2015, 32(8).
Abstract:In order to endow microporous polypropylene membrane (MPPM) antibacterial capability and improve MPPM surface hydrophilicity, AgCl modification layer was fabricated on MPPM via dopamine oxypolymerization and alternate soaking technique. The chemical change of the membranes in the fabrication process was analyzed by FTIR and XPS. Surface morphology and AgCl distribution of the membranes were investigated by SEM-EDX. Surface hydrophilicity of the membranes was analyzed by the combination of water contact angle and water flux. Antibacterial capabilities of the membranes for E. coli and S. aureus were evaluated via plate counting method. The results indicated that the modified membranes have strong antibacterial capability and favorable hydrophilicity, their antibacterial rate for E. coli and S. aureus are 99.2% and 100%, respectively.
SHI Kai-yun , YU Qing-bao , ZOU Xiao-chuan
2015, 32(8).
Abstract:Ketoprofen is a good 2-aryl propanoic acid non-steroidal anti-inflammatory drug (NSAID). The new advances on its synthetic methods and applications of Ketoprofen in recent years have been reviewed in this paper. Based on systematically summarizing the research, improvement, and development of Ketoprofen production process, the typical process routes for synthesis of Ketoprofen with certain industrial potentials, including 2 (or 4)-aminobenzophenone method, 3-methyl-2-indolinone method, 2-(3-benzoylphenyl)propanenitrile method, 3-cyanomethylbenzoic acid method, asymmetric synthesis and enzymatic resolution of S-(+)-Ketoprofen, were analyzed and evaluated. Among these process routes, 2 (or 4)-aminobenzophenone method, 3-methyl-2-indolinone method, 2-(3-benzoylphenyl)propanenitrile method, and 3-cyanomethylbenzoic acid method may be suitable for large-scale production of Ketoprofen. The main directions to processes improvement were also indicated.
Yang Fan , Ha Chengyong , Hu Zhizhong , Wang Zhu
2015, 32(8).
Abstract:In this work, monomer miniemulsion of 3-[tris(trimethylsilyoxy)silyl]propylmeth- acrylate(TRIS) was prepared by a method of mechanical stirring with ultrasonic homogenization, with DNS525 and DNS500 as composite emulsifier(mass ratio of DNS525 and DNS500 was 1:1). The effects of mechanical stirring time, ultrasonic homogenization time, dosage of emulsifier, and mass ratio of TRIS and water on performance, stability and particle diameter of TRIS monomer miniemulsion were studied. The optimum condition was obtained as follows: mechanical stirring time was 60min, ultrasonic homogenization time was 15 min, dosage of emulsifier was 6%, mass ratio of TRIS and water was 2:3. The polymer miniemulsion obtained under this condition was white with blue light, homogeneous liquid. The gel content was 0.62%, the conversion rate was 98.32%, average particle diameter was 226.4nm, and the value of polydispersity index was 0.143.
2015, 32(8).
Abstract:The native collagen with triple helix structure was modified by lauric aldehyde and succinic anhydride, and the biosurfactant retaining native collagen structure was prepared (BCB). The basic surface activity of BCB was investigated and the results showed that the emulsion types of BCB and native collagen were o / w. Compared with native collagen, BCB exhibited better surface activity such as the foam expansion, foam stability, oil absorption capacity, emulsion activity and emulsion stability, but presented lower water absorption capacity. Moreover, the surface tension of BCB decreased with the increased storage time. The wetting power increased with increasing the concentration of BCB.
JIANG Jin-mei , LV Zheng-wei , MengTingting , CHEN Yong-kang , JI Yong-xin
2015, 32(8).
Abstract:With using silicone oil containing hydrogen and alkenyl succinic anhydride as raw materials and chloroplatinic acid as the catalyst,alkenyl succinic anhydride modified silicone was synthesized through the silicon hydrogen addition reaction.Then alkenyl succinic anhydride modified silicone was estedfied by alcohol ether.The influence of reaction temperature,reaction time and material mole ratio on degree of esterification were investigated by single factor experiment.And the appropriate reaction conditions as follows:the reaction temperature is 150℃,the reaction time is 17 h, the ratio of reactants [n (anhydride): n (alcohol ether)] is 1 : 2.6. Under these conditions, the conversion of product is 98.22%.And test the surface performance of the product.
2015, 32(8).
Abstract:A series of amphoteric polyurethane surfactant (APU) with long side chain alkyl and side chain carboxyl, as well as the structure of polyether (EO) embedded in main chain were synthesized, which was mainly based on H-MDI, PAE and DMPA. The properties were measured by infrared spectroscopy (FTIR), surface tension, critical micelle concentration, laser-particle size analyzer and electrical conductivity. The study indicated that when the PAE to DMPA ratio was 1:1, APU-2 with excellent comprehensive performance was obtained. The critical micelle concentration of APU-2 was 32.26 mg/L and the surface tension could be as low as 40.42 mN/m. Additional, the isoelectric zone of amphoteric polyurethane was in the region of pH 3.5~5.5 . With a narrow isoelectric zone distribution, APU-2 can be used in waterborne dispersions of a wide pH range.
LU Yang , WU Si-ping , ZHANG Hong-juan , LIU Qian , JIAO Qing-cai , LIU Jun-zhong
2015, 32(8).
Abstract:This study indicates the design and investigation of two continuous reaction processes for efficient production of D-lysine including an enzymatic racemization step and an enzymatic decarboxylation step. Firstly, L-lysine was racemized to the DL-lysine by whole cells containing amino acid racemase (AAR) ; then eliminating AAR and adding whole cells containing lysine decarboxylase (LDC), L-lysine in the mixture was selectively decarboxylated to 1, 5-pentanediamine and CO2; finally D-lysine was separated from mixture by isoelectric point crystallization and ion exchange resin. An optimal condition of the cascaded enzyme system is as follows: reaction temperature 40 oC, 0.2 mol/L of potassium phosphate buffer (pH=5.8), 50 g/L of L-lysine, 10 g/L whole cells of AAR and LDC, respectively, 4 mmol/L of PLP, 0.1 g/L of Triton-X 100. Under the optimal conditions, after 12 h including 2 h of racemization step and 10 h of decarboxylation step the enzymatic catalysis reaction was completed, and the yield of D-lysine could reach 42%, enantiomeric excess (e.e.) =98%.
DING Chun-hua , ZHANG Yu-lian , ZHANG Jun-ning , XIONG Chun-rong
2015, 32(8).
Abstract:A kind of quaternary ammonium salt was immobilized onto the coconut shell activated carbon, which was exploited to catalyze continuous cycloaddition of CO2 to epichlorohydrin (ECH) in packed bed. The samples were characterized by N2 Adsorption-desorption, Fourier transform infrared spectroscopy (FT-IR), hermogravimetric analysis, and X-ray photoelectron spectroscopy (XPS). The effects of pressure, temperature and reaction time on the cycloaddition reaction were investigated. The catalyst showed a high selectivity of over 98% to chloropropene carbonate(CPC) with a conversion of 50.3% in the packed bed as the WHSV of ECH was 14.1 h-1 at 140 °C and 1.4 MPa.
2015, 32(8).
Abstract:In this paper, four different Salen-Al was prepared, The structures of Salen-Al have been investigated using different characterization techniques such as IR, UV, 1H-NMR, EA and ICP, chose one of the four Salen-Al which had the highest catalytic activity, and compounded with quaternary ammonium salt to form the binary catalyst system. Carbonated soybean oil was prepared by the reaction of epoxidized soybean oil and carbon dioxide, and characterized by IR, 1H-NMR. While the reaction pressure, composite ratio were examined. Studies had shown that binary catalytic system in the temperature of 120 ℃, pressure at 2 MPa, Salen-Al and quaternary ammonium salt composite ratio at 1:1 had high catalytic efficiency, reaction time at 8h the conversion was as high as 76.8%, compared with using single catalyst the catalytic efficiency had improved significantly.
2015, 32(8).
Abstract:A simple and efficient method was developed for the synthesis of 4-phenyl-2-arylaminothiazoles from α-bromoacetophenone and aryl amine in ionic liquid [bmim]SCN. The reaction conditions were optimized. α-Thiocyanatoacetophenone was formed by substitution reaction of α-bromoacetophenone with thiocyanate in [bmim]SCN. After that, 4-phenyl-2-arylaminothiazoles were synthesized in 81.6%~95.2% yields via addition and cyclization of aryl amine with α-thiocyanatoacetophenone catalyzed by acetic acid. Ionic liquid [bmim]SCN could be reused at least five times without significant decrease in yield.
2015, 32(8).
Abstract:In this article, fomepizole was prepared from isobutyraldehyde or 2-methyl-2-propenal in three ways. Both of the starting materials were reacted with 80% hydrazine hydrate (w%), sulfuric acid and potassium iodide. By exploring the influence of adding order, concentration and reaction temperature on the yield, optimize the process. The first process started with isobutyraldehyde, with low boiling point. It was convenient by changing the way of feeding, which can avoid using of autoclave, and the yield was 40%. The second process had been changed to use 2-methyl-2-propenal, avoiding weakness of low boiling point. By optimizing the reaction conditions, the yield can reach to 80%. The third one showed complex operation, with the usage of hydrogen peroxide, which was not suitable for industry. Conclusion: Among those three, the second one, which was operated simply with high yield, was most suitable for industry.
GAO Hui , FU Ju , ZHANG Lei , YANG Ping , 宋新建
2015, 32(8).
Abstract:Thirteen fluorinated thieno[2,3-d]pyrimidine derivatives were synthesized in the yields of 69 ~ 83% by the SNAr reaction of substituted benzylamines with 4-chloro-2-trifluoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyridine, which was prepared directly from 2-amino-3-carbo-nitrile-tetrahydro[4,5]benzothieno[2,3-d]pyrimidine and trifluoroacetic acid (TFA) in the presence of phosphorous oxychloride via one-pot procedure. While 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile was first obtained according to the modified Gewald reaction with cyclohexanone, malononitrile and elemental sulfur as staring materials. The structures of these title compounds were confirmed by 1H NMR, IR, MS and elemental analysis. The crystal structure of compound IIIa was determined by single-crystal X-ray diffraction. The results show that this compound crystal belongs to monoclinic crystal system, space group C2/c with a = 2.6959(4) nm, b = 0.77245(13) nm, c = 1.6885(3) nm, α = 90? β = 109.320(2)? γ = 90? V = 3.3182(9) nm3, Z = 8, Dc = 1.455 Mg?m?3, μ = 0.23 mm?1, F(000) = 1504, R1 = 0.0579, wR2 = 0.1604. The preliminary bioassay results suggested that some of the title compounds exhibit good in vitro antitumor activity against HepG2 and MCF-7, especially the compounds IIIc, IIIf and IIIj exhibited higher inhibitory activity than the positive control gefitinib.
LIU Fa-bang , JIA Ming-chun , MEN Jin-feng , WANG Xiao-wei
2015, 32(8).
Abstract:Glu-Co/Mn-CCTS was synthesized via the combination of amino group of glutamic acid with imprinted crosslinked chitosan (Co/Mn-CCTS) by combining sol-gel method with reverse phase suspension method involving both manganese nitrate and cobalt nitrate as imprint molecules. Their structures were analyzed utilizing the techniques of FTIR and SEM. The static adsorption experiments for Co2 and Mn2 with low concentration indicate that the initial pH, temperature and initial Co2 and Mn2 concentrations, contact time, presence of other cations have great effects on the adsorption performance. The adsorption datas fit to pseudo-second-order , Langmuir and Freundlich models for both Co2 and Mn2 . The removal rates of Co2 and Mn2 are all above 98% at pH values from 4 to7 at 303K, which reach 96% after 2 h at pH value of about 5.5. The adsorption performance of Co2 on Glu-Co/Mn-CCTS compared favorably with that of Mn2 in presence of other cations.
HU Bing , TAN Ji-huai , XIE Bing-xue , ZHANG Hai-fei , YIN Jia-wei , ZHU Xin-bao
2015, 32(8).
Abstract:Bronsted-Lewis acidic ionic liquids [3-(1-Py)-(CH2)3-SO3H]Cl-xSnCl2 wi-th different mole fractions of SnCl2 was prepared(where x is the mole fractio-ns of the Lewis acid).The acidity of the group was characterized and compare-d to each other by means of FTIR in virtue of pyridine molecular probe,the d-ual acidic ionic liquids were then employed to the synthesis reaction of di(2-(2-butoxyethoxy)ethanol) terephthalate.The influences of catalyst type and amount,ratio of reactants,dosage of water-entrainer,reaction temperature,reaction time we-re investigated .In addition,the target product by 1HNMR .The results show that [3-(1-Py)-(CH2)3-SO3H]Cl-0.5SnCl2 had the highest catalytic activity.With [3-(1-Py)-(CH2)3-SO3H]Cl-0.5SnCl2 as catalyst,the optimal reaction conditions were as follows:n(DGBE):n(PTA)=2.3:1,catalyst (4.0% of mass of PTA),water-entrainer (60.0% of mass of PTA),reaction time (2.5h) and the speed stirring was 300r/min.the esterification rate was 99.43%.Catalyst in the case of without any proc-essing, can be recycled five times.
ZHOU Yi-ning , XU Miao-jun , SUN Cai-ying
2015, 32(8).
Abstract:A spiro-cyclic phosphate SPMA was synthesized from N-Methylol acrylamide (NMA) and pentaerythritol spiro phosphoryl dichloride(SPDPC).The reaction time and reaction mechanism were determined by tracking the reaction process using ultraviolet spectrum. It was found that the reaction could achieve the optimum state of chemical equilibrium in 1h. At first, the –NH- of NMA quickly reacted with SPDPC, then the –OH slowly reacted to form the final product by equilibrium reaction. The melt point of the product SPMA is 126~130 ℃. The thermal stability of SPMA was evaluated by Thermogravimetry and it was found that SPMA has better thermal stability and carbonization performance with 313℃of the initial decomposition temperature, 343℃ of the maximum weight loss temperature (Tmax) and 32.6% of residue under 800℃. With SPMA flame retardant finishing of cotton cloth and the addition was 5%, the limiting oxygen index increased by 2%, the combustion and smoldering time reduced by more than 70%.
2015, 32(8).
Abstract:Labile polymer microspheres were prepared by inverse emulsion polymerization by using acrylamide (AM), 2 - methyl - 2 - acrylic amide propyl sulfonic acid (AMPS) as monomers. Morphology of labile polymer microspheres is irregular spherical particles, microsphere size matches the micro/sub-micro size of pore throat. The structure of labile polymer microspheres were confirmed by Infrared spectroscopy. Secondary gelling results show that the gelling time extended with the increase of salinity and apparently shortened with the increase of temperature, Secondary crosslinker FQ has little effect on gelling time, but significantly affect gel strength. the gel with controllable gelling time(about 1 ~ 3 days),good thermal stability and without dehydration can be obtained when the temperature > 90 ℃, degradable polymer microspheres with amount of 1.5% ~ 2% and the secondary crosslinker FQ with amount of 0.5% ~ 1.2%. In the oil phase, degradable polymer microspheres can’t conduct secondary crosslinking which indirectly prove its plugging selectivity . SEM experiment confirmed that the secondary gel process of degradable polymer microspheres, namely particles crosslinked to form particles aggregate, and then particle aggregats crosslinked to form large aggregate and the finally to form bulk gel.
2015, 32(8).
Abstract:Static adsorption characteristics of dendronized polymers for EOR at different branching degree on quartz sand were studied via soaking method, and the molecular size, microstructure of polymer solution were investigated though Dynamic and static laser light scattering instrument and Environmental Scanning Electron Microscope respectively. It was found that, all of isothermal adsorption curves of dendronized polymer solutions were presented to three stages; At initial stage, polymers owed small branching degree had smaller steric hindrance than polymers of large branching degree on quartz sand possessed constant surface area due to its fewer number of branched chains and smaller hydrodynamic radius, resulting that its adsorbing capacity greater. In the phase of multilayer adsorption, dendronized polymers had strong branching degree could easily wind and form a network structure because of the intense interaction of branched chain, leading that its adsorption layer and adsorption quantity on the quartz sand surface were more than polymers of weak branched degree.
2015, 32(8).
Abstract:Abstract: Nine reactive aldehyde dyes were synthesized by “grafting” colorant groups to the α-C of several aldehyde compounds. The structures of the target products were characterized by means of FTIR, UV-vis, and ESI-MS. Aluminum-pretanned wet-white sheep leather was chosen as a substrate for the application experiments, and four dyeing property indexes, i.e., substantivity (S), exhaustion (E), fixation (F) and reactivity (R) were measured. The results indicated that, without the addition of neutral salts and under mild conditions (T = 35-45 °C,pH = 4.0-6.5), all the dyes could dye wet-white leather within 1.5 h, and the dyed leather possessed a satisfactory washing-fastness. Key words: aldehyde; reactive dyes; identification; application
2015, 32(8).
Abstract:In order to explore the action mechanism of high polymer (HP-SRA) by comparison, the self-made high polymer (HP-SRA) and Eclipse-Floor shrinkage reducing admixture (Eclipse-SRA) were selected as two shrinkage-reducing materials. The results indicate that the shrinkage reducing ability is improved through reducing the average adsorption rate of high polymer (HP-SRA) on the surface of cement particles, the surface tension and the evaporation of pore solution, and through improving the kinematic viscosity of pore solution and the distribution of capillary structure of cement. Meanwhile, The dispersion ability is improved through improving the initial fluidity cement paste, and the fluidity had nearly no loss after 1 h. The unity of shrinkage-reducing and dispersing performance is achieved.
LIU Hai-feng , YANG FAN , CHEN QIU FEN , LI TIAN LONG
2015, 32(8).
Abstract:Tri-silane coupling agent(TI-MPS) was synthesized with the yield of 94% by reacting 3- mercaptopropyltrimethoxysilane(MPS), triallyl isocyanurate(TI) and photoinitiator 2,2-dimethoxy-2-phenylacetophenone(DMPA) under 365nm UV-light. The structure of reaction product TI-MPS was confirmed by Fourier Transform Infrared Spectroscopy and 1HNMR spectrum. Properties of TI-MPS hydrolyzate after curing was studied. The results showed that the cured TI-MPS layer on iron sheet could withstand more than 100 cm?kg impact and bending level 1. The polarization resistance of the layer is 7459.3Ω?cm2. The performances of TI-MPS layer were superior to the single silane MPS layer. Salt spray accelerated corrosion tests showed the protective performance of TI-MPS is better than that of MPS. Especially the TI-MPS layer on aluminum sheet could resist 1000h salt spray test.
2015, 32(8).
Abstract:Morpholine was found to be an effective catalyst for the synthesis of 3-acetyl coumarin through Knoevenagel condensation of 2-hydroxybenzaldehyde with ethyl acetylacetate. Reaction conditions such as solvent, base, catalyst loading, and reaction time were carried out to scrutiny. The results showed that under ultrasonic condition, 2-hydroxybenzaldehyde reacted with ethyl acetylacetate in ethanol at room temperature catalyzed by morpholine and Na2CO3, giving 3-acetyl coumarin after 20 min in 90% yield. The product was characterized with NMR and IR. A plausible catalytic mechanism was also proposed.
2015, 32(8).
Abstract:A novel and mild synthesis method of deuterated carbamate compounds (3a'~3c') was designed. Organic phenol as raw material, the intermediate chloroformate(2a~2c) was prepared by triphosgene under the NaOH as the catalyst, the target compound carbamate compounds (3a'~3c') was obtained by condensation with methylamine-D3-hydrochloride. Synthesis route can avoid the use of highly toxic isocyanate, and had the advantages of simple operation, short process flow, less side product, the yield of carbamate compounds was more than 60%, deuterium labeled isotope abundance is not diluted. The product was characterized by HPLC、MS、 1H NMR and 13C NMR, the chemical purity was more than 99%, the deuterium enrichment was more than 99 atom% .
2015, 32(8):0-0.
Abstract:Using inexpensive and readily available m-hydroxybenzaldehyde, primary amine and dimethyl carbonate, ortho-anisicaldehyde was synthesized by simple condensation, nucleophilic substitution and hydrolysis reactions under moderate condition. Through screen experiments, excellent synthetic condition which is ortho-hydroxy-benzylidene-butylamine/DMSO/KOH/85oC/24h was established. Comparing to reported methods in 60%-70% yields , the good yield was achieved up to 81% and the method is environmentally friendly. The product was characterized through 1H NMR, 13C NMR spectra and elemental analysis.