乳液型过氧化新癸酸异丙苯酯的稳定性研究

通过对乳液型过氧化新癸酸异丙苯酯(CNP)的制备进行研究,监测其稳定性,得到W40型CNP最佳配方为:乳化剂0.5%、分散剂0.75%、甲醇11%;放置90天后质量稳定,粒径为3.709μm。

微反应器制备过氧化新癸酸异丙苯酯

基于微反应器的发展及其固有的安全特性,探讨了用微通道反应器制备对过氧化新癸酸异丙苯酯工艺。研究了反应温度、物料配比、停留时间等对反应固含量和收率的影响,以及合成的最佳条件。结果表明,最佳反应条件为氢氧化钾∶异丙苯∶新癸酰氯(摩尔比)=1.30∶1.05∶1.00,玻璃模块反应温度50℃,碳化硅模块反应温度60℃,反应停留时间57 s,收率和固含量最佳,含固质量分数为86.14%,收率为92.46%。

Sensitivity of green and blue-green algae to methyl tert-butyl ether

The toxicity of methyl tert-butyl ether （MTBE） to Chlorella ellipsoidea and Aphanizomenon flos-aquae was tested and assessed for a 15-d incubation with concentrations of MTBE from high （2.00×10^4 mg/L） to low （2 mg/L）. The results showed that the toxicity was low when the concentration of MTBE was in the range 1.00× 10^4-2.00× 10^4 mg/L （the greatest inhibition of growth-rate was 70%-71%, occurred during the day 1-5）. Low concentrations （2-500 rag/L） stimulated algal growth up to the greatest effect of 85%-200% when the concentration of MTBE was 50-100 mg/L during day 3-5. The toxicity of MTBE （72-120 h EC50） was 6.65×10^3-9.58×10^3 mg/L for C. ellipsoidea and that is 1.14× 10^4-2.00× 10^4 mg/L for A. floc-aquae. We found that the toxicity and ecological risk of MTBE for the algal community structure were low and the toxicity was influenced by the duration time of the test.

Tert-butylation of Toluene with Tert-butyl Alcohol over Realuminated H-mordenite Zeolite

The realuminated H-mordenite catalysts （HM1-4） treated with different concentrations of NaOH and NaAlO2 aqueous solutions were prepared, and characterized by inductively coupled plasma （ICP）, X-ray diffraction （XRD）, Fourier transform-infrared spectroscopy （FT-IR） and temperature-programmed desorption of ammonia, They are of lower Si/AI ratio and higher acid amount while keeping a high relative crystallinity. Their catalytic performances were evaluated with the liquid-phase tert-butylation of toluene with tert-butyl alcohol in a 100 ml stainless steel batch reactor equipped with a stirrer. HM2 zeolite catalyst, obtained by treating HM in 0.1 mol.L-1 NaOH followed by 0.05 mol·L^-1 NaAlO2 aqueous solution, shows a higher catalytic activity because of its highest acid amount. For HM2 catalyst the influences of reaction conditions on catalytic performance were investigated. The conversion of toluene is 50.3% and the selectivity ofp-tert-butyltoluene is 74.7% at a temperature of 180℃, 2 of molar ratio of tert-butyl alcohol to toluene, 4h of reaction time and 0.2 of M（catalyst）/M（toluene）.

Aerobic degradation of methyl tert-butyl ether by a Proteobacteria strain in a closed culture system

The contamination of methyl ten-butyl ether （MTBE） in underground waters has become a widely concerned problem all over the world. In this study, a novel dosed culture system with oxygen supplied by H2O2 was introduced for MTBE aerobic biodegradation. After 7 d, almost all MTBE was degraded by a pure culture, a member of β-Proteobacteria named as PMI, in a closed system with oxygen supply, while only 40% MTBE was degraded in one without oxygen supply. Dissolved oxygen （DO） levels of the broth in closed systems respectively with and without H2O2 were about 5-6 and 4 mg/L. Higher DO may improve the activity of monooxygemase, which is the key enzyme of metabolic pathway from MTBE to tert-butyl alcohol and finally to CO2, and may result in the increase of the degrading activity of PM1 cell. The purge and trap GC-MS result of the broth in closed systems showed that tea-butyl alcohol, isopronol and acetone were the main intermediate products.

The Inhibition Effect of Tert-Butyl Alcohol on the TiO_2 Nano Assays Photoelectrocatalytic Degradation of Different Organics and Its Mechanism

The inhibition effect of tert-butyl alcohol(TBA), identified as the·OH radical inhibitor, on the TiO_2 nano assays(TNA) photoelectrocatalytic oxidation of different organics such as glucose and phthalate was reported. The adsorption performance of these organics on the TNA photoelectrode was investigated by using the instantaneous photocurrent value, and the degradation property was examined by using the exhausted reaction. The results showed that glucose exhibited the poor adsorption and easy degradation performance, phthalate showed the strong adsorption and harddegradation, but TBA showed the weak adsorption and was the most difficult to be degraded. The degradation of both glucose and phthalate could be inhibited evidently by TBA. But the effect on glucose was more obvious. The different inhibition effects of TBA on different organics could be attributed to the differences in the adsorption and the degradation property. For instance, phthalate of the strong adsorption property could avoid from the capture of·OH radicals by TBA in TNA photoelectrocatalytic process.

Porous alumina ceramic via gelcasting based on2-hydroxyethyl methacrylate dissolved in tert-butyl alcohol

To obtain porous alumina ceramic with high strength,a novel gelcasting system based on 2-hydroxyethyl methacrylate(HEMA)dissolved in tert-butyl alcohol(TBA)was developed.The polymerization of the HEMA-TBA gelcasting system,the thermal behavior of obtained green body,and the microstructures and mechanical properties of the sintered bodies were investigated by rheometer,TG-DSC,SEM and bending strength testing,respectively.The results show that,(1)10 mg/mL of the initiator(benzoyl peroxide)is the optimal amount for polymerization of this gelscasting system at 25 ℃;(2)The alumina suspension of the HEMA-TBA gelcasting system showing shear-thinning behavior is sufficiently low for gelcasting process;(3)The bending strength of porous alumina ceramic samples,whose porosities range from 42% to 56%,is from(8±0.5)to(91±4.5)MPa.

Determination of methyl tert-butyl ether(MTBE) in Chinese fuels by gas chromatography/mass spectrometry and gas chromatography/flame ionization detector

A method was developed to determine the concentration of methyl tert-butyl ether(MTBE) in gasoline, diesel and heating oil by gas chromatography(GC) with mass spectrometry(GC-MS) or flame ionization detection(FID). The diluted gasoline was directly injected into the GC, and the complete separation of MTBE from co-eluting hydrocarbons was not required. GC/MS or GC/FID method can be used to analyze MTBE in different concentration range and have good consistency.

Synthesis and phosphorescent properties of two novel iridium (Ⅲ) complexes bearing bulky tert-butyl substituents

The synthesis and phosphorescence properties of two novel Ir(Ⅲ)complexes bearing tert-butyl substituents,bis(4-tert-butyl-2- phenylbenzothiozolato-N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tbt)_2Ir(acac)]and bis(4-tert-butyl-1-phenyl-1H-benzimidazolato- N,C^(2′))iridium(Ⅲ)(acetylacetonate)[(tpbi)_2Ir(acac)],are reported,their molecular structures are confirmed by^1H NMR,ESI-MS and elementary analysis.Photoluminescence(PL)studies revealed that they can emit strong green and orange phosphorescence in high quantum yields.Compared to their prototypes lacking of tert-butyl substituents,the two novel iridium(Ⅲ)complexes both have shorter lifetimes and improved or nearly similar PL quantum efficiencies,implying that the exciton quenching is inhibited effectively when molecular steric hindrance increases.The two chelates have great potential to be used as electrophosphorescent materials.

2D-Cell Experiment on Methyl Tert-Butyl Ether Transport in Saturated Zone of Groundwater

As an additive of gasoline,methyl ten-butyl ether(MTBE)has a higher solubility in water,which is about 20 times as high as that of benzene.This characteristic results in MTBE dissolving out of the gasoline into the soil and groundwater.Due to relative unique physicochemical behavior of MTBE it would be an ideal candidate for use in environmental forensic investigations.In order to study the transport and distribution of MTBE in saturated zone of ground water,a two-dimensional experimental cell was setup to simulate the real environment of the groundwater flow.The effects of soil and groundwater flow velocity on the MTBE transport were investigated.The results show that the mobile distance of MTBE in vertical direction was smaller than that in horizontal direction paralleling with the groundwater flow.Because the main dynamics of groundwater flow direction was convection and dispersion,the movement of MTBE is also diffusion in the vertical direction.In addition,the transport of MTBE was more quick in high permeability porous media,and the increase of groundwater flow velocity can accelerate the MTBE plume development,but the irregularity and randomness of the plume are enhanced synchronously.These research results can give some helps for the investigation of MTBE movement in the groundwater,also can make some references for other petroleum contamination behavior.

Measurements and correlation of liquid–liquid equilibrium data for the ternary(methyl tert-butyl ketone + o, m, p-benzenediol + water)system at(333.2, 343.2 and 353.2) K

In this work, liquid–liquid equilibria(LLE) data for the ternary system methyl tert-butyl ketone(MTBK)+ o, m,p-benzenediol + water were investigated at 333.2 K, 343.2 K and 353.2 K under 101.3 kPa. The performance of MTBK to extract o, m, p-benzenediol from wastewaters was estimated by partition coefficients and separation factors. The Hand and Bachman equations were both applied to check the reliability of the experimental LLE data. Furthermore, the Non-Random Two-Liquid(NRTL) and Universal Quasi Chemical(UNIQUAC) models were applied to correlate the measured LLE data. The results showed a good agreement with the determined ternary LLE data with the root-mean-square error(RMSE) values below 0.71%. MTBK was proved to be a promising extracting agent in extracting benzenediols from effluents.

Surface Properties of the Microgels Based on N-isopropylacrylamide and Tert-butyl Acrylate by Using N,N′-methylene-bis(acrylamide) and Clay as Cross-linker

Adopting N, N＇-methylene-bis （aculamide） （MBA） and inorganic clay （hectorite） as chemical and physical crosslinking agent, respectively, a series temperature sensitive microgels, based on N-isopropylacrylamide （NIPAM） as a main monomer and tert-butyl acrylate （tBA） as a comonomer were synthesized by surfactant-free emulsion polymerization （SFEP）. The microgel particle size and morphology was investigated by means of Atomic Force Microscope （AFM）. The surface tension of latex particles was measured by OCA 40 Micro Video based contact angle measuring device. The results showed that the particle size of the microgels with clay as cross-linker was smaller than that using MBA as chemical cross-linker, but exterior morphology of physical microgels is not as clean and neat as chemical microgels. In general, surface tension decreases with increasing hydrophobic tBA content. These smart microgels varied with tetnperature have the potential applications in the field of drug delivery and intelligent gel fiber.

Optimizing the Synthesis of Ethyl tert-Butyl Ether in Continuous Catalytic Distillation Column Using New Ion Exchange Resin Catalyst

Liquid phase synthesis of one of the important fuel oxygenate, ethyl tert-butyl ether （ETBE）, from etha-nol and tert-butyl alcohol （TBA） has been studied in catalytic distillation column （CDC） using ion exchange resin catalyst CT-145H. A packed CDC of 1.2 m height and 50 mm diameter with indigenously developed reactive sec-tion packing was used to generate experimental data. Effect of different key variables on product purity in distillate, was investigated to find the optimum operating conditions for ETBE synthesis. The optimum conditions for 0.2 kg·s-1 of ethanol feed were found：reboiler duty of 375 W, molar feed ratio of 1︰1.3 of reactants, and reflux ratio of 7. Concentration profiles for each component along each column section at optimum conditions were also drawn. Neither output nor input multiplicity was observed at experimental conditions.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

Study on Pervaporation Membranes for Removing Methanol from C_5 or Methyl Tert-butyl Ether Mixtures

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA), MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmenthanol =350g.m-2.h-1 and separation factor a > 400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.

Phenol Tert-Butylation Catalyzed by Zeolite H-Mordenite

Para-tert-butyl phenol (p-TBP) and 2,4-di-tert-butyl phenol (2,4-DTBP) are widely used for the preparation of antioxidants. Zeolite catalysts showed good performance for the synthesis of p-TBP and 2,4-DTBP. In this work, zeolite H-mordenite (HM) catalyst was prepared and the alkylation of phenol with tert-butyl alcohol over zeolite HM catalyst was investigated at different reaction conditions. It is found that increasing temperature enhances the selectivity to p-TBP and the optimum reaction temperature for phenol conversion is 438 K. Increasing flow rate decreases phenol conversion apparently while the selectivity to p-TBP has a little increase. The suitable tert-butyl alcohol/phenol molar ratio is 2. Lower alcohol/phenol molar ratios are beneficial to p-TBP while higher ones are helpful for producing 2,4-DTBP.

Catalytic Synthesis of Tert-Butyl Acetate by Nd_2O_3/Al_2O_3-Nd_2O_3/ZnO

Nd2O3 was used to support Al2O3 and ZnO to prepare a supported solid base catalyst and investigate the effect of catalyst and reaction conditions on the synthesis of tert-butyl acetate. The composited oxide of Nd2O3/Al2O3-Nd2O3/ZnO exhibited excellent catalytic activity for the synthsis of tert-butyl acetate. The molar ratio of tert-butanol to acetic anhydride is 3∶1, the catalyst in total amount of reactant nearly 0.5%, and reaction time 6 h. With the above conditions, yield of the reaction could reach to 65%. The structure of product were verified by the FT-IR, Element analysis, and MS, which proved that the product was tert-butyl acetate.

Synthesis, Crystal Structure and Antitumor Activity of 4-(tert-butyl)-5-(1H-1,2,4-triazol-1-yl)-N-(2-hydroxy-3,5-diiodinebenzyl)-thiazol-2-amine

The title compound, 4-（tert-butyl）-5-（1 H- 1,2,4-triazol- 1 -yl）-N-（2-hydroxy-3,5-diio- dinebenzyl）thiazol-2-amine, was synthesized via the reduction of 4-（tert-butyl）-5-（1H-l,2,4- triazol-l-yl）-N-benzylidene-thiazol-2-amine with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, space group P21/c with a = 7.91944（19）, b = 10.5250（3）, c = 24.4985（6） A, Z = 4, V = 2041.66（9） A3, Mr = 599.22, Dc = 1,949 Mg/m3, S = 1.120, p = 3.203 mm-1, F（000） = 1152, the final R = 0.0283 and wR = 0.0592 for 3490 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the crystal water takes part in three intermolecular hydrogen bonds of O（2）-H（2A）…O（1）, O（2）-H（2B）…N（I） and N（5）-H（5）…O（2）, and an octatomic ring R^（8） is formed via intramolecular hydrogen bond of O（I）-H（IA）…N（4）. Furthermore, the I…I contacts are involved in stabilizing the overall three-dimensional network structure. The preliminary biological test shows the title compound has good antitumor activity with the IC50 value of 26 μM against the Hela cell line.

Isobaric Vapor–Liquid Equilibrium for tert-Butyl Alcohol + Water + Propane-1,3-Diol + 1-Ethyl-3-Methylimidazolium Chloride at 101.3 kPa

In this study, we used a mixture of organic liquid propane-1,3-diol and ionic liquid 1-ethyl-3-methylimidazolium chloride([emim]Cl) as the entrainer to separate tert-butyl alcohol(TBA) + water. We measured the isobaric vapor–liquid equilibrium(VLE) for the quaternary system TBA + water + propane-1,3-diol + [emim]Cl at 101.3 kPa, and found the VLE data to be well correlated with the nonrandom two-liquid model. These results show that the mixed solvent of propane-1,3-diol + [emim]Cl can increase the relative volatility of TBA to water and break the azeotropic point. We found no notable synergetic effect between them, and observed that the liquid mixed solvent of propane-1,3-diol and [emim]Cl had lower viscosity than [emim]Cl, which makes it a promising entrainer for separating the TBA + water azeotrope in industrial applications.