the propylene epoxidation increased markedly.Moreover,all the catalysts had the same selectivity to propylene epoxide.However,when the molar ratio of TPAOH/SiO_2 was further increased to 0.55,the particles became large hexagons with the size distribution in a wide range,and the catalytic stability decreased sharply although the amount of the framework Ti increased further,which can be attributed to the long diffusion paths of the reactants in the zeolite.
文摘Bipolar membrane electrodialysis(BMED) has already been described for the preparation of quaternary ammonium hydroxide. However, compared to quaternary ammonium hydroxide, di-quaternary ammonium hydroxide has raised great interest due to its high thermal stability and good oriented performance.In order to synthesize N,N-hexamethylenebis(trimethyl ammonium hydroxide)(HM(OH)_2) by EDBM,experiments designed by response surface methodology were carried out on the basis of single-factor experiments. The factors include current density, feed concentration and flow ratio of each compartment(feed compartment: base compartment: acid compartment: buffer compartment). The relationship between current efficiency and the above-mentioned three factors was quantitatively described by a multivariate regression model. According to the results, the feed concentration was the most significant factor and the optimum conditions were as follows: the current efficiency was up to 76.2%(the hydroxide conversion was over 98.6%), with a current density of 13.15 m A·cm^(-2), a feed concentration of 0.27 mol·L^(-1) and a flow ratio of 20 L·h^(-1):26 L·h^(-1):20 L·h^(-1):20 L·h^(-1) for feed compartment, base compartment, acid compartment, and intermediate compartment, respectively. This study demonstrates the optimized parameters of manufacturing HM(OH)_2 by direct splitting its halide for industrial application.
基金Supported by the Natural Science Foundation of Guangdong(Nos.2014A030313241,2014B090901068,and 2016A010103003).
文摘The flame-retardant properties of polyurethane(PU)containing ammonium polyphosphate(APP)and aluminum hydroxide(ATH)were investigated.Moreover,the flame retardant performance was investigated through thermogravimetric analysis,limiting oxygen index(LOI),vertical combustion(UL 94),and cone calorimeter.When 15 wt%APP and 5 wt%ATH were added together,the PU/15%APP/5%ATH sample shows better thermal stability and flame-retardant properties.When 15 wt%APP and 5 wt%ATH were added together,the LOI value of the PU/15%APP/5%ATH sample was 30.5%,and UL 94 V-0 rating was attained.Compared with PU,the peak heat release rate(PHRR),total heat release(THR),and average effective heat combustion(av-EHC)of the PU/15%APP/5%ATH sample decreased by 43.1%,21.0%,and 29.4%,respectively.In addition,the flame-retardant mechanism was investigated through cone calorimeter.The APP/ATH addition simultaneously exerted condensed phase and gas phase flame retardant effects.APP and ATH have synergistic flame retardant properties.
文摘The precursor of ammonium aluminum carbonate hydroxide was synthesized by using aluminum sulfate（Al2（SO4）3） and ammonium carbonate（（NH4）2CO3）. The effects of α-Al2O3 seeds and mixture composed of α-Al2O3 and ammonium nitrate, as well as multiplex catalysts （AT） on phase transformation of alumina in sintering process were investigated respectively. The results show that the α-Al2O3 seeds and the mixture of α-Al2O3 and ammonium nitrate can lower the phase transformation temperature of α-Al2O3 to different extents while the particles obtained agglomerate heavily. AT has great potential synergistic effects on the phase transformation of alumina and reduces the phase transformation temperature of α-Al2O3 and the trends of necking-formation between particles. Therefore the dispersion of powder particles is improved significantly.
文摘An optimal concentration of the etching solution for deep etching of silicon, including 3% tetramethyl ammonium hydroxide and 0.3% (NH4)2S208, was achieved in this paper. For this etching solution, the etching rates of silicon and silicon dioxide were about 1.1μm.min^-1 and 0.5 nm.min^-1, respectively. The etching ratio between (100) and (111) planes was about 34:1, and the etched surface was very smooth.
文摘Under the conditions of tetramethyl ammonia chloride (TMAC) used as starting material, Ti-based Dimensionally Stable Anode (DSA), stainless steel used as cathode and Nafion 900 cation membrane as cell diaphragm, this paper studies the synthesis of tetramethyl ammonium hydroxide (TMAH) by cell diaphragm electrolytic method, examining not only the effects of current density, concentration of starting material and cell temperature, on the product purity and current efficiency, but also the effects of electrolyte circulation rate on the service life of Ti-based DSA. The experiment puts forward an optimum processing condition, and experimental findings show that preparing TMAH by using this technique can obtain a current efficiency 74.7% and get product with a purity greater than 99.9%.
基金the financial support from Research Institute Technology Development Special Fund of Ministry of Science and Technology(No.2012EG11120)
文摘A series of long-chain quaternary ammonium hydroxides were synthesized from tertiary amines and confirmed by ~1H NMR and FTIR.Surface properties and pH of these surfactants were investigated.The critical micelle concentrations（CMC） of the synthesized quaternary ammonium hydroxides are lower than the conventional quaternary ammonium surfactants.The micelles shapes of these long-chain quaternary ammonium hydroxides in aqueous solution are spherical at a concentration of 0.1 mol/L.The pH values of the synthesized quaternary ammonium hydroxides are 12.25-12.51.
基金supported by the National Natural Science Foundation of China(Nos.11105085,11275116,and 11375108)the Excellent Youth and Middle Age Scientists Fund of Shandong Province(No.BS2012CL024)the Fundamental Research Funds of Shandong University(No.2015JC007)
文摘A simple and versatile strategy is designed to successfully fabricate ultrafine TiO2 nano-cages based on the rapid decomposition reaction between amphoteric hydroxide and ammonia solution by pulsed laser ablation of Ti/Al alloy in liquid. With the ammonia concentration （ V ammonia ：V water, where V is volume） increasing from 1 ： 10 to 1：4, the diameter and shell thickness of quasi-spherical TiO2 nano-cages substantially decrease from 300 and 60 nm to 9.2 and 2.8 nm, respectively. The obtained results have significant implications for obtaining insight into the properties of the TiO2 porous nano-cages, offering the basis for further fabrication of other nano-cages.
文摘Ammonium aluminum sulfate hydroxide[NH4Al（SO4）2·12H2O], the precursor of Al2O3, was prepared with the method of sintering, leaching and adjusting the pH value by using fly ash and ammonium sulfate as raw materials.High-purity alumina was prepared by calcining NH4Al（SO4）2·12H2O.The effects of the temperature and time of sintering, molar ratio of（NH4）2SO4 vs the Al2O3 in fly ash and the grain size of fly ash on the extraction efficiency of Al2O3 from fly ash were studied.The efficiency of Al2O3 extraction could reach 95.6 percent under the optimum conditions.The purity of the Al2O3 from calcining NH4Al（SO4）2·12H2O that was refined by recrystallization was higher than 99.9 percent.
文摘针对聚磷酸铵(APP)有一定的水溶解性和阻燃效率不高等问题,提出了采用氢氧化铝(ATH)包覆改性APP的方法。X射线荧光光谱(XRF)和扫描电镜(SEM)分析结果显示,在APP颗粒表面实现了ATH的包覆改性。测试表明,ATH包覆改性后的APP溶解度明显下降,比表面大幅增加。将改性后的APP与双季戊四醇(DPER)复配,作为膨胀阻燃剂添加到PP中,阻燃PP的燃烧性能测试结果表明:阻燃剂总添加量为25%时,包覆ATH的APP使阻燃PP 3.2 mm样条的垂直燃烧级别从V-1提高到V-0,氧指数(LOI)从26.6%增加到31.8%,热释放速率峰值(PHRR)从475 k W/m2下降至308 k W/m2,下降了约35%。对阻燃PP的燃烧残炭研究说明,APP经ATH包覆改性后,促进了阻燃PP在燃烧时形成更加完整均匀的炭层,因而改善了阻燃性能。
