• Volume 27,Issue 12,2010 Table of Contents
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    • >Review and monographs
    • Research progress in the biocidal performance and mechanism of quaternary ammonium salt biocide

      2010, 27(12).

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      Abstract:Quaternary ammonium salt (QAS) biocide and the researches of its biocidal performance and mechanism were reviewed. Based on the development course of existing QAS seven generations products, they were classified into four types biocides, i.e. single-chain QAS, double-chain QAS, polymer QAS and mixed QAS, according to the structural characteristics. The biocidal performance and mechanism of QAS biocide were described by combining the structural characteristics of four types biocides and using bacterial and algae as the action objects. Six basic steps of biocidal process and four basic modes of biocidal action were concluded. Based on the statements above, it was especially emphasized that study on the key action site and lethal action mode of QAS molecule on its action object was the main points of mechanism research. Aiming at concentration of a concrete action object, the researches of obtaining the relationship between the concentration and action time of biocide were the important foundation of application. Finally, some research suggestions of the biocidal performance and mechanism of QAS biocide were put forward.

    • >Functional materials
    • The Preparation and Characterization of Waterborne Polyurethane/Colloidal Silica Hybrid coatings

      2010, 27(12).

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      Abstract:Hybrid emulsions containing inorganic nano particles were prepared by blending waterborne polyurethane (WPU) emulsions with colloidal silica. The hybrid emulsion and its film were characterized by TEM, laser particle analyzer, rheometer, ATR-FTIR, and TG respectively. The effects of silica content on the properties of the film were studied. The ATR-FTIR test results confirm that there is no chemical bond formation between silica particle and urethane polymer chains but hydrogen bonding. TEM and laser particle analyzer examinations showed that the average particle size of the hybrid emulsions increases and particle size distribution become wider with the increasing content of colloidal silica, the aggregation of silica particle in the hybrid emulsion would happen in the case of SiO2wt%>20%. The rheological analysis reveals that the apparent viscosity ( ) and pseudoplasticity of the hybrids are increased with increasing silica content. The property tests indicated that at about 20% silica content, the stability of the hybrid emulsion is good, its films show much better thermal stability, its water absorption was only 18. 94%(after 48h) also with higher performance in solvent resistance, tensile strength increases to 28.98MPa, pencil hardness is 2H,adhesion is 0 grade.

    • Synthesis of Diarylthiourea(DATU)/CdS Composite Nanoshperes and Effects of Groups on Benzene

      2010, 27(12).

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      Abstract:N,N′-diarylthiourea(DATU)/CdS with groups of 4-(H,Me,MeO,Cl and COOH) and 3-NO2 on benzene, the organic-inorganic nanocomposites, were successfully synthesized by reacting CS2 with aryl amines and CdCl2 at 50℃ in water and triethanolamine(TEA)(Vwater:VTEA=1:1). The products were characterized by XRD, FT-IR, SEM, TG, UV–vis and PL. The results reveal the formation of the organic-inorganic nanocomposites in good disperse nanospheres. The electron-withdrawing groups on benzene effectively prevent the aggregation of DATU/CdS particles, thus resulting in good disperse spheres. Furthermore, bigger blue shift of CdS UV-Vis is also caused by electron-withdrawing groups. The strong interaction between DATU and CdS results in higher thermostability of DATU in nanocomposites and increasing intensity at 529nm PL emission peak.

    • Synthesis and properties of Superabsorbent resin of Binary Copolymer by Microwave

      2010, 27(12).

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      Abstract:Poly(2-acrylamido-2-methylpropa-nesulfonic acid/acrylamide) superabsorbent resin was synthesized by microwave irradiation and charactered by means of FTIR.The impact factors of synthesizing superabsorbent resin, such as the ratio of monomer, the amount of crosslinker ,the amount of initiator , neutralization degree ,reaction time and microwave power, on absorption properties of liquid absorbency rate were discussed. Meanwhile, water absorption rate of resin was studied,the results showed that the water absorption rate of resin was 1495g/g in distilled water and 93g/g in normal saline respectively when the optimum conditions. However ,the absorbency was decreased sharply with increasing of salt concentration in solution,and with radius decreasing of anion copuled with potassium ion when the same concentration of salts in solution.Moreover, the water absorption rate had something to do with valence of cation for the electrolyte solution,the higher of the valence, the lower of the water absorption rate .

    • Study on preparation and performance of sulfonic/carboxylic waterborne polyurethane

      2010, 27(12).

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      Abstract:Waterborne polyurethane emulsions with sulfonic group were synthesized by a prepolymer process using dimethylol propionic acid (DMPA) and self-prepared sulfonic hydrophilic monomer (namely 1 2-dihydroxy-3-propanesulfonic acid salt DHPA). The structure of the films was confirmed by means of FTIR. The test results indicated that the DHPA has been synthesized and introduced into the chain of polyurethane. The results indicated that the average particles diameter of polyurethane emulsions became smaller and particles distribution width became narrower, with the increase of the weight of DHPA. TEM photos show that PU emulsions were well-dispersed with neat appearance. The viscosity of emulsions decreased, with the increase of shear rate, showing pseudo-plastic characteristics.

    • Study on synthesis and coating properties of fumaropimaric acid epoxy resin

      2010, 27(12).

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      Abstract:Fumaropimaric acid was synthesized via D-A reaction of rosin acid and fumaric acid, and was characterized by 13CNMR spectroscopy, electrospray mass spectrometry and infrared spectrum. Then through esterification between FPA and 1,4-butanediol diglycidylether (or 1,6-hexanediol diglycidylether), epoxy prepolymer was prepared. The prepolymer and hardner were blended at different ratio and the coating properties of the cured resins were tested. When the molar ratio of activated hydrogen and epoxy group (n activated hydrogen /n epoxy group) was 1.0 or 1.2, the coating with good properties can be obtained. The experimental results were shown as follows: hardness, more than HB; adhesion testing, less than 2; T-Bend, less than 2T; impact resistance, more than 9.8J; chemical resistance, passed.

    • >Surfactants
    • Strengthen Amination of α-Chlorododecanoic Acid with Trimethylamine in Hydrothermol System by means of Kinetic Control

      2010, 27(12).

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      Abstract:α-Capric betaine(α-CB), a new type of zwitterionic surfactant was synthesized by amination of α-chlorododecanoic acid(α-CDA) with trimethylamine(TMA) under hydrothermal condition, and the bothering was that the yield of α-CB was lower caused by the side effect of hydrolysis. Based on the optimal factors such as solvent, feed ratio, etc, the temperature program, a means of kinetic control, was applied to effectively inhibit hydrolysis and thus the yield of α-CB was markedly improved. When kept n(trimethylamine) / n(α-CDA) = 3, 1% of KI as catalyst and 0.5% of α-CB as solubilizer added in advance, the amination proceeded at 70 ℃ for 8 h followed 100 ℃ for 2 h, the yield of α-CB was improved from 62.4% to 92%.

    • Synthesis and Micellization of a novel bolaamphiphile derived from tyrosine

      2010, 27(12).

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      Abstract:l,12-tyrosine diaminododecane(DADT) was synthesized by L-Tyrosine and 1,12-dodecanediamine and the structure of DADT was characterized by 1H NMR. The self-aggregation behavior of DADT in water was determined by conductivity, isothermal titration calorimetry and fluorescence spectroscopy. The critical micelle concentration (cmc) of DADT is ca.0.16 mmol/L. The cmc value displays a weak trend of increase along with the increase of temperature and it decreases remarkably with the ionic strength increase. Meanwhile, the fluorescence intensity increases with the concentration of DADT when its concentration is lower than 0.18 mmol/L. When its concentration reaches 0.18 mmol/L , DADT monomers can self-aggregate into micelles so that the fluorescence intensity decreases accordingly. Meanwhile, it is found that the concentration of self-quenching of DADT is consistent with its critical micelle concentration which provides a convenient way for the study of the micellization behavior of bolaamphiphiles.

    • >Catalysis,separation and purification technology
    • Study on extraction of collagen by enzyme-acid method from the cattleskin

      2010, 27(12).

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      Abstract:The collagen from cattle skin has been extracted by using the pepsin, the composition of cattle skin was also analyzed. Effects of enzyme addition, temperature and extract time as well as solid-liquor ratio on extraction efficiency of collagen were investigated in this paper.The optimal processing conditions were obtained by orthogonal experiments as follows: 0.5 mol/L acetic acid as extraction solvent, the added pepsin dosage of 3000 U/g and the ratio of material to liquor 1:30, extraction at 35℃ for 8 h, the recovery yield of the collagens was 61.7%. The maximum absorb wavelength of sample is 232nm by UV scan, which is consistent with the Sigma product.

    • Microwave assisted extraction technology and radical scavenging activity of total flavonoids from the nutlets of Clausena anisum-olens

      2010, 27(12).

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      Abstract:The paper studied the extracting of flavonoids in the nutlets of Clausena anisum-olens with Microwave assisted extraction (MAE). The single factor and orthogonal designmethods L9(34) were applied for the optimal technologicalconditions:70 ◦C,(EtOH)=60 %,m(the nutlets of Clausena anisum-olens):m(EtOH)=1:16,440 W,10 min. Under the optimized conditions, the extraction percent of total flavonoids is about 1.340 % from the nutlets of Clausena anisum-olens.There was a positive correlation between hydroxyl radical scavenging activity and concentration of total flavonoids from the nutlets of Clausena anisum-olens.Observed at five experimental levels, and the hydroxyl radical scavenging rates at the concentration level of 0.442 g/L were 81.4 %.

    • Preparation, Characterization and Catalytic Performance of HPW/Al2O3 for THF polymerization

      2010, 27(12).

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      Abstract:A series of HPW/Al2O3 solid acid catalyst with loading from 10% to 70% was synthesized. These catalysts were characterized by N2 adsorption-desorption, XRD, NH3-TPD, FT-IR spectroscopy and Py-IR spectroscopy. The above studies indicated that HPW kept its Keggin type structure in the loading range of 50%~70% .The catalysts had strong Brönsted acid and their total acidity increased with the laoding of HPW. The catalytic activity of these catalysts were evaluated by carrying out polymerization of tetrahydrofuran (THF).The results indicated that higher acidic catalyst led to the higher yield of PTMEG, yet the lower average molecular of PTMEG.

    • >Drug and cosmetic materials
    • The New Process Research of Hydroxytyrosol Synthesis

      2010, 27(12).

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      Abstract:The new process of hydroxytyrosol synthesis had been discovered, which starts from catechol protection, followed by 3-bromation to give 1-Bromo-3,4-(methylenedioxy)benzene, then preparation of Grignard reagent and reaction with ethylene oxide and, finally, deprotection. Hydroxytyrosol was obtained by five-step reaction with high purity in the overall yield of 24%. The title compound was characterized with IR and MS.

    • Preparation and Quality Evaluation of Compound Diclazuril Nanoemulsion

      2010, 27(12).

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      Abstract:Compound diclazuril nanoemulsion was prepared and its quality was evaluated. The preparation of compound diclazuril nanoemulsion was optimized by studying the pseudoternary phase diagrams. Compound diclazuril nanoemulsion was prepared, its shape and particle size distribution were detected by TEM and Nicom p388/Zeta PALS Particle Sizing System and its stability was verified by high speed centrifuge test and long term storage test. The optimum preparation was w(diclazuril)=5%, w(Vitamin K3)=10%, w(Tween-80)=30%, w(ethanol)=5%, w(ethyl acetate)=3.9%, w(Dimethylformamide)=2.5%, w(distilled water)=43.6%. The shape of compound diclazuril nanoemulsion was spherical, with mean diameter of 14.0 nm and polydispersity index was 0.064. The high speed centrifuge test and long term storage test showed that it was still clear, lucent and uniform. The preparation procedure of compound diclazuril nanoemulsion is simple and the stability is good. It is expected to be applicable to the veterinarian clinic.

    • Synthesis and Characterization of 7-Hydroxyl-4’-(β-D-glucopyranosyloxy)puerarin Derivatives

      2010, 27(12).

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      Abstract:Glucose via acylation and bromization pathway gave acetobromo-α-D-glucose. The etherification of puerarin to 7-Hydroxyl-4′-(2,3,4,6-tetraacetyl- β-D-glucopyranosyloxy) puerarin with acetobromo-α-D-glucose was carried out in acetone in the presence of potassium carbonate. The isolated yield was 61.4% (based on puerarin). Finally, 7-hydroxyl-4′-(β-D- glucopyranosyloxy)puerarin was obtained via deacetylation in anhydrous methanol in the presence of potassium carbonate with isolated yield of 90.5%. Structures of intermediates and final product were characterized by 1H NMR spectra and MS. Compared to puerarin, the water-soluble of 7-hydroxyl-4′-(β-D-glucopyranosyloxy) puerarin was increased by 15.3 times.

    • Synthesis of Nitazoxanide by an One-step Process

      2010, 27(12).

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      Abstract:A newtype drug-nitazoxanide (2-Acetyloxy-N-(5-nitro-2-thiazolyl)benzamide) was synthesized through amidation from acetylsalicylic acid and 2-Amino-5-nitrothiazole in the presence of P2O5 as dehydrant. The effects of the amount of acetylsalicylic acid, 2-Amino-5-nitrothiazole and P2O5, the temperature and time of amidation on the yield were investigated. The optimal conditions were as follows: n (acetylsalicylic acid): n (2-Amino-5-nitrothiazole): n (P2O5): 1.2: 1.0: 2.5, in DMF at 90℃ for 2.0h, the yield can be higher than 75%.

    • Green synthesis of L-citrulline and L-homocitrulline

      2010, 27(12).

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      Abstract:An novel method for synthesis of L-citrulline and L-homocitrulline was reported. In this process, L-ornithine monohydrochloride was reacted with copper Sulfate pentahydrate to protect α-NH2, and δ-NH2 was carbamylated with carbamide, then copper ion was removed through combination with oxalate dihydrate to give L-citrulline with an overall yield of 49.5 %. L-homocitrulline was prepared from L-lysine monohydrochloride in the same method with an overall yield of 53.5%. The structure of aimed compound was confirmed by IR, melting point and optical rotation. This synthetic route was convenient, safe, economical, and environmental friendly.

    • A Convenient Method for the Synthesis of 13C labelled Glycocholic acid

      2010, 27(12).

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      Abstract:With isobutyl chloroformate as active agent, Glycocholic acid-glycyl-1-13C, a 13C-breath test substrate and applications in clinical practice, was synthesized by one pot method of condensation of glycine-1-13C directly with cholic acid. 13C labelled Glycocholic acid was characterized by HPLC, LC-MS and 1HNMR. The yield of 13C labelled glycocholic acid was 80.3% (based on glycine-1-13C), with 99.1% atom13C abundance, 99.2% optical purity and 97.7% chemical purity, at optimized conditions, which were n(isobutyl chloroformate) : n(cholic acid) : n(glycine) : n(triethylamine)=1 : 1 : 1 : 1, 10 oC reaction temperature and 1 h reaction time.

    • >Starch chemicals
    • Methylation of starch by dimethyl carbonate under the activation of inorganic salt

      2010, 27(12).

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      Abstract:Inorganic salts, like ammonium chloride(NH4Cl) and sodium chloride(NaCl), was used to intensify activation of starch, and further to improve methylation of starch with dimethyl carbonate by the help of tetrabutyl ammonium bromide (TBAB).It is showed that the methoxyl content of methyl starch gets to 5.9%, by mass ratio m (starch): m (NH4Cl): m (NaCl): m (K2CO3): m (TBAB)=10:5:5:10:1 and volume ratio v(C2H5OH):v(H2O):v(( H3CO)2CO)=30:10:150, at 55℃ for 1h activation , and 80℃ for 12h reaction.

    • >Papermaking chemicals
    • Synthesis and Application of Nanoparticles Core/Shell Styrene-acrylic copolymer latexes

      2010, 27(12).

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      Abstract:Styrene (St) as hard monomer, butyl acrylate (BA)as soft monomer, N-Methylolacrylamide (N-MAM) as functional monomer, styrene/acrylic latexes was synthesized by semicontinuous emulsion polymerization. The performances of emulsion and impregnated auto-industry filter paper were examined and analyzed. The optimal condition of synthesizing emulsion was gained as that the best monomer compound of ST: BA was 0.49, the emulsifier’s dosage was 0.93%, the initiator’s dosage was 0.63%, the N-MAM’s dosage was 5.3%.The latex’s average particle diameter was 50nm and distributed equally. The performance indexes of impregnated filter paper were greater than 350kPa of bursting strength, more than 99min of water resistant property, over than 520L?m-2?s-1 of air permeability and at least 4.03 mN.m stiffness.

    • >Oil field chemicals and petroleum additives
    • The Effects of Extreme Pressure-antiwear Additives on Tribological Properties of Polyurea Grease

      2010, 27(12).

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      Abstract:Put three kinds of extreme pressure-antiwear additives(T204,T304andA88) into the same polyurea grease, the effects of three additives on tribological properties of polyurea grease have been studied respectively in this paper. The results showed that T204 could only improve significantly load-carrying capability, when the additive content of T204 was 1%, its load- carrying capability was greatly improved from 400N of base grease to 900N improved by 125%. When the additive concent of T304 was 0.5%, the wear volume of polyurea grease was reduced by 52% and its load- carrying capability was improved by 125%. When the additive concent of A88 was 1%, the wear volume of polyurea grease was reduced by 58% and its load- carrying capability was improved by 75%.

    • >Building chemicals
    • Influence of Molecular Weight of Sulfonated Acetone–Formaldehyde Polycondensate on Its Dispersing Performance

      2010, 27(12).

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      Abstract:Sulfonated acetone–formaldehyde polycondensate(SAF) was fractioned by ultrafitration into four fractions with molecular weight range of <2500、2500~10000、10000~50000 and >50000. Structural analysis showed the weight-average molecular weight and intrinsic viscosity of the four fractions successively increased while their sulfonation degree decreased. Meanwhile, properties of SAF with different molecular weight as water reducer of cement were studied. Results showed with the increasing of molecular weight of SAF, the water-reducing ratio of cement paste containing SAF increased remarkably, but the paste tended to lose fluidity easier with time-lapse. And the retardation effect of SAF decreased because the content of sulfonic groups and hydroxyl reduced and the complexation of these two groups to calcium ion was weakened. The 7d and 28d compressive strenght of harden mortar added fracioned SAF were enhanced by 30%~60% in contrast with the reference and the strenght increased as molecular weight of SAF increased. The two fractions of higher molecular weight had dosage and water-amount sensitivity ,and when their dosage was above 0.3%, mortar became bleeding. It thus decreased the compressive strenght.

    • >Fine chemical intermediates
    • Study on influencing factors of synthesis process of epoxy hexanoate catalyzed with acetylacetone chromium (щ) and its rinetic analysis

      2010, 27(12).

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      Abstract:The addition-esterification of epoxy resin and caproic acid catalyzed by acetylacetonate chromium (щ) was studied. The effects of temperature and the catalyst concentration on the reaction were investigated, and the catalytic ability was examined by comparing with tertiary amine and quaternary ammonium salt. And the reaction product was characterized by FT-IR and 1HNMR. The result showed that acetylacetonate chromium (щ) was a high-efficiency catalyst, with 0.4% of which the conversion of caproic acid could achieve 86.2% at 120℃. The reaction between epoxy resin and caproic acid was a second-order reaction, and the apparent activation energy (Ea) of the reaction was 142.668kJ/mol by kinetic calculations of the experimental data according to the integrated reaction rate equation.

    • Catalytic Hydrogenation of Dimethyl Terephthalate to Dimethyl 1,4-cyclohexanedicarboxylate over Modified Skeletal Nickel

      2010, 27(12).

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      Abstract:The modified skeletal Ni catalyst was prepared by quenching technique, and it was employed for the catalytic hydrogenation of dimethyl terephthalate(DMT) to Dimethyl 1,4-cyclohexanedicarboxylate (DMCD). Effects of solvent, reaction temperature, pressure, initial concentration of DMT and amount of catalyst have been investigated. Under optimal reaction conditions: c(DMT) =1.0 mol/L, m(DMT): m(catalyst) = 4:1, 95 ℃, 6.0 MPa pressure, the selectivity of DMCD was up to 92.3% in 140 min with 100% conversion of DMT in isopropanol solvent. After QS-Ni catalyst was recycled for 16 times, conversion of DMT and selectivity to DMCD still remain at 99.3% and 92.0%, respectively.