甲酸甲酯氯化制双光气

介绍了甲酸甲酯及氯甲酸甲酯氯化制双光气的方法，并对两种方法进行了比较。

A change of phenolic acids content in poplar leaves induced by methyl sali-cylate and methyl jasmonate

The contents of seven different phenolic acids such as gallic acid, catechinic acid, pyrocatechol, caffeic acid, coumaric acid, ferulic acid and benzoic acid in the poplar leaves （Populus Simonii×Populus Pyramibalis c.v and Populus deltoids） suffocated by Methyl jasmonate （MeJA） and Methyl salicylate （MeSA） were monitored for analyzing their functions in interplant communications by using high-pressure liquid chromatography （HPLC）.The results showed that the contents of phenolic acids had obviously difference in leaves exposed to either MeSA or MeJA.When P.deltoides leaves exposed to MeJA or MeSA, the level of gallic acid, coumaric acid, caffeic acid, ferulic acid and benzoic acid was increased, gallic acid in leaves treated with MeJA comes to a peak at 24 h while to a peak at 12-d having leaves treated with MeSA.When P.Simonii ×P.Pyramibalis c.v leaves were exposed to MeJA or MeSA, the level of gallic acid, pyrocatechol and ferulic acid was increased; The catechinic acid and benzoic acid had a little drop; The caffeic acid and coumaric acid were undetected in both suffocated and control leaves.This changed pattern indicated that MeJA and MeSA can act as airborne signals to induce defense response of plants.

Synthesis of Toluene-2,4-Bisurea from 2,4-Toluene Diamine and Urea and the Reaction Kinetics

Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance. Firstly, thermodynamic analysis shows that the reaction is exothermic and a high equilibrium conversion of TDA is expected due to its large reaction equilibrium constant. Secondly, under the suitable reaction conditions, 130 °C, 7 h, and molar ratio of TDA/zinc acetate/urea/sulfolane 1/0.05/3.5/10, TDA conversion is 54.3%, and TBU yield and selectivity are 39.8% and 73.3% respectively. Lastly, the synthesis of TBU is a 1st order reaction with respect to TDA and the reaction kinetics model is established. This work will provide useful information for commercializing the urea route to toluene-2,4-dicarbamate (TDC).

Toxic effects of several phthalate esters on the embryos and larvae of abalone Haliotis diversicolor supertexta

As the most widely used plasticizers in the world, phthalate esters （PAEs） are potential endocrine disruption compounds （EDCs）. In the present study, the toxicity of dimethyl phthalate （DMP）, diethyl phthalate （DEP）, dibutyl phthalate （DBP）, di （2-ethylhexyl） phthalate （DEHP） on embryogenesis and larvae development of the marine univalve Haliotis diversicolor supertexta was examined in laboratory. The results show that the malformation of embryos appeared during the experiment, such as embryos died or lysed, small transparent flocculent rings studded on the periphery of the embryo, and the larvae could failed to hatch. In embryo toxic test, embryos incubated at the highest concentration of DMR DEP and DBP solutions showed significantly high abnormal rate compared with the control, while DEHP solutions displayed no significant difference. In larval toxic test, in all concentrations of DMP, DEP and DBP solutions, larval settlement rates were low significantly than that of the control. Similarly, DEHP solutions show nearly no effect on the larval settlement. The order of toxicity on embryos and larvae is DBP〉DEP〉DMP〉DEHE Being a simple and easy stimulation to indoor spawn, sensitive to environmental factors, and short culture time, the embryos of H. diversicolor supertexta can be used to indicate toxicity of the PAEs.

Modification of methyl oleate for silicon-based biological lubricating base oil

A new kind of silicon-based biological lubricating base oil with good viscosity-temperature behavior,viscosity index,thermostability,oxidation stability and wear resistance performance was synthesized as a derivative of methyl oleate.Trimethylsilylation reaction was introduced to further improve methyl oleate oxidation stability and lubricity after epoxidation and open-ring reactions.The order of effectiveness of acid binding agent was N,N-diisopropylethylamine(DIEA) > pyridine > diethylamine > triethylamine,and the effects of various parameters on the trimethylsilylation reaction as well as on the silicon-oxygen bond stability and reaction yield were studied.A maximum yield of 34.54%was achieved at hydroxyl/trimethyl chlorosilane/DIEA molar ratio of1:1.25:1,reaction temperature 40℃,reaction time 1.5 h.

Isobaric Vapor-Liquid Equilibrium of Binary Systems： p-Xylene ＋ （Acetic Acid, Methyl Acetate and n-Propyl Acetate） and Methyl Acetate ＋ n-Propyl Acetate in an Acetic Acid Dehydration Process

The vapor-liquid equilibrium data of four binary systems (acetic acid +p-xylene, methyl acetate +n-propyl acetate, n-propyl acetate +p-xylene and methyl acetate +p-xylene) are measured at 101.33 kPa with Ellis equilibrium still, and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems. The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate +p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points. The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase, and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate +n-propyl acetate system, for which the latter gives more accurate correlations.

Effective production of γ-valerolactone from biomass-derived methyl levulinate over CuO_x-CaCO_3 catalyst

The production of?-valerolactone(GVL)from lignocellulosic biomass has become a focus of research owing to its potential applications in fuels and chemicals.In this study,(n)CuOx-CaCO3(where n is the molar ratio of Cu to Ca)compounds were prepared for the first time and shown to function as efficient bifunctional catalysts for the conversion of biomass-derived methyl levulinate(ML)into GVL,using methanol as the in-situ hydrogen source.Among the catalysts with varied Cu/Ca molar ratios,(3/2)CuOx-CaCO3 provided the highest GVL yield of 95.6% from ML.The incorporation of CaCO3 with CuO resulted in the formation of Cu+species in a CuOx-CaCO3 catalyst,which greatly facilitated the hydrogenation of ML.Notably,CuOx-CaCO3 also displayed excellent catalytic performance in the methanolysis products of cellulose,even in the presence of humins.Therefore,a facile two-step strategy for the production of GVL from cellulose could be developed over this robust and inexpensive catalyst,through the integration of cellulose methanolysis catalyzed by sulfuric acid,methanol reforming,and ML hydrogenation in methanol medium.

Kinetics of esterification of methanol and acetic acid with mineral homogeneous acid catalyst

In this work, esterification of acetic acid and methanol to synthesize methyl acetate in a batch stirred reactor is studied in the temperature range of 305.15–333.15 K. Sulfuric acid is used as the homogeneous catalyst with concentrations ranging from 0.0633 mol·L-1to 0.3268 mol·L-1. The feed molar ratio of acetic acid to methanol is varied from 1:1 to 1:4. The influences of temperature, catalyst concentration and reactant concentration on the reaction rate are investigated. A second order kinetic rate equation is used to correlate the experimental data. The forward and backward reaction rate constants and activation energies are determined from the Arrhenius plot.The developed kinetic model is compared with the models in literature. The developed kinetic equation is useful for the simulation of reactive distillation column for the synthesis of methyl acetate.

Ternary Liquid-Liquid Equilibrium for Systems of Fatty Acid Methyl Ester(Methyl Palmitate/Methyl Stearate)+Ethanol+Glycerol at Atmospheric Pressure

Liquid-liquid equilibrium data of two ternary systems methyl palmitate+ethanol+glycerol and methyl stearate+ethanol+glycerol at(318.2 and 333.2)K and atmospheric pressure were measured. The values of distribution coefficient and selectivity were calculated, which indicates that glycerol can be separated from fatty acid ester by using ethanol as an extraction solvent. The consistency of the isothermal tie-line data were checked by the Othmer-Tobias equation. The correlation coefficients R2 are higher than 0.993,9 for all the fitted curves. The NRTL activity coefficient model was applied to the correlation of the measured tie-line data. The root mean square deviation(RMSD)values are less than 0.007 for all the systems, which shows a good predictive capability of this model for such systems.

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.

Heterogeneous synthesis of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine and methyl carbonate in methanol over a CeO_2 catalyst

The efficient synthesis of dimethylhexane-1,6-dicarbamate(HDC)from 1,6-hexanediamine(HDA)and methyl carbonate over a series of heterogeneous catalysts(e.g.,Mg O,Fe2O3,Mo2O3,and Ce O2)was investigated.The reaction pathway was confirmed as an alcoholysis reaction through a series of designed experiments.Under optimized conditions,100%HDA conversion with 83.1%HDCtotaland 16.9%polyurea was obtained using a onestep with high temperature procedure with Ce O2as the catalyst.A new two-step with variable temperature technology was developed based on the reaction pathway to reduce the polyurea yield.Using the proposed method,the HDCtotalyield reached 95.2%,whereas the polyurea yield decreased to 4.8%.The Ce O2catalyst showed high stability and did not exhibit any observable decrease in the HDC yield or any structural changes after four recycling periods.

Effect of dosage of expandable graphite,dimethyl methylphosphonate,triethanolamine,and isocyanate on fluidity,mechanical,and flame retardant properties of polyurethane materials in coal reinforcement

In this study,orthogonal experiments were conducted to investigate the influence of expandable graphite(EG),dimethyl methylphosphonate(DMMP),triethanolamine(TEA),and isocyanate content on the compressive and bonding strengths,oxygen index,and fluidity of rigid polyurethane foam(RPUF).The results revealed that EG significantly increased the oxygen index of RPUF,enlarged the diameter of foam cells,and decreased the cell-closed content in foam;thus,leading to a pressure drop in RPUF.However,excessive EG was capable of reducing the fluidity of polyurethane slurry.TEA exhibited significant influence on the compressive strength of RPUF,which dropped initially,and then increased.DMMP had a remarkable effect on the flame retardant property and compressive strength of RPUF.Compressive strength of RPUF initially displayed an increase followed by a decrease with increasing dosage of DMMP,and achieved the maximum value at DMMP dosage of 4%.DMMP could effectively reduce the diameter of RPUF cells leading to an increase in the percentage of close area in foam.DMMP displayed the flame-retardation effects mainly in the gas phase leading to a significant enhancement in the oxygen index of RPUF.Moreover,the compressive strength and bonding strength of RPUF decrease significantly with the increase of isocyanate content due to the increased blowing efficiency by the CO_2.The oxygen index and flowing length of foam increased with the increase in isocyanate dosage.

Environmentally Degradation of r-PMMA/PMMA-Blend-PU/Ecoflex Sheet

Poly （methyl methacrylate） scrap was applied to prepare the impact modification of r-PMMA/PMMA-blend-PU/Ecoflex sheet by casting process. The Ecoflex and polyurethane were used as biodegradable polymer and impact modified respectively. This research was ascertained tile way to reduce the processing cost of PMMA sheet and the industrial waste by recycled PMMA scrap into the production process. The r-PMMA/PMMA-blend-PU/Ecoflex sheet was studied potential degradation by landfills for six months. After degradation the percentage of weight loss of specimens was increasing depend on amount of Ecoflex content and degradation period. While, the surface morphology of r-PMMA/PMMA-blend-PU/Ecoflex sheet after six months was damaged and demonstrated that Ecoflex had an effect on PMMA-blend-PU sheet in potential biodegradation. The mechanical and physical properties of r-PMMA/PMMA-blend-PU/Ecoflex sheet were described. Finally, the impact strength of r-PMMA/PMMA-blend-PU/Ecoflex sheet from this research, it is possible to use r-PMMA and Ecoflex in the acrylic casting sheet product.

A novel method for fabricating polydimethylsiloxane microfluidic chip master molds

We proposed a novel method of fabricating polydimethylsiloxane (PDMS) microfluidic chip polymer master molds in this paper. The method mainly includes two steps. First, a stainless steel slice was laser etched to form a metal model. Then, the organic solution of poly(methyl methacrylate) (PMMA) was casted onto the metal model to fabricate the PMMA master which subsequently would be used to fabricate PDMS chips. We systematically researched different laser parameters influencing the surface status of microchannels and obtained optimized etching parameters. We investigated and optimized the organic solution composition of PMMA while casting chip masters, and developed a method to form fine polymer masters using two different viscosity solutions to cast the model in turn, and studied the repeatable replication. Then, we investigated physical performance of this chip and evaluated the practicability by analyzing Rhodamine B. Compared with present methods, the proposed method does not need photolithography on photoresistant and chemical etching. The entire fabricating progress is simple, fast, low-cost and can be controlled easily. Only several minutes are required to make a metal model, 3 hours for a PMMA master, and one day for PDMS chips.

Modified graphite filled natural rubber composites with good thermal conductivity

The rubber composites with good thermal conductivity contribute to heat dissipation of tires. Graphite filled natural rubber composites were developed in this study to provide good thermal conductivity. Graphite was coated with polyacrylate polymerized by monomers including methyl methacrylate, n-butyl acrylate and acrylic acid. The ratios between a filler and acrylate polymerization emulsion and those between monomers were varied. Eight types of surface modification formulas were experimentally investigated. Modification formula can affect coating results and composite properties greatly. The best coating type was achieved by a ratio of1:1 between methyl methacrylate and n-butyl acrylate. The coating of graphite was thermally stable in a running tire. Filled with modified graphite, the tire thermal conductivity reached up to 0.517–0.569 W·m-1·K-1. In addition, the mechanical performance was improved with increased crosslink density, extended scorch time and short vulcanization time.

Reduction in Fertility by Nerium indicum Leaves Extract in Adults of Red Flour Beetle, Tribofium castaneum （Coleoptera： Tenebrionidae） Compared with Coopex （Bioallethrin： Permethrin）

Recent trend for the control of insect pests has been towards the use of substances of plant origin. Reductionin fertility was determined in red flour beetle, Tribolium castaneum （Herbst.） by Nerium indicum Millleaves extract compared with coopex applied by contact method under laboratory condition. When adults were placed on filter paper treated With 7.86, 9.43, 11.01, 12.58 and 14.15 μL/cm2 doses of N. indicum leaves extract, fertility was 154 ± 15.2, 139 ± 15.0, 126 ± 6.0, 89 ± 12.2 and 72 ± 13.6 larvae/pair, compared with untreated and controls fertility （233 ± 16.0 and 190 ± 15.1 larvae/pair, respectively）. However, the reduction in fertility was 33.2 ± 6.4%, 39.7 ± 3.7%, 45.7 ± 2.9%, 58.0 ± 4.4% and 66.3 ± 5.1% by the same doses ofN. indicum extract. Moreover, adults treated with the same doses of coopex with the same method, fertility was 160 ± 14.6, 154 ± 9.3, 140 ± 11.2, 113 ± 7.5 and 71 ±- 4.8 larvae/pair, compared with controls fertility （211 ± 8.5 larvae/pair）, respectively. Furthermore, reduction in fertility was 24.3 ± 5.2%, 30.2 ± 6.4%, 37.2 ± 8.0%, 51.3 ± 1.4% and 58.8 ± 4.7% by the same doses of coopex. Minimum fertility was found in August and maximum was in July in both, N. indicum extract and coopex treated batches. The trend of reduction in fertility was the same in both N. indicum leaves extract and coopex, i.e., it was increased gradually from lower to higher doses. Nerium indicum leaves extract reduced fertility significantly compared with coopex.

GC-MS Spectrums and Their Close Match Methyl Esters from Mushrooms of Papua New Guinea

The GC-MS spectrums of a sample from Amanitaceae family and Mycenaceae family were matched with their close match GC-MS spectrums from the spectrum library. The samples from Amanitaceae family （KMsp027） and Mycenaceae family （KMsp039） were found to contain fatty acid methyl esters （methyl palmitate and methyl linoleate）. It is proposed that the presence of methyl linoleate and methyl palmitate in the samples may show antibacterial activities if tested against different bacterial strains.

HIGH SOLIDS-CONTENT NANOSIZE POLYMER LATEXES MADE BY A MODIFIED EMULSION COPOLYMERIZATION

Polymer nanoparticles were prepared in the methyl methacrylate (MMA)/buty lmethacrylate (BA) emulsion copolymerization process by a modified microemulsion copolymerization method. 2-Hydroxyethyl methacrylate(HEMA), acrylate (AA) and methyl acrylate (MAA) were used as reactive cosurfactants. With this process high polymer: surfactant weight ratios (40:1 or greater),relatively concentrated (~30wt. %) latexes and small (~60nm) particle diameters were obtained.Properties of the latexes were characterized by TEM, DSC, dynamic light scattering, and IR spectroscopy.

Study on Modification of Octyl-α-Cyanoacrylate Medical Adhesive

Objective:In order that the adhesive character could be improved to modify the octyl-α-cyanoacrylate(OCA) medical adhesive.Methods:Suitable modifiers involving polycaprolactone(PCL),dibutyl phthalate (DBP),dioctyl phthalate(DOP) and poly octyl methacrylat(POMA) have been chosen to modify the OCA adhesive,then tensile shear strength and adhesive strength are tested to evaluate the bond character of adhesives.Results:The PCL group's tensile shear strength and adhesive strength in normal temperature are descended while the other groups'are all enhanced.Conclusion:The modification of properties of the other groups is effectively promoted in the aspect of the bond character,except the PCL group treated in normal temperature and the PCL modified group treated by rectification get a best improvement in the agglutinate intention, while the stability is expected to be improved.

柳蒿化学成分研究(Ⅱ)

目的研究柳蒿Artemisia integrifolia的化学成分。方法采用溶剂萃取、硅胶柱色谱、高效液相色谱等方法进行分离纯化,通过核磁共振谱等波谱数据分析鉴定结构。使用DPPH进行抗氧化活性测定。结果从柳蒿中分离得到21个化合物,分别鉴定为2R-(2Z-戊烯酸甲酯基)-3S-(乙酸甲酯基)环戊酮(1)、methyl-4S-6α-hydroxy-3-oxoeudesma-1,11(13)-dien-12-oate(2)、咖啡酸甲酯(3)、右旋肌醇甲醚(4)、富马酸单丁酯(5)、咖啡酸(6)、丙二酸单丁酯(7)、6,8-二甲氧基香豆素-7-O-β-D-葡萄糖苷(8)、3,5-O-二咖啡酰基奎宁酸丁酯(9)、3,4-O-二咖啡酰基奎宁酸丁酯(10)、4,5-O-二咖啡酰基奎宁酸丁酯(11)、3,5-O-二咖啡酰基奎宁酸甲酯(12)、4,5-O-二咖啡酰基奎宁酸(13)、1,5-O-二咖啡酰基奎宁酸(14)、3,5-O-二咖啡酰基奎宁酸(15)、邻羟基桂皮酸葡萄糖苷(16)、1,3-O-二咖啡酰基奎宁酸(17)、绿原酸(18)、3,4-O-二咖啡酰基奎宁酸(19)、3,4-O-二咖啡酰基奎宁酸甲酯(20)、邻羟基桂皮酸甲酯葡萄糖苷(21)。结论化合物1为新天然产物,化合物2、5、7~11、14、16、21为首次从蒿属植物中分离得到,其余均为首次从柳蒿中分离得到。二咖啡酰基奎宁酸类化合物均具有较强的抗氧化能力,活性与维生素C(Vc)基本相当。