• Volume 33,Issue 1,2016 Table of Contents
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    • >Oil field chemicals and petroleum additives
    • Synthesis and Properties of Heavy Oil-in-Water Emulsion Demulsifier

      2016, 33(1).

      Abstract (1068) HTML (0) PDF 0.00 Byte (0) Comment (0) Favorites

      Abstract:Redox initiator of ammonium persulfate/sodium bisulfite, styrene,butyl methacrylate, acrylamide and methacryloyloxyethyl trimethyl ammonium chloride as the synthesis of the monomers , which synthesizing tetrapolymers heavy demulsifier styrene / butyl methacrylate / acrylamide / methacryloyloxyethyl trimethyl ammonium chloride by emulsion copolymerization . The structure of tetrapolymers heavy demulsifier was characterized by Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy. The optimum conditions of synthetic quaternary copolymer heavy demulsifier were as follows: reaction temperature 65 ℃, emulsifier dosage 1.6% (the total mass quality system) , initiator dosage 1.1% (the total mass of the monomers) , monomer concentration 30% . Using Shengli Oilfield chenzhuang heavy oil simulated heavy oil emulsion to evaluate the performance of homemade tetrapolymers heavy demulsifier.Effects of demulsification conditions on demulsification performance. Under the condition of demulsification temperature 60 ℃, demulsification dosage 200 mg/L , demulsification time 120 min, the dehydration was reached up 89.3% , the oil content of water 198.6 mg/L, the oil-water interface was neat and clear water prolapse. The performances tests of the O/W demulsifier were superior to those of industrial demulsifiers AE-8051, YT-100, SP-169, BQ-05.

    • >Drug and cosmetic materials
    • Synthesis of Sotalol Hydrochloride

      2016, 33(1).

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      Abstract:Sotalol hydrochloride was prepared form aniline by sulfonylation,Friedel-Crafts reaction,isopropylamination and hydrogen reducing reaction.The total yield is above 75.4%(based on aniline)and purity is above 99.8%.The methord is very simple,economic and green chemistry process.

    • >Functional materials
    • Preparation and Characterization of Metal Phosphate Nano-hybrid Materials with Controlled Morphology

      2016, 33(1).

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      Abstract:Abstract: Metal phosphonates nanosheets and nanorods were prepared from the reaction of three metal precursors, including aluminium hydroxide, ferric hydroxide and zinc acetate, with phenyl or diphenyl phosphonates without the assistance of templates. Structures of materials were characterized by Fourier transform infrared (FTIR) spectra, thermogravimetric analysis (TGA), scanning electron microscopy(SEM), powder X-ray diffraction (XRD), demonstrated a structure of Me—O—P(Me=Al, Fe, Zn) main chains and the existence of π−π stacking, which enabled the assembly into nanorod and nanosheets. The results show that the dimension of nanostructure is largely determined by phosphonate precursors rather than metal centers. Two-hydroxyl functionality tends to generate a layered nanostructure, while one-hydroxyl functionality results in nanorod structure. TGA spectra show that when organophosphonic ligands are incorporated into the hybridized materials, their thermal stability is significantly improved.

    • >Catalysis,separation and purification technology
    • Effect of Ni Precursors on the Performance of Ni/SBA-15 Catalysts for Methane Dry Reforming

      2016, 33(1).

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      Abstract:The catalytic properties of Ni/SBA-15 catalysts that prepared by different nickel precursors were studied for carbon dioxide methane dry reforming. The catalyst prepared by nickel acetate exhibited the best catalytic activity among the samples and the excellent stability and selectivity were obtained at 700篊 for 20 h. The structure, surface species and redox properties of the catalysts were investigated by N2 adsorption-desorption, XRD, H2-TPR and XPS techniques. The results indicated that the superior catalytic activity was ascribed to a lower crystallinity and the excellent redox ability. Besides, the interaction between metal (Ni) and support (SBA-15) was responsible for the outstanding performance.

    • >Rubber and plastics auxiliaries
    • Synthesis and Characterization of Triallyl Isocyanurate

      2016, 33(1).

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      Abstract:Triallyl isocyanurate (TAIC) was synthesized by quaternary ammonium salt catalytic of isocyanuric acid and chloropropene in the solvent of N,N-dimethyl formamide (DMF). The parameters of the process affected on production were investigated. The product was analyzed by high performance liquid chromatography (HPLC), infrared spectroscopy (FTIR) and carbon nuclear magnetic resonance spectroscopy (13CNMR). The results showed that the yield of TAIC based on isocyanuric acid was 93.3% when n (isocyanuric acid): n (chloropropene) was 1:4, the temperature of dropping allyl chloride was 100 ℃, dropping time was 2 h, reaction temperature was 120 ℃, reaction time was 1.5 h, and the catalyst was tetramethylammonium chloride. The purity of TAIC was 97.9% (HPLC).

    • >Functional materials
    • Preparation of graphene dispersing system stabilized by ethanol amine and its pH-response property

      2016, 33(1).

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      Abstract:A stable graphene dispersing system was prepared by using ethanol amine as dispersant and hydrazine hydrate as reductant. UV-vis spectroscopy (UV-vis), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the dispersion and pH-response properties of the system. The results show that the graphene can be modified by ethanol amine to form the composite (ETA-RGO), leading to a stable and uniform graphene dispersion. AFM and TEM show that the maximum width of graphene in the system is about 1 μm, and the thickness is about 0.8nm. In addition, graphene tended to agglomerate when the pH value of the system was decreased to 6. This system can not only disperse graphene in aqueous solution, but also endow graphene with pH-response property. It is expected to extend the application range of graphene related materials in the biological field.

    • >Electro-organic chemistry and industry
    • Synthesis and photoelectric properties research of two fluorene sensitized dyes

      2016, 33(1).

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      Abstract:Thiophene and furan at the 9th position of the fluorene were prepared through condensation reaction as the starting materials, followed with formylation on 2th position of thiophene and furan, then the Knoevenagel condensation of intermediate and acrylic acid gave two simple structure dyes F-S and F-O, which were consisted of flourene as the electron donor, while thiophene and furan as the π bridge. All the intermediates and target dyes were characterized by 1H NMR. After testing the optical properties found that only a single atom change lead to a greatly difference about the two dyes. The maximum absorption wavelengths of UV-vis of dye F-O was 22 nm red shift compared to F-S. The batteries were also assembled and tested, the photoelectric conversion efficiency (PCE) of F-O was 2.76 %, while the efficiency of F-S was just 1.98 %. The results illustrated that the introduction of appropriate π bridge structure can significantly improve the photovoltaic properties of fluorene dyes.

    • >Rubber and plastics auxiliaries
    • Application of Polyoxymethylene Dimethyl Ethers in the Synthesis of Bisphenol F

      2016, 33(1).

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      Abstract:Bisphenol F (BPF) was synthesized from polyoxymethylene dimethyl ethers (PODEn, n=1~5) instead of formaldehyde (FA) of traditional process catalyzed by phosphorous acid (PA). Results showed that the yield of BPF was parabolic with the increase of n under the same temperature, that is, the yield firstly increased and then decreased. And the yield of BPF synthesis from PODE2 reached the maximum of 95.8%. The selectivity decreased with the increase of n. However, the selectivity of BPF synthesis from PODEn had obvious advantage compared with traditional synthesis technology from FA. By comprehensive consideration, PODE2 is the best starting material for substituting FA to synthesize BPF. Meanwhile, the effects of mole ratio of phenol (Ph) to PODE2, mole ratio of PA to PODE2, reaction temperature and reaction time on yield, selectivity and isomer distribution were also investigated. Based on single factor experiments, response surface methodology (RSM) was conducted to create a quadratic regression equation and obtain the optimal conditions of BPF synthesis from PODE2, which were mole ratio of Ph to PODE2 of 16.4, mole ratio of PA to PODE2 of 5.49 and reaction temperature of 90 ℃. At the optimum conditions, the yield reached 99.0% and the selectivity reached 95.8%.

    • >Oil field chemicals and petroleum additives
    • Study on the Temperature-resistant and Salt-tolerant Surfactant BHJ-2 for EOR

      2016, 33(1):0-0.

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      Abstract:In view of high temperature and salt of carbonate reservoirs, a novel temperature-resistant and salt-tolerant surfactant BHJ-2 was synthesized. The temperature- resistance and salt-tolerance performance, interfacial activity, ability of changing wettability, adsorption property, washing oil property and displacement efficiency were evaluated. The results showed that BHJ-2 has capacity of temperature-resistant 140°C and salt-tolerant 2.33×105 mg/L, respectively, reduce adsorption loss to 0.574 mg/g, change oil-formation water-rock contact angle from 109.6° to 61.4°. After aging for 30 days under temperature of 140°C, the oil-water interfacial tension and washing oil efficiency of BHJ-2 were almost unchanged, interfacial tension between BHJ-2 and oil was 0.576 mN/m, washing oil efficiency under static condition was 83.7%, enhancing the displacement efficiency by 36.7%. BHJ-2 has a promising application in high temperature and salinity carbonate reservoirs with lipophilicity.

    • >Surfactants
    • Synthesis and Performance of Quaternary Ammonium Bis-imidazoline as Emulsifier

      2016, 33(1).

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      Abstract:Firstly, Gemini imidazoline quaternary ammonium was prepared with butyl amine and epoxy chloropropane and long chain imidazoline. And the structure of the synthesized product was characterized by FTIR and HNMR. Then, emulsified asphalt was made by the Gemini imidazoline quaternary ammonium and Qin huangdao AH-70 asphalt and the preparation conditions of emulsified asphalt was investigated. In addition, the economic benefit of Gemini imidazoline quaternary ammonium was analyzed. The results show that the optimal conditions were as follows: pH value was 5.0, the asphalt temperature was 135℃, the soap liquid temperature was 55℃, the mass ratio of water and oil was 6:4, and emulsifier dosage was 1.5%.

    • >Fine chemical intermediates
    • Synthesis of 9-Ethyl Tetrahydro-Carbazole

      2016, 33(1).

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      Abstract:Tetrahydro-carbazole was synthesized by cyclization reaction of phenyl-hydrazine and cyclo-hexanone with the yield of 70.5%. And 9-ethyl tetrahydro-carbazole was synthesized by alkylation of tetrahydro-carbazole with ethyl bromide. The structures of product were characterized by 1HNMR和13CNMR. The optimum reaction conditions for synthesis of 9-ethyl tetrahydro- carbazole were as follows: n(tetrahydro-carbazole) : n(ethyl bromide) : n(sodium hydroxide)=1:4:1.5, m(tetra- hydro-carbazole) : m(potassium iodide)=1:0.01, c(hexadecyl trimethyl ammonium bromide)=2.5×10-3 mol/L, c(tetrahydro-carbazole) =0.50 mol/L. The yield of 9-ethyl tetrahydro-carbazole was 86.0% under the optimum conditions in the solvent of acetonitrile for 9 h. Compared with the traditional process (chlorination of cyclohexanone with chlorine, followed by condensation), the synthesis could avoid the formation of chlorinated by-products and is easily to be commercialized.

    • Synthesis of Dimethylhexane-1,6-dicarbamate over Supported Zinc Acetate Catalyst

      2016, 33(1).

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      Abstract:A series of supported Zn(OAc)2 catalysts were prepared by incipient impregnation and used for synthesis of dimethylhexane-1,6-dicarbamate(HDC) by methoxycarbonylation of 1,6-hexanediamine (HDA) with dimethyl carbonate (DMC). The catalysts were characterized by XRD, BET, NH3-TPD, TG-DTG, FTIR, XPS and the results confirmed that the SiO2 supported Zn(OAc)2 catalyst showed the best activity owing to the formation of Si-O-Zn and the surface acidity which facilitated the activation of DMC and HDA. Under the optimum reaction conditions of 0.02 mmol Zn(OAc)2/mmol HDA, DMC to HDA molar ratio=2, 80 °C and 6 h, the conversion of HDA was 96.0%, the yield of HDC was 68.5%. The used catalyst can be recycled by simply separation and wash, and no obvious deactivation was found even after 5 cycles.

    • Research on Green Synthesis of N-(n-butyl)thiophosphoric Triamide

      2016, 33(1):0-0.

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      Abstract:N-(n-butyl)thiophosphoric triamide (NBPT) was synthesized successfully by modified “one-pot” method. During the experiments, the ammonia was used as acid-binding agent to replace traditional liquid reagent and the raw materials of subsequent amination reaction. The effect of the reaction temperature, the mole ratio of substrates, the flow rate of ammonia, the intermittence time of flowing ammonia and the temperature of amination reaction on yield of the product were investigated. The optimized experimental parameters were as follows: the reaction temperature was 0 ℃, the mole ratio of n-butylamine (0.42mol) and thiophosphoryl chloride (0.35mol) was 1.2:1, ammonia flow rate was 15 mL/min, the intermittence time of flowing ammonia was 30 min and the temperature of amination reaction was 10 ℃. Under the optimized conditions, the yield of NBPT was 75.6% and the purity was 97%. The sample with the highest yield was characterized by infrared spectroscopy (IR), elemental analysis, nuclear magnetic resonance spectrum (NMR) and liquid chromatograph-mass spectrometer (LC-MS). The synthesis process, an innovative green one, had advantages of simple operation steps and low production cost. At the same time, the only by-product was ammonium chloride.

    • >Electronic chemicals
    • Preparation and Capacitance Performance of Co3O4 Nanocluster Arrays

      2016, 33(1).

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      Abstract:Co3O4 grown on nickel foam and carbon fiber substrate with different morphologies were synthesized by hydrothermal synthesis method using different filling volume. The structure and morphology of the products were characterized by X-ray diffraction (XRD),Fourier Transform Infrared Spectroscopy (FTIR)and scanning electron microscopy(SEM). The results showed that by changing the filling volume can prepared the cobalt oxide products with thesame phase and different morphologies in the hydrothermal reaction system.Electrochemical properties of Co3O4grown on nickel foam electrode were characterized by cyclic voltammetry (CV), chronopotentiometry, and electrochemical impedance measurements method.The results indicated that the70%filling volumereaction system prepared uniform Co3O4nanocluster arrays,which exhibited noticeable pseudocapacitive performance with a high capacitance of 961F?g-1 at 1A?g-1in 2mol ? L-1KOH electrolyte, and 76% was maintained when the current density increased to 20A?g-1.

    • >Biological engineering
    • Immobilization of gene engineering bacteria with Tryptophan synthetase and the synthesis of L – tryptophan

      2016, 33(1).

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      Abstract:Using sodium alginate as embedding agent, glutaraldehyde as crosslinking agent and calcium chloride as filling agent immobilize the genetic engineering bacteria with tryptophan synthetase. The effect of the concentration of sodium alginate, glutaraldehyde and calcium chloride and the bacteria load were investigated. And then these factors were optimized by response surface method, in order to determine the optimal immobilized conditions. After that, using the best immobilized bacteria synthesize L-tryptophan and making sure the optimum substrate concentration and the amount of immobilized bacteria. The best preparation conditions for the immobilized bacteria are 28.92 g/l sodium alginate, 0.95% glutaraldehyde, 19.82 g/l calcium chloride and 25 g/l bacteria load. The best synthesis conditions of tryptophan are 1% L-serine and 8 g immobilized bacteria. The average conversion rate from substrate is 28.16%. The immobilized bacteria can be used continuously for 15 times.

    • >Catalysis,separation and purification technology
    • Catalyzed Synthesis of Trioctyl Trimellitate by Nb2O5/ Palygorskite Solid Acid

      2016, 33(1).

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      Abstract:The palygorskite was ion-exchanged with NbCl5 and calcined at 300°C to prepare solid acid of palygorskite supported Nb2O5 (300-Nb2O5/PG). This modified palygorskite was characterized by XRD, XPS, UV–Vis, N2 adsorption/desorption, ICP and NH3-TPD. The material was used in the esterification of trioctyl trimetabenzoate (TOTM) as catalyst. The esterification yield of trioctyl trimetabenzoate was 95.3% at 210°C to reflux 5 h when catalyst amount was 5 wt. % of trimellitic anhydride, trimellitic anhydride: 2-ethyl hexanol = 4:1(mol/mol). The esterification yield was 89.2% when the catalyst was reused ten times.

    • Synthesis of Dialkyl Adipate using Ammonium and Silver Co-doped Phosphotungstic Acid as Catalyst

      2016, 33(1).

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      Abstract:Ammonium and silver co-doped phosphotungstic acid was prepared by ion-exchange method and used as catalyst for the synthesis of dioctyl adipate. The structure, acid strength and surface acid density of (NH4)0.5Ag0.5H2PW12O40 were characterized by FT-IR, XRD and Hammett indicator method. As shown by the results, (NH4)0.5Ag0.5H2PW12O40 performed the highest activity, and the esterification rate reached 99.8%. The catalytic activity of (NH4)0.5Ag0.5H2PW12O40 was higher than that of traditional single cation doped phosphotungstic acid. The catalytic property of (NH4)0.5Ag0.5H2PW12O40 for the synthesis of other dialkyl adipate was also investigated. And the esterification rate was over 99.5%. In addition, the esterification rate still reached up to 98.6% after (NH4)0.5Ag0.5H2PW12O40 recycling in 4 runs.

    • >Perfumes and essences
    • Analysis of Volatile Flavor Constituents of Fried Zanthoxylum Essential Oil by SPME and SAFE

      2016, 33(1).

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      Abstract:The volatile flavor constituents of fried zanthoxylum essential oil were extracted by solid phase micro-extractioon(SPME)and solvent-assisted flavor evaporation(SAFE)and analyzed by gas chromatography mass spectrometry(GC-MS). A total of 103 volatile compounds were identified in fried zanthoxylum essential oil, including 36 hydrocarbons, 12 aldehydes, 8 ketones, 28 alcohols,12 esters, 2 ethers and 5 heterocyclic compounds. There are some certain differences in volatile compounds extracted by SPME and SAFE.

    • >Drug and cosmetic materials
    • Preparation And Characterization of CoQ10-Loaded Nanostructured Lipid Carriers

      2016, 33(1).

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      Abstract:Abstract: The aim of this research was to prepare the CoQ10-loaded nanostructured lipid carriers by high pressure homogenization method. The optimized CoQ10-NLC was assessed for particle size、polydispersity index、Zeta potential、retention rate and in vitro permeation in pig skin. The results showed that CoQ10-NLC had good dispersing and high physical stability. Especially, after a month the retention rate of CoQ10 was higher than 80% at the storage condition of 4 ℃ . In vitro transdermal study indicated CoQ10-NLC enhanced the permeation of CoQ10 in the viable epidermis and dermis.

    • Improved Synthesis of Oxiconazole Nitrate

      2016, 33(1).

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      Abstract:With 1,3-dichlorobenzene as raw materials, 2-chloro-1-(2,4-dichlorophenyl) ethanone (Ⅲ) was synthesized by Friedel-Crafts acylation, N-alkylation and oximation, then it was reacted with 2,4-dichlorobenzyl chloride and salinized by nitric acid, and got the final product oxiconazole nitrate (Ⅰ). The N-alkylation and oximation were performed by a "one-pot" reaction, and the key factors of the reaction were investigated. The improved synthetic route simplified the operation procedure, and the overall yield of oxiconazole nitrate was increased from 41.8% to 70.8%, with a purity of 99.9%.The structures of the products were characterized by IR, 1HNMR and HRMS spectra.

    • New Method for Preparation of ( ) - 1,2,3,4-Tetrahydropapaverine

      2016, 33(1).

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      Abstract:Merrified resin-bound BINOL–derived phosphoric acid has been employed for the catalytic transfer hydrogenation of 3,4-dihydropapaverine to synthesize ( )-1,2,3,4-tetrahydropapaverine. Several catalysts were selected and the excellent catalyst was bounded on Merrified resin. The effects of solvent type, reaction temperature and structure of Hantzsch ester on yield and ee value of ( )-1,2,3,4-tetrahydropapaverine are investigated in detail. Under the optimal conditions (toluene as solvent, 40℃ and dimethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate as hydride source), the ( )-1,2,3,4-tetrahydropapaverine was obtained in 95% yield and 98% ee. The catalyst can be easily separated and recycled. After reused seven times, the activity of catalyst was observed a small drop in ee, but can regained by simple cleaning in hydrogen chloride - ethyl acetate solution.

    • Synthesis of a Bismuth Schiff Base Complex and its Interaction with Bovine Serum Albumin

      2016, 33(1).

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      Abstract:In the non-aqueous solvent system, a ternary complex was synthesized with o-vanillin-glycine Schiff base, 8-hydroxyquinoline and anhydrous bismuth chloride, which was confirmed to be [Bi(C10H10NO4)(C9H6NO)2], by elemental analysis, thermal analysis, spectral analysis, etc. Phenolic hydroxyl oxygen and the nitrogen of carbon-nitrogen double bond in the Schiff base were bonded to Bi(III) ion, and the oxygen atom and heterocyclic nitrogen atom of 8-hydroxyquinoline were bidentate-coordinated with Bi(III) ion, forming a five-member chelate ring. In particular, the interaction between the complex and bovine serum albumin (BSA) was investigated by fluorescence spectroscopy at different temperatures. It was proved that the fluorescence quenching of BSA by Schiff base-complex was a result of the formation of a complex with a stoichiometric ratio of 1:1. The quenching constant was calculated to be 6.21×104 L/mol. And the positive ΔH and ΔS values indicated that hydrophobic force might play a major role during the binding process. Finally, synchronous fluorescence spectroscopy was applied to examine the effect between complex and BSA. The tryptophan residue was found to decrease with a red shift of emission wavelength, which demonstrated that the complex changed the conformation of BSA.