• Volume 29,Issue 11,2012 Table of Contents
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    • >Functional materials
    • Phase Transfer of Interaction on Alkylation of Dendritic Poly(amine-ester) and Dye Molecules

      2012, 29(11).

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      Abstract:Poly(amine-ester)-lauric acid dendrimer (PAE-LA) is synthesized from ethylenediamine (EDA), trimethylolpropane triacrylate (TMPTA) and Lauroyl chloride, the yield is 56.09%. The structure of PAE-LA is charactracterized by IR and 1HNMR. The effects of PAE-LA concentraction and water phase pH on the phase transfer rates of dyses(such as methyl orange, titan yellow and xylenol orange) were investigated. The results show that the phase transfer rate of dyes increase with the increase of the concentraction of PAE-LA. In the mixture with 20 mL PAE-LA- chloroform solution1.2 ?0-5 mol/L (c)),and 20 mL dye(methyl orange, titan yellow ,or xylenol orange) water solution(about1.200?0-5 mol/L(c)) ,when water phase pH is 2, the phase transfer rates of titan yellow, methyl orange, xylenol orange reach the maximum (83.75%、81.96%、57.35%) respectively.

    • Syntheses of Labeled Enrofloxacin-D5

      2012, 29(11).

      Abstract (831) HTML (0) PDF 0.00 Byte (0) Comment (0) Favorites

      Abstract:This article presents efficient synthesis of labeled standard Enrofloxacin-D5,with CD3CD2OD as the common substrate.Iodonation of CD3CD2OD with I2 provided CD3CD2I,which was subsequently used to ethylate Ciprofloxacin to get Enrofloxacin-D5。The yield of Enrofloxacin-D5 was 69.9% based on CD3CD2OD consumed.The product was confirmed by NMR and LC-MS to be target compound.Its chemical purity was 99.0% and isotopic enrichment was 99.6 %.It could be used as internal standard in the field of food safety testing.

    • Synthesis of UV Curable Organosilicon and The Curing conditions Research

      2012, 29(11).

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      Abstract:The Ultraviolet (UV)-curable organosilicon material has been synthesized by sol-gel method using polymethyl triethoxy silane(PTS), γ-methacryloyl propyl trimethoxyl silane (KH570), dimethyldiethoxysilane(DDS) as a raw material and HCl as catalyst. The obtained materials were characterized by means of FT-IR, 29Si-NMR, and studied the degree of siloxane condensation of organosilicon and the conversation rate of C=C double bonds after UV curing. The results showed that the UV-curing system composed of Irgacure369 has higher curing rate than that with other photoinitiators, The conversation rate of C=C double bonds of organosilicon has reached 95.89% after UV-cured with Irgacure369. When the concentration of the photoinitiator is 2% and the illumination time is 15s, the best result can be obtained.

    • >Surfactants
    • Synthesis and Antitumor Activity of Novel Castor Oil-Based Quaternary Ammonium

      2012, 29(11).

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      Abstract:Abstract: Two novel castor oil-based quaternary ammonium were synthesized from the starting material of methyl ricinoleate by aminolysis reaction and quaternization reaction. Their structures were characterized by means of FTIR, 1H NMR, 13C NMR and ESI (MS) . Bactericidal activity of novel castor oil-based quaternary ammonium salts were evaluated by inhibitory zone diameters against E. coli and S. aureus. It was found that castor oil-based quaternary ammonium salts have antibacterial activity. Antibacterial activity of the N, N-dimethyl-N-ethyl-castor oil acid amide propyl bromide than N-benzyl-N, N-dimethyl-castor oil acid amide propyl bromide.

    • >Catalysis,separation and purification technology
    • Effect of Reduction Temperature on Reduction Degree and Performance of CuO-ZnO-ZrO2 Catalyst for Carbon Monoxide Oxidation at Low Temperature

      2012, 29(11).

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      Abstract:Influence of reduction temperature on the reduction degree and performance of CuO-ZnO-ZrO2 catalyst for carbon monoxide oxidation at low temperature is investigated by means of reduction thermodynamic calculation, H2-TIR, H2-TPR and catalytic tests. It is found that the introduction of ZrO2 to CuO-ZnO improves the dispersion of active sites CuO with easy redox capacity and the transformation of valence state from Cu2 to Cu1 is easier than to Cu0. H2-TIR results indicate that the H2 consumption during reduction process increases, and the reduction peaks move forward with the increase of reduction temperature from 100℃ to 200℃. From the calculations by method of H2 consumption, the reduction degree of catalyst is found to increase with reduction temperature, in the order of 0% (100℃) < 45.7% (140℃) < 77.3% (160℃) < 86.2% (200℃). The catalyst activated at the optimal reduction temperature of 160℃ exhibits good catalytic performance, that shows 100% CO conversion in CO-probe oxidation at 100℃,and 0.02 ppm CO removal depth in the application of CO removal from liquid propylene.

    • Effect of template content on the physicochemical properties and the catalytic performance of SAPO-11 for the alkylation of naphthalene with methanol

      2012, 29(11).

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      Abstract:Effects of the concentration of di-n-propylamine (DPA) in gel on the physicochemical properties and the catalytic performances of the alkylation of naphthalene with methanol as-synthesized SAPO-11 zeolites have been studied. Products were characterized using XRD, SEM, N2 adsorption-desorption, NH3-TPD, FT-IR and 29SiMAS. The results indicated that different template contents had strong influence on the pore structure, the Si distribution and thus the acidity of SAPO-11. The sample prepared at DPA:Al2O3 ratio of 1.5 (SAPO-11-1.5) possessed large surface area and pore volume, which was 215 m2٠g-1和0.173 cm3٠g-1, respectively, and small Si domains, large amount of Si (nAl) (0

    • Development and its performance evaluation of energy saving catalyst for ethylbenzene dehydrogenation

      2012, 29(11).

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      Abstract:The energy saving catalyst for ethylbenzene dehydrogenation to styrene which was based on GS-11 catalyst was developed by increasing the content of CeO2, introducing selective assistant and optimizing pore structure. The evaluation results on a negative pressure adiabatic reactor showed that ethylbenzene conversion was 67.3% and styrene selectivity was more than 97.0%, which were obtained under the operation condition of Inlet temperatures for the 1st and 2nd reactors: 615℃and 620℃, LHSV: 0.5h-1, outlet pressure for the 2nd reactor: -50KPa, mass ratio of steam to ethylbenzene: 1.15. Results of accelerated aging test indicated that deactivation rate of the catalyst was -0.00404%/h and better than the newest imported catalyst and GS-11 catalyst.

    • Heteropolyacid Cobalt Salt Immobilized on Silyated Acid-activated

      2012, 29(11):0-0.

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      Abstract:The heteropolyacid cobalt salt catalyst immobilized on silyated acid-ctivated palygorskite(PG) was prepared and characterized by infrared spectroscopy. The effects that preparation conditions acted on acetophenone generation were also investigated. Experimental results indicated that the supported CoHPAs heteropolyacid(CoHPAs) cobalt salts (CoHPAs/MPG) exhibited high activity for the reaction, the conversion of ethylbenzene was 72.74 % and the selectivity of acetophenone was 95.42 %. The stability and reusability of the catalyst were investigated and the catalytic activity was retained after recycling 5 times, it has certain use prospects.

    • >Perfumes and essences
    • Study on the Cyclocondensation Products of Propional with Ammonium Sulfide

      2012, 29(11):0-0.

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      Abstract:2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine was synthesized by the reaction of 0.10mol propional with 0.18mol aqueous solution of ammonium sulfide in ethanol. Its structure was characterized by FTIR, FTMS,1HNMR and 13CNMR. The crude product obtained was analyzed by GC-MS. The analytical result showed that its constituents mainly included 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine, 2,4,6-triethyl-hexahydro-1,3,5-trizine, N-propylidene-1-amino-1-propene, 3,5-diethyl-1,2,4-trithiolane, 2,4,6-triethyl-tetrahydro-1,3,5-thiadizine, N,N’-dipropylidene-1,1-propylenediamine and 3,5-diethyl-4,5-dihydro-1,2,4-dithiazole. The formation mechanisms for main product and by-products were speculated. Meanwhile, thermal decomposition process of products, including 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazine, 2,4,6-triethyl-tetrahydro-1,3,5-thiadizine and 2,4,6-triethyl-hexahydro-1,3,5-trizine, were discussed when they were analyzed by GC-MS. Finally, the safety issues of 2,4,6-triethyl-5,6-dihydro-4H-1,3,5-dithiazines as potential food flavor were evaluated.

    • >Drug and cosmetic materials
    • New Method for the Synthesis of Ethyl 7-Chloro-2-oxoheptanoate

      2012, 29(11).

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      Abstract:Ethyl 7-chloro-2-oxoheptanoate is an important intermidiate of cilastatin. Using macronano-K2CO3 as base, 2-(5-chloropentyl)malonate was synthesized from 1-bromo-5-chloropentane and diethyl malonate in anhydrous EtOH, and then it was oxided by air catalized by Cu(NO3)2.3H2O in CH3CN to give ethyl 7-chloro-2-oxoheptanoate. The influence factors of the first-step reaction and the second-step reaction were investigated. The optimaized overall yield was 90.2%. The target product was characterized by means of 1HNMR and 13CNMR.

    • Preparation and properties of low molecular weight chondroitin sulfate

      2012, 29(11).

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      Abstract:Low molecular weight chondroitin sulfate was first prepared by free radical polymerization with hydrogen peroxide in the presence of copper(Ⅱ) iron. Its characterization and physicochemical properties were investigated by physicochemical methods including chemical composition, elementary analysis, IR and AFM. The result showed that molecular weight of chondroitin sulfate from 56956Da to 6906Da by copper catalytic oxidation. The major ingredient such as hexuronic acid, hexosamine and sulfate radical were no significant difference after degradation. The TG-DSC analysis showed the mechanism of thermal decomposition is similar. The AFM analysis indicated this samples exists in aqueous solution with stranded spiral. Part spiral is breaking during degradation. IR analysis showed that the degradation process may caused β-1,4 glycosidic bond fracture but no effect on β-1,3 glycosidic bond.

    • >Food and feedstuff chemicals
    • Optimization of the Composite wall material of Microencapsulation by Response Surface Methodology

      2012, 29(11).

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      Abstract:The wall material which is an important part of the microencapsulation,determines the characteristics of the microencapsulation. In this paper,the wall materials were sodium alginate etc , the high-voltage electrostatic microcapsule forming device was used , the qualified rate was chosen as the indicator, the Box-Behnken central composite design and response surface analysis were used, the main factors which affect the microcapsules were regression modeling and optimization. The optimal wall materials were 1.53% of sodium alginate, 4.52% of polyvinyl alcohol , 1% of gelatin content, 1% of glycerol , the 22.86g/L of encysted solution of calcium chloride ,and the qualified rate of microencapsulation was 87.37%. The special stability and strength of wall material ratio which provide reference for the microencapsulation of food, medicine were obtained.

    • >Starch chemicals
    • Synthesis and Application of Hyperbranched Polymer with Terminal Carboxyl groups-Al Chrome-free Tanning Agent

      2012, 29(11).

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      Abstract:The paper uses the terminal carboxyl groups of hyperbranched polymer complexing the Al3+ in aluminum sulphate synthesis a new chrome-free tanning agent (HPC-Al). Through single-laboratory methods optimize the conditions. The molecular structure of HPC-Al was characterized and analyzed by IR and XRD. The results indicated that the reaction raw ratio was m(HPAE-C):m(Al2(SO4)3)=2:1, pH was 3, reaction temperature was 30℃, and the time was 3h. Thermal decomposition temperature is 243℃. Application results show that: the shrinkage temperature of HPC-Al tanning leather is 76.6 ℃, The shrinkage temperature greater than 95℃ after chrome retanning,and it has greatly improved leather fullness, softness and physical- mechanical properties.

    • Preparation of the hydroxypropyl corn starch for glass fibre sizing agent

      2012, 29(11).

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      Abstract:Corn starch was used as raw material to produce film-forming agent for glass fiber sizing in this study. The starch was modified with isoamylase firstly, and then reacted with epoxypropane. The optimum conditions were obtained via orthogonal text, emphasizing the effects of the dosage of propylene oxide, sodium sulfate and sodium hydroxide, the temperature and the time of etherification. The optimum reaction conditions were obtained: etherification time etherification time 12 h,etherification temperature 50℃, propylene oxide 4g, sodium sulfate 0.24g, sodium hydroxide 4.8g. The results show the scenario could ensure the glass fibre forming process smoothly.

    • The Affect of Crystal Nano-TiO2 on Performance of negative ion Water-borne Polyurethane used by synthetic leather

      2012, 29(11).

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      Abstract:By dispersing nano-particle directly to get nano-TiO2/WPU composite membrane, meanwhile, we observed the affect of performance which added to crystal nano-TiO2(rutile and anatase type) on the composite membrane. The analysis of viscosity showed the rutile type had better effects on the increase of viscosity. The analyses of grain diameter showed that there were no differences on the stability of polyurethane-emulsion whether adding nano-TiO2 or not, and the composite particle still existed as the state of nanoscale, still, both type of rutile and anatase nano-TiO2 dispersed uniformly in composite film and had no effects on the flatness of it. The contacting angle and hygiene performance tests indicated that both crystal-size of composite film had no water-proof properties, the one which added anatase type had better hygiene function; the mechanical and anti-bacterial tests manifested the one added anatase type had better mechanical and anti-bacterial properties.

    • >Water treatment technology and environmental protection
    • Synthesis of PAMAM Dendrimers with carboxylic as Terminal groups and Its Performance on Scale Inhibition

      2012, 29(11).

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      Abstract:The dendrimers with four, eight and sixteen carboxylic methyl groups as outmost dendrons (denote as MCMD4、MCMD8 and MCMD16)were synthesized by divergent methodology using ethylenediamine and methyl acrylate as raw stuffs, and their terminal groups were turned into –COOK (denote as MCD4, MCD8 and MCD16) by basic hydrolysis. The results of scale inhibition experiment of the two hydrolysates which were used as scale inhibitors showed that MCD4, MCD8 and MCD16 has excellent scale inhibition on calcium carbonate, but the scale inhibition of MCD16 and MCD8 is much better then MCD4, the scale inhibitive rate of MCD4, MCD8 and MCD16 are 90%, 96% and 98% respectively. The structure of calcium carbonate scale inhibited by the scale inhibitor was investigated by FTIR and SEM, the scale inhibition mechanism of hyperbranched polymer with terminal carboxyl group was further explored.

    • Preparation of amphoteric polyacrylamide “water-in-water ”emulsion

      2012, 29(11).

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      Abstract:Amphoteric polyacrylamide (AmPAM) was prepared successfully through dispersion polymerization with acrylamide and amphoteric monomer 3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate in ammonium sulfate solution, using 2,2'-Azobis(2-methylpropionamide )dihydrochloride as initiator and poly methacrylatoethyl trimethyl ammonium chloride ( PDMC ) as stabilizer. The influences of concentration of stabilizer, inorganic salt and initiator ,monomer mass fraction and monomer ratio on dispersion polymerization were investigated. The optimum reaction conditions were ascertained as follows: ammonium sulfate concentration was from 22.3 to 26.3wt%, stabilizer concentration was from 0.195 to 0.248 g•(g(monomer))-1, the monomer ratio n (AM): n (DMAPS) was 9:1, the monomer mass fraction was 14%, the amount of initiator was 4.5×10-4 g•(g(monomer))-1. The structure of AmPAM was characterized by infrared spectrum and 1H nuclear magnetic resonance (1HNMR).

    • >Papermaking chemicals
    • Preparation and Application of Blocked Polyurethane Paper Strength Agent

      2012, 29(11).

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      Abstract:Cationic imidazole-blocked polyurethane (CBPU) was prepared by the reaction of isophorone diisocyanate (IPDI), Polycaprolactone glycol, methyldiethanolamine (MDEA), ADH, bisphenol A, N-[(1, 1-dimethyl-2-acetyl) ethyl]-β-dihydroxyethylamino propanamide (DDP) and imidazole as blocking agent. Fourier transform infrared spectroscopy (FT-IR), dynamic laser light scattering (DLS) and SEM were used to characterize the structure of CBPU, the particle size and the surface morphology of the paper. Influence of the blocked ratio on the particle size was studied. At the same time, effects of the blocked ratio and the dosage of CBPU on the physical properties of the treated paper were also studied. The experimental results show that structures of tertiary amine group, imidazole ring and urethane group are found in CBPU molecular structure. The particle size is nearly related to the blocked ratio of CBPU. The paper strength, especially the wet strength can be obviously increased with the increasing of the blocked ratio and the dosage of CBPU. The wet strength is 30.32% when the blocked ratio and dosage of CBPU are 10% and 5%.

    • >Acrylic series chemicals
    • Precipitation Polymerization of Low Molecular Weight Acrylic Acid and Recycling of Polymerization Residue

      2012, 29(11).

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      Abstract:The low molecular weight acrylic acid was synthesized by precipitation polymerization in petroleum ether utilizing azo-bis-isobutyronitrile (AIBN) as a free radical initiator and isopropanol as chain transfer agent. The influences of monomer concentration, initiator and chain transfer agent amount on the yield of polyacrylic acid are investigated. And the results showed the optimal polymerization conditions were that: the mass percent of initiator (AIBN) was 10% relative to monomer, the chain transfer agent was 100% relative to monomer, the monomer concentration was 100 g/L, and at 80 ℃ for 4h. Product was precipitated in bottom and the solvent can be removed and recycled. A monomer conversion of 92.6% was achieved after the residue was recycled for 5 cycles under the optimized polymerization conditions. The results of the gel permeation chromatography (GPC) showed that the weight average molecular weight (Mw) of polyacrylic acid was kept at 1000~1300 with minimal change and a polydispersity index (PDI) of 1.92~3.38 was obtained.

    • >Building chemicals
    • Effect of Sepiolite and Expandable Graphite on Thermal Degradation of Water-based Intumescent Flame-retardant Coatings for Steel Structure

      2012, 29(11).

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      Abstract:Expandable Graphite (EG) and sepiolite were added to the traditional APP/PER/MEL systems to get a new kind of water-based intumescent flame retardant coatings for steel structure. The effects of EG/ sepiolite on the fireproofing time and char formation of the coatings were investigated by using heat insulation test, thermo gravimetric analysis (TGA), derivative thermogravimetry (DTG) and X-ray diffraction (XRD). The results of TGA and DTG showed that the use of EG and sepiolite together could exert the flame retardant synergy effects: EG could postpone the formation of char layer at quite low temperature zone while sepiolite increased the stability of the residual char at higher temperature. XRD analysis indicated that the performance of anti-oxidation of the coatings was improved by adding EG and sepiolite. In addition, the fireproofing time of the steel structure was up to 72min when the film thickness of the coatings, which contained 3wt% sepiolite and 2%EG, was 1mm.

    • >Fine chemical intermediates
    • Scale-up Synthesis of Key Intermediate 4-AA of Penem and Carbapenem Antibiotics

      2012, 29(11).

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      Abstract:Abstract :The synthetic process of important penem and carbapenem antibiotics intermediate 4-AA was studied. Intermediate (A) in 74.5% yield was prepared by diazotization and nucleophilic substitution reaction of L-thronine with sodium nitrite, hydrochloride acid and sodium hydroxide at -5℃. Intermediate (A) reacted with Intermediate (B) (p-methoxylphenylaminoethyl acetate) for 5 h t o give intermediate(C) in 84.3% yield. Then intermediate (D) in 72.1% yield was synthesized by cyclization reaction of intermediate(C) in the presence of hexamethyldisilazane and lithium amide. Finally, 4-AA was prepared by Hydroxyl protection agent, Hydrolysis, decarboxylation oxidation reaction and deprotection agent with ozone. The tolal yield is 34.5%, HPLC purity is 99.34%.

    • Synthesis of 4-bromo-2-fluorobiphenyl by SuzukiCoupling Reaction with Pd(PPh3)4 Catalysis

      2012, 29(11).

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      Abstract:Abstract:More than 99.5% purity of medicine and liquid crystal intermediate of 4-bromo-2-fluorobiphenyl was synthesized via Suzuki coupling reaction with phenyl boric acid and 2-fluoro-4-bromo-iodobenzene as starting materials.The target compound was characterized by 1HNMR、IR and GC-MS. The generation cause of the by-product of boric acid self-coupling and terphenyl by-product was investigated, and the generation mechanism of by-products was speculated.