Hao Wen-yue , Ma Xiao-lei , Ma Rui , Tian Ye
2014, 31(9).
Abstract:Elementary and X-Ray Fluorescence analysis were used to investigate the elemental component of Kraft lignin. Kraft lignin was valorized in water-ethanol mixture (v(water):v(ethanol)=50:50) with 2 MPa initial H2 pressure. FT-IR was used for the analysis of the structure of Kraft lignin before and after reaction, and the results showed that ether bond decreased while C-H bond increased in the products. The monomer products were qualitative and quantitative analyzed with GC-MS and GC-FID, respectively. The total yield of monophenols was 4.57 wt% without catalyst. The introduction of Ni2P doubled the monophenols yield. When MoP was used as the catalyst, the yield of monophenols is similar to that obtained through Ni2P catalyzed process. However, benzyl alcohols and considerable amount of linear oxygen-containing organics were observed, leading to decrease of monophenols selectivity.
Su Er-zheng , YOU Peng-yong , WEI Dong-zhi
2014, 31(9).
Abstract:The low cost naturally immobilized lipase CPL from the Carica papaya was used to catalyze kinetic resolution of aromatic secondary alcohols. Taking the 4-phenyl-2-butanol as the model substrate, the effects of reaction temperature, reaction solvent, acyl donor and substrate molar ratio on the resolution ability of CPL were investigated. The results showed that the optimum reaction conditions were as follows: reaction temperature of 30~45℃, acyl donor of active vinyl ester, n-hexane or cyclohexane as reaction solvent and substrate/acyl donor molar ratio of 1:2. Under these conditions, the substrate conversion was close to 50%, e.es was more than 99%, and enantiomeric ratio E was higher than 200. CPL also showed good resolution ability to other similar structure aromatic secondary alcohols. This work provides a new biocatalyst alternative for economic preparation of chiral aromatic secondary alcohols.
YAN Jun , YU Li-mei , Zhang Wenzhu , GAO Zhan-xian
2014, 31(9).
Abstract:In this article ,we used GC-MS to confirm the structure and content of the impurities in fluorene. The material balance of each component of reactants and products reveals that in the preparation of fluorenone from the oxidation of solid fluorene reaction with xylene used NaOH as catalyst and quaternary ammonium salt as the phase transfer agent and air as oxidant, conversion yield of fluorene is 100%,product yield of fluorenone and water is 100% with no other by-products, meanwhile, there was no change in the number of the impurities in fluorene during the reaction, the moles of each component also remained the same. The result was verified by the reaction of pure fluorenone from the oxidation reaction of pure fluorene in the same condition. After fluorenone was isolated from the reaction, solvents, catalysts, phase transfer reagent can be recycled. The reaction mechanism was also discussed.
2014, 31(9).
Abstract:The synthesis of 6-methoxy-2-naphthaldehyde (Ⅰ) was explored. The treatment of 2-acetyl-6-methoxynaphthalene (Ⅱ) with sodium hypochlorite resulted in the formation of 6-methoxy-2-naphthoic acid (Ⅲ). Esterifying of compound Ⅲin the presence of CH3OH/H2SO4 afforded 6-methoxy-2-naphthoate (Ⅳ), followed by Red-Al reduction of the ester group, led to 6-methoxy-2-naphthyl methanol (Ⅴ), a selective oxidation was then performed with MnO2 to provide the target compound 6-methoxy-2-naphthaldehyde (Ⅰ) in an overall yield of 73.2%. The structure of Ⅰ was characterized by MS and 1H NMR.
2014, 31(9).
Abstract:Abstract: Poly(amine-ester)-1,8-naphthalimide dendrimer (PAE-1,8-NL) is synthesized from ethylenediamine (EDA), trimethylolpropane triacrylate (TMPTA) and 1,8-naphthalic anhydride. In the energy transfer systems of PAE-1,8-NL and dyes (Eosin B, Rhodamine B, Titan yellow , Methylene blue and Methyl orange) , The changes of fluorescence intensity were studied. The results show that the fluorescence of dyes increased when PAE-1,8-NL added the dyes DMF solutions. The fluorescence of dyes is increased and then decreased by PAE-1,8-NL. The rank of their fluorescence enhancement ability was Methylene blue > Rhodamine B > Methyl orange > Eosin B > Titan yellow. In DMF, acetone and acetonitrile solvent respectively, the different fluorescence intensity of the effect of PAE-1,8-NL on dyes.
2014, 31(9).
Abstract:Abstract:The synthesis and characterization of emulsion possessing core-shell structure and containing short-chain fluorinated acrylate were studied in this paper. A series of emulsion possessing core-shell structure and containing fluorinated acrylate copolymer in shell was synthesized via a multi- stepped seed emulsion polymerization, and meanwhile, by using the copolymer of methyl meth acrylate(MMA) with butyl acrylate(BA) as the core and the copolymer of 2-(perfluorinated hexyl)ethyl methacrylate ( FMA6) with acrylate linking various length of n-alkyl chain (n=4, 8, 12, 16 and 18, respectively)as the shell. The effects of both the content of the fluorinated monomers and the length of n-alkyl chain of acrylate in the shell on oil and waterproof performances were especially investigated, based on a systematical optimization of process conditions. The obtained products were then characterized and analyzed. The results showed that the emulsion with w(FMA6)=8.5% and methyl hexadecyl methacrylate rich in shell could make the latex film possessing the best hydrophobic and oleophobic performance. The contact angle of the film with water was 124.67°and methylene diiodide was 112.76°. The characterization results of FTIR, TEM and DSC/TGA indicated that the prepared emulsion containing fluorinated acrylate copolymers showed the typical core-shell structure. The synthesized polymer emulsion has two glass transition temperatures(Tg1=-18.87℃and Tg2=32.08℃), indicating their decomposition temperature increased by 20℃.Thereout, the latex film made by short-chain fluorinated acrylate emulsion displayed excellent oil and waterproof performances, and thermal stability .
CHEN Yao-bin , LUO Ru-xian , JIANG Shao-hua , HU Bin
2014, 31(9).
Abstract:1,6-hexamethylene diurethane was synthesized with allyl polyoxyethylene ether and hexamethylene diisocyanate as raw material in the presence of tin catalyst. Gemini polyoxyethylene ether trisiloxane surfactant (GPETS) was prepared by the hydrosilylation from 1,1,1,3,5,5,5-heptamethyltrisiloxane(MDHM) and 1,6-hexamethylene diurethane in the presence of Pt catalyst. The chemical structure of GPETS was confirmed by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. The interfacial properties of GPETS were studied. GPETS can reduce the surface tension of water to approximately 22.0 mN?m-1 at the concentration of 5.9?0-5mol?L-1. The hydrolytic stability of GPETS was compared to polyoxyethylene ether trisiloxane surfactant in different pH value. The result showed that the hydrolytic stability of cationic polyether trisiloxane surfactant is better than the latter, suitable for use in the wide range of pH value.
LIU Shan-he , GU Shun-ming , YANG Hong-bing , WEI Yong-fei , WANG Wei-cheng , WANG Peng-fei , FENG Yi-si
2014, 31(9).
Abstract:4-dimethylaminopyridine (abbreviation DMAP) is a widely used catalyst in a variety of organic reactions, so it is called super-catalyst. In this article, we designed and researched a new synthesis route by Using 4-cyanopyridine and styrene as raw materials. The optimum conditiongs were given n(4-cyanopyridine)/ n(styrene)= 1:1.2, and w (40 %) sodium hydroxide solution was added to decompose the intermediate under reflux for 2h. The yield of the product reached 73.8% and styrene could be recovered. The structure of target compound was confirmed by IR, HNMR..
2014, 31(9).
Abstract:Titanium dioxide (TiO2) inorganic particles were surface modified by using silane coupling agent KH-570 to improve its dispersion in organic systems. The superhydrophobicity of surface modified TiO2 was characterized using FT-IR, contact angle, sedimentation tests, and SEM. And the form mechanism of the superhydrophobicity surface was also analyzed. The results showed that the hydrophobicity and dispersibility of the surface modified TiO2 particles with KH-570 were significantly improved, the surface modified TiO2 coating with KH-570 15 wt % showed good superhydrophobicity that the water static contact angle reached 152.5°.
SONG Zi-fan , WEI Jun , FU Cao-fei , LI Xiang , CHANG Zhen-qi
2014, 31(9).
Abstract:An assembly-disassembly capillary-based microfluidic system was demonstrated for fabricating highly monodisperse (CV = 3.78%) poly(styrene-co-divinylbenzene-co-TPGDA) porous microspheres. The size of as-prepared ploy(SDB-TPGDA) microspheres can be precisely controlled in the size range of 250~1550 μm by manipulating flow rates radio of continuous phase to dispersed phase and continuous phase viscosity. Polymer microspheres with good sphericity (Max.D./Min.D. < 1.05)were fast prepared by photopolymerization. The rate of photopolymerization increased rapidly with the increases of the TPGDA content of the mixed monomer. This study provided an effective approach to the synthesis of monodisperse polystyrene-base porous microspheres with large particle size.
2014, 31(9).
Abstract:In this study the potential use of ionic liquid-based aqueous two phase system (ILATPS) for the extraction of ursolic acid from Cynomorium songaricum Rupr was evaluated and optimized. The effects of independent variables(the mass fraction of [Bmim]Cl and KH2PO4, mass fraction of crude extract, mass fraction of NaCl and pH)were evaluated by single factor analysis. The optimization ATPS of 25%[Bmim]Cl-21%KH2PO4were selected based on their higher upper phase partitioning coefficient and the recovery .Using the optimized ILATPS solvent, the Box-Benhnken Design results showed mass crude extract 8.5%,NaCl 1%, pH4.7 were the optimal ILATPS extraction conditions. Maximum yield of extracted ursolic acid from the experiments was determined to be 97.85% under the optimal conditions, which was in good agreement with the predicted one of 98.3%. In conclusion, the optimized process has good reliability.
2014, 31(9).
Abstract:Phosphotungstic acids with Dawson structure(H6P2W18O62) supported on SiO2 were prepared by sol-gel method. The properties of the catalyst were characterized by TGA, FT-IR, SEM and XRD. The results showed that H6P2W18O62 had been well dispersed into the SiO2 support, and the immobilized catalyst exhibited high catalytic activity in the Biginelli reaction for the synthesis of 4-phenyl-6-methyl-5-ethoxycarbonyl-3,4-dihydropyrimidin-2(H)-ketone. The optimized conditions were as follows: fixing benzaldehyde consumption is 0.04 mol, n(benzaldehyde): n(ethylacetoacetate):n(urea)= 1: 1.5: 1.5, the mass ratio of the catalyst to total reactant was 2.0%, the reaction temperature was 80℃, and the reaction time was 75min. The yield of the product could reach 82.3% under the optimum conditions. It also maintained satisfactory catalytic activity for the synthesis of Biginelli compound after 10 rounds of recycling, and the yield was still above 57.2%.
2014, 31(9).
Abstract:In order to find more activity antitumor PI3K inhibitors, pyrimidine-2,4-diol as raw material, after chlorinated by POCl3, coupled with morpholine, then lodine generation, followed with Sonogashira coupling and remove the trimethylsilyl to get the triazolyl intermediate, finally, Suzuki coupling to get 2-aryl-4-morpholino-6-triazolylpyrimidine 14~27, their structures were confirmed by 1H NMR and LC-MS. The in vitro anti-proliferative activity assay against A2780 has been cacacarried out by MTT detection method, the result showed that under the test concentration of 10 μmol L-1, the compounds 14 and 25 were more potent than clinical candidates GDC-0941 and BEZ-235, inhibition rate reached 76.7%, 77.2% respectively. Furthermore, the result of pharmacokinetic study suggested that compounds 25 was desirable.t1/2=3.2 h, AUC0-∞ was 34193 ng•h•mL-1.
2014, 31(9):0-0.
Abstract:The article is about the researches of the mechanical properties, optical property and their influencing factors of rapeseed proteins-agar blend films. The results show that the mechanical properties are significantly influenced by the rapeseed proteins/agar ratio, pH and the content of glycerol but the temperature and ultraviolet ray have little influence. After the blend processing, the mechanical properties of the films improved by 6-10 times compared with the proteins films, illustrate that the blend method is a effective means to improve the properties of the films.
2014, 31(9):0-0.
Abstract:The polyurethane modified fluorinated polyacrylate (PUAF) is obtained with 2-(perfluorohexy) Ethyl Acrylate(C6F) and hydroxypropyl acrylate as polymerization monomers, azobisisobutyronitrile as a radical polymerization initiator, in the polyurethane prepolymer. The structure, film morphology and application performance of PUAF were studied by infrared spectroscopy, nuclear magnetic resonance spectroscopy (1H-NMR) and field spectrum scanning electron microscopy (FE-SEM), etc. PUAF can form dense membrane which is hydrophobic on the surface of fiber.The dried fabric samples was submerged for one time into 1%solution of PUAF in ethyl acetate ,then dried at 180℃during 1.5min.The water contact angle of fabric is133.5 ?
2014, 31(9).
Abstract:The multifunctional light stabilizer were synthesized through joining the 2,4-dihydroxy-benzophenone (a ultraviolet absorber), triazine - stilbene fluorescent brighteners and the series of polyethylene glycol (PEG) in the same molecule with cyanuric chloride as the crosslinking monomer. The molecular structures were characterized by IR spectra and 1H NMR, the physical properties were examined by UV spectra and photoluminescence (PL) spectra, the application effect of the light stabilizer in paper sheet were tested. The results showed that the active ingredient of triazine - stilbene fluorescent brighteners (VBL)was 28.86 %, while the active ingredient of the multifunctional light stabilizer (FBs-400) was 61.8 % after illumination. The fluorescence was quenched when the concentration of the light stabilizer was over 1g / L, its usage can be enlarged than VBL (1×10-5 kg / L). The brightening effect and light stability of the multifunctional light stabilizer are nice in the performance of application. At the same time, its light stability are improved obviously.
2014, 31(9).
Abstract:A polymer microsphere was prepared using stable crosslinker typeⅠ(MBA) and typeⅡ(PEGDA) labile crosslinker composite,typeⅡcross-linking agent has a decomposition temperature of 60-65℃ tested by bulk polymerization and the microspheres were prepared by inverse emulsion polymerization. The impacts of type Ⅱcrosslinkers to microsphere size and expansion properties were investigated using particle size analyzer,We also observed microspheres morphology before and after hydration combined with Scanning Electron microscope (SEM) . The results showed that the right amount of typeⅡcrosslinkers and MBA can reduce the primary particle diameter; microspheres were approximately spherical shape before and after hydration and the primary particle size was about 3μm,reunite effect was observed between particles after expansion;Unstable cross-linked microspheres had wide size distribution and swelled hardly at room temperature and the failure of type Ⅱ crosslinker resulted microspheres swelled faster after 60℃,Microspheres median diameter (D0.5) ranged from 13.94μm to 70.71μm at 19.5×104mg/L salt solution within 18h.
2014, 31(9).
Abstract:In order to investigate a fast preparation method of modified nanocellulose, the polyelectrolyte brush type cellulose nanowhiskers (CNW) were prepared by surface grafting with low molecular weight poly (acrylic acid) (PAA) using the UV photo-radiation method. The grafted products (CNW-g-PAA) were characterized by FTIR, 13C NMR, TEM, XRD, DSC etc. The effects of the grafting polymerization conditions, such as the monomer content, the photo-initiator amount, the graft time, which influenced the carboxyl content of the grafted products, were investigated in details. The optimum grafting condition was that the mass ratio of PAA and CNW was 1:1, the mass ratio of the photo-initiator and CNW contents ranged from 8‰ to 10‰, the graft time was 90 seconds, respectively. The optimum highest grafting ratio of carboxyl groups was about 0.01275 mol/g. This UV-grafting method utilized less chemical reagents, less synthesis steps and shorter reaction time. The synthesized CNW-g-PAA would have a lot of applications.
2014, 31(9):0-0.
Abstract:mono-trimethylolpropane trimaleates(TMPTM) and methacrylic acid(MAA) were employed to produce linear-hyperbranched block copolymers. Reactivity ratios of monomers indicated block copolymerization occured between TMPTM and MAA and produced linear-hyperbranched block copolymers, the indication was then confirmed by NMR, law of lg[η]-lgMw and branching factor g’. Furthermore, DSC revealed the Tg of LHBP is 209.98℃, TGA showed two-stage degradation occurred during heating-up from 50℃ to 600℃,first stage at 206.38℃(decarboxylization) and second at 429.57℃(backbone degradation).
2014, 31(9).
Abstract:A quinoline imidazole boron fluoride dye was synthesized through four -step reactions, starting from methylquinoline. The structure of the compound was characterized by the 1H NMR, 13C NMR, MS. Its ultraviolet and fluorescence properties had been studied in different solvents, different concentrations and solid film. The results showed that stokes shift of the dye in polar solvent(methanol) was 134 nm, the fluorescence quantum yield was 0.1; stokes shift in nonpolar solvent (hexane) of the dye was 66 nm, the fluorescence quantum yield was 0.468.
2014, 31(9).
Abstract:The type and dosage of dispersant, resin and wetting agent directly affect the dispersion and stability of pigment particles and the construction of thixotropic system in pigment gel ink system. The rheological behavior of pigment slurry with different amount of dispersant BYK–191, and gel ink with different quantities of styrene acrylic resin M101 and wetting agent 4187 was investigated. The particle size of pigment, microscopic imaging, CMC (critical micelle concentration) were studied by laser particle analyzer, optical microscope and surface tensiometer. Besides, it was the first time to use rheometer to optimize the gel ink formula. It turned out that not only a well thixotropic system of gel ink but also the ultra-fine dispersion and long-term stability of pigment could be realized when the adding quantity(mass fraction)of dispersant BYK–191, styrene acrylic resin M101 and wetting agent 4187 reached 2.0%, 4.0% and 2.5%, respectively.
ZHANG Tian-yong , LI Wei , LI Bin , JIANG Shuang , LV Dong-jun , FEI Xue-ning
2014, 31(9).
Abstract:The synthesis of the C.I. Pigment Red 177(PR177) was developed by the desulfonation of 4,4'-diamino-1,1'-dianthraquinonyl-3,3'-disulfonic acids(DAS) in ionic liquids ([BSMIm]HSO4, [BSMIm]OTF) instead of H2SO4. The influences of the acidity, dosage and recycle of ionic liquids, reaction time, reaction temperature on the yield of PR177 were studied. The acidity of ionic liquids satisfied the acidity requirement of desulfonation of the DAS. The recycle of ionic liquids was convenient, and it reduced the discharge of wastewater. The synthesis technology was environmentally friendly. The optimal reaction conditions were as follows: The dosage of DAS and [BSMIm]OTF were 2.0g and 10g separately, the reaction temperature was 150℃, the reaction time was 5h, the number of recycle of ionic liquids after dichloromethane extraction was 6, the average yield of PR177 was 92.3%.
DAI Yu-sen , WANG Zi-jian , SUN Xiao-yang , DU Hong-guang
2014, 31(9).
Abstract:2-Amino-6-chloropurine as the starting material was treated with 2-bromoethyl acetate to product 9-acetoxyethyl-2-amino-6-chloropurine (Ⅰ, 65.6% yield). Compound Ⅰwas diazotized and reacted with disulfides to afford 9-acetoxyethyl-2-alkythio-6-chloropurine (Ⅱ, 58.3-72.1% yield). NaN3 was reacted with Ⅱto acquire 9-acetoxyethyl-2-alkythio-6-triazo purine (Ⅲ, 86.4-92.0% yield). The result of NMR test (Ⅲ)showed that there were azido tautomer(A)and tetrazolyl tautomer(T) in the solution, and the ratio of azido tautomer was 61.5-67.2%. We use PPh3-HCl-DMSO as the reaction solvent to reduced trizao to amino and hydrolyzed the ester completely to afford the 2-alkylthio-6-amino-9- (2-hydroxylethyl)purines (Ⅳ) in the good yield(~90%) in one pot. All the compounds synthesized were comfirmed through IR, 1H NMR, 13C NMR, and HRMS.
2014, 31(9).
Abstract:Zinc salts are active catalysts for the reation of urea and 1,2-propylene glycol, especially zinc perchlorate hexahydrat which shows very excellent catalytic activity.The effects of reaction time,dosage of catalyst and reaction temperature on the synthesis are investigated.The optimized reaction conditions are shown as follows: 4 of molar ratio of 1, 2-propanediol to urea, 3 h of reaction time, 1.5% of catalyst mass fraction ( based on all reaction materials) and170℃ of reaction temperature. Under the optimal reaction condition,the yield of propylene carbonate can reach over 94.2% . Electron withdrawing ability of perchlorate ion might be the key factors that influenced the catalytic activities.
2014, 31(9):0-0.
Abstract:(R)-3-chloro-1-phenyl-1-propanol was enantioselectively synthesized with 3-chloropropiophenone as raw material and spiroborate ester as catalyst. The influence of solvent on catalyst activity and the effects of catalyst dosage, borane dosage and reaction temperature on the purity and optical purity of (R)-3-chloro-1-phenyl-1-propanol were investigated, respectively. With chiral spiroborate ester prepared in ethyl acetate solvent as catalyst, when n(3-chloropropiophenone):n(spiroborate ester):n(borane)=1:0.1:0.6, and temperature 5~10℃, the product purity and optical purity of (R)-3-chloro-1-phenyl-1-propanol reached 99.5% and 96.3% e.e., respectively.