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    24 November 1993, Volume 14 Issue 11
    Articles
    Synthesis of Copper(Ⅱ) Phthalocyanine Derivatives and Their LB Films
    ZHANG Yin, CHEN Wen-Qi, SHEN Qi
    1993, 14(11):  1483-1486. 
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    In this paper, copper (Ⅱ)-tetra-4-(8-quinoloxy) phthalocyanine (A), 4-(8-quinolyoxy)tris-4-(2,4-di-t-pentyl phenoxy)phthalocyanine(B), tetra-4-(β-naphthoxy)phthalo-cyanine(C); 4-(β-naphthoxy)tris-4-(2, 4-di-t-pentyl phenoxy)phthalocyanine(D), tetrakis-4-[4'-4''-benzyloxy phenyl sulfonyl) phenoxy]phthalocyanine(E) and 4-[4'-4''-benzyloxy phenyl sulfonyl) phenoxy]-tris-4-(2, 4-di-t-penoxy)phthalocyanine(F), were synthesized and characterized by elemental analysis, IR, ESR, MSand 1H NMR.UV-Vis spectra indicate that most of them are monomeric molecules in CHCl3 solution.Surface pressure(π-area (A) isotherms for the six kinds of compounds in CHCl3 solution in subphase (water) at 25℃ showed the existence of the obvious changes in the states of “gas", “liquid" and “solid" phases and six kinds of compounds could form monomolecular layer film.
    Synthesis, Properties and Crystal Structures of RE(CCl3COO)3(phen)2 · nH2O Complexes
    CHENG Yi-Xiang, LU Wei-Min, DONG Nan, CHEN Cheng-Gang
    1993, 14(11):  1487-1491. 
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    The complexes of lanthanides(Nd, Sm, Eu) trichloroacetate(CCl3COO)3 with two 1,10-phenanthroline were synthesized in the mixed solvent of water and alcohol.The crystal structures of the two complexes Nd(CCl3COO)3 (phen)2 and Eu (CCl3COO)3 (phen)2· 2H2Ohave been determined by four-circle X-ray diffractometer.The Nd(CCl2COO)3(phen)2 belongs to triclinic system with space group P1.The coordination number of Nd is 10.The crystal Eu(CCl3COO)3(phen)2 · 2H2Obelongs to monoclinic system with space group P21/c.The coordination number of Eu is 8.
    Studies on the Synthesis and Intramolecular Energy Transfer of the Ruthenium(Ⅱ)-Ferrocene(Ⅱ) Polynuclear Complexes
    DUAN Chun-Ying, YOU Xiao-Zeng, TAO Hui, ZHU Long-Gen
    1993, 14(11):  1492-1497. 
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    Akind of polynuclear ruthenium-ferrocene complexes [Fc-C(R)=N-(C6H4)n-N=C(C10H6N2)]m[Ru(bpy)3-m][(PF6)2] (R=H,CH3, n=0,1,2 and m=0,1,2) have been synthesized and characterized.The luminescence of the chromophore Ru(Ⅱ) is quenched by the luminophore Fe(Ⅱ), and efficient intramolecular energy transfer from the chromophore Ru(Ⅱ) to the luminophore Fe(Ⅱ) occurs in these bimetallic complexes.The efficience of the intramolecular energy transfer is related to the number of the luminophore Fe(Ⅱ) around the chromophore Ru(Ⅱ) and the distance between the Ru(Ⅱ) and Fe(Ⅱ) in the bimetallic complexes.
    A New Approach to Investigation of Polymerization of Silicic Acid
    AN Yong-Lin, LI Shou-Gui, XU Ru-Ren, TANG Ao-Qing
    1993, 14(11):  1498-1501. 
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    In this paper, a new approach to the study of polymerization of silicic acid in aqueous solution is described in terms of the statistical theory of polymeric reaction involving intramolecular cyclization.Trimethylsilylation-gas chromatography technique is applied to the characterization of the polymeric reaction.The number fraction distributions of polymeric molecules are obtained in various polymeric systems with [SiO2]=0.05-0.5 mol/L, pH=1-3.The experimental results show that the polymeric behavior of silicic acid at the early stage of polymerization is in agreement with that predicted by the statistical theory for A4 type crosslinking reaction involving intramolecular cyclization, and intramolecular cyclization is the characteristics of the polymeric reaction.
    Investigation on the Theory of Quasi-Steady-State Reversible Wave in Linear Sweep, Derivative and Semi-Differential Voltammetry at Ultramicroband Electrode
    WU Zhi-Bin, JIN Bao-Kang, GAO Shou-Guo, ZHANG Zu-Xun
    1993, 14(11):  1502-1505. 
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    In this paper the theory of quasi-steady-state reversible wave in linear sweep, derivative and semi-differential voltammetry at ultramicroband electrode is described.The properties of the current-potential curves are discussed.Experiments were carried out on an oscillopolarograph to verify the theory.The theoretical conclusions are in good agreement with experimental data for the oxidation of K4Fe(CN)6 in 0.5 mol/L KCl solution at gold ultramicroband electrode.
    Signal Acquisition and Processing in Transient Introduction Techniques On-line Hyphenated with Multichannel ICP-AES
    YAN Xiao-Mei, WANG Xiao-Ru, YANG Peng-Yuan, HANG Wei, HUANG Ben-Li
    1993, 14(11):  1506-1509. 
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    The method and related software for multichannel ICP-AESmultielement transient signal acquisition and processing were developed in the present paper.It has been successfully applied to some new hyphenated techniques such as FIA-ICP-AES, HPLC-ICP-AES, HG-ICP-AES … etc..The characteristics and advantages of this software have been mentioned.It is believed that this software is becoming a powerful tool to exploit the potential of multichannel ICP-AESin combining with transient introduction techniques.
    Study on Synthesis and Properties of Chelate-forming Fiber
    JIANG Gui-Lan, WANG Duo-Xi, GONG Zhen-Bin
    1993, 14(11):  1510-1513. 
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    The selectivity of CPA-mA, a chelate reagent, is about the same for all REEincluding Y.The VS-2 fiber, being basic anion exchange fiber, has larger exchanging capacity and faster exchanging with CPA-mA.The CPA-mAchelate-forming fiber has been prepared by means of combining CPA-mAwith VS-2 fiber in this paper.The stability of the CPA-mAfiber was studied and the test results shown that the fiber was stable in the solutions of ClO4-, CO32-, SO42-, Cl- and CH3COO- with pH1.0, respectively.The exchanging capacity of VS-2 fiber with CPA-mAis about 0.26 mmol/g.The CPA-mAchelate-forming fiber can be used to separate and preconcentrate the trace amounts of REE.The experiment results have demonstrated that REEcould be separated from a large quantities of matrix elements without elution under the given experiment conditions.The pHof the analyzed solutions was 1.0 to 2.0, the flowing speed was more than 12mL/min, it is many times as fast as the analogous resins.The cations, such as ions of Fe, Ca, Al, Mn, Cu, Pb, Co, Ni, Th, Zr and Vetc., do not have influence on the separating REEwith CPA-mAfiber under the condition of existing ascorbic acid, EDTA, CyDTAand EGTA.The test results have shown that the CPA-mAfiber was characterized by litter interelement interference, larger exchanging capacity and lower cost when it was used to separate and preconcentrate the trace REEin complex.It is an effective substance for separating the rare earth elements.
    Calculating Analysis of Acid-Base Titration Without Standard Solution
    ZHANG Yun
    1993, 14(11):  1514-1517. 
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    The calculating analysis of titration without standard solution is a method that can be used to determine the concentration of substance titrated and titrant at the same time.In this paper, the calculating analysis of acid-base titration without standard solution has been described for the determination of monobasic acids, polybasic acids and mixed acids with potentiometric titration and the simplex optimization method.The relative error is less than 2% for monobasic and polybasic acids and 10% for mixed acids.
    Orthogonal ization Recurrence Selection Method and Its Application
    ZHU Er-Yi, YANG Peng-Yuan, DENG Zhi-Wei, HUANG Ben-Li
    1993, 14(11):  1518-1521. 
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    Anew model selection method named orthogonalization recurrence selection (ORS) method is proposed.By use of this method the model with higher predictive ability can be ob-tainded or the lower PRESSstatistic values of the model can be achieved.The comparison is made among forward selection method in the stepwise regression and PLSas well as ORSmethods through the example of QSAR(quantitative structure activity relationship).
    Enrichment of Gold(Ⅲ) by Polyaniline Modified Electrode
    LI Gen-Xi, FANG Hui-Qun, CHEN Hong-Yuan
    1993, 14(11):  1522-1525. 
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    Reaction of the coordinating preconcentration of gold(Ⅲ) by polyaniline modified electrode was studied and verf ied using the methods of cyclic voltammetry, FTIRand scanning electron micrograph.On the basis of the experiments, the optimums reaction conditions were obtained.The cathodic peak current was proportional to the concentration of Au (Ⅲ) in the range of 5.07 × 10-6-5.07× 10-5 mol/Lunder this optimum condition.So this method could be used for the determination of gold in real samples.
    An Electrochemical Detector Cell for Flow Injection Analysis of Glucose in Serum
    XU Hong-Ding, ZOU Ming-Zhu, CAO Zhan-Shuang, PAN Shu-Hong
    1993, 14(11):  1526-1527. 
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    An electrochemical detector cell for FIAof glucose in serum has been developed.It was a three electrodes system involved a homemade copper-PTFEcomposite plated film electrode (working) and other two electrodes, silver (reference) and platinum(auxiliary) wires.The carrier liquid for FIAwas 0.5 mol/L NaOHand flowed through the cell at 2.1 mL/min.The working electrode potential was set at 0.6 V(vs.reference) by potentiostat.Sampling 30 ftLtest solution which was 1% serum sample diluted with water, a peak current was recorded by chronome-try.The peak current was linearly related with the concentration of glucose in the range of 5 × 10-3-2×10-1 mmol/L.The analytical results from our method were pretty correlated to those from glucose oxidase-4-aminoanti-pyrine-phenol method(Trinder method).The regression equation from the results of twenty samples was Y=-0.039 + 1.005X, r=0.9999.It was shown that our method was speedy, cheap and reliable.
    Studies on Electroosmotic Flow in High Performance Capillary Electrophoresis
    LI Hong-Qi, SHEN Zhong-Yao
    1993, 14(11):  1528-1530. 
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    Factors affecting electroosmosis in high performance capillary electrophoresis has been studied in detail.The electroosmotic flow rates are measured at different voltages, electrolytic concentrations, pHvalues in 0.2 mm I.D.silica capillaries.Modified silica capillaries coated with KH-570 or (C6H5)2SiCl2 are also investigated in the paper.It shows that the ξ voltage and electroosmotic flow rates can be reduced by lowering pHvalues and coating capillaries.
    Studies on Polarographic Adsorptive Complex Wave of Gallium (Ⅲ)-Lumogallion
    LI Nan-Qiang, HE Wei-Jun
    1993, 14(11):  1531-1533. 
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    In ClCH2COOH-ClCH2COONa buffer solution at pH 2.8, a sensitive adsorptive complex wave of Ga(Ⅲ)-lumogallion(LMG) was obtained by single-sweep polarography.The detection limit is down to 8.0× 10-9 mol/L.The proposed method has been applied to the determination of gallium content in catalyst.The composition of the complex was detected as Ga(Ⅲ):LMG=1:1.The rate constant of the surface electrochemical reaction was determined as k8=0.56 s-1.
    Using Molecular Graphics, Molecular Mechanics, Quantum Chemistry and Electrostatic Potential Methods to Study Structure-Property Relationship on Pesticides(Ⅳ) --Study on Characteristics of Conformations of Sulfonylureas Herbicides by MMX and Conformation-Superimposition Method
    YAN Bo, LAI Cheng-Ming, LIN Shao-Fan, LI Zheng-Ming
    1993, 14(11):  1534-1537. 
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    Here we have reported the study on the characteristics of conformations of a series of DPXsulfonylurea molecules by molecular mechanics MMXand with the help of conformation-su-perimposition method.a crude model of interaction between sulfonylurea molecule and acceptor has been suggested.
    The Chemistry of α-Oxo Ketene Cyclic Dithioacetals(X) --Studies on the Orientation of Acid Catalyzed Reaction to the Adducts of α-Oxo Ketene Cyclic Dithioacetals with Allyl Grignard Reagents
    LIU Qun, ZHU Zai-Ming, YANG Zhi-Yun, HU Yu-Lan, JING Feng-Ying, XIAO Yan-Wen
    1993, 14(11):  1538-1542. 
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    Addition of aliphatic title compounds 2b with 2-methyl allyl Grignard reagent afforded the corresponding carbinols 3b.Catalyzed by BF3 · Et2O, 3b were converted to the arylthio ether 5b via a cyclization-aromatization process.When water or methanol was present in the reaction mixture, 3b were converted to the phenols or arylether 5'b via a substitution-cyclization aromati-zation process under similar conditions as above.The adducts 4 formed by the addition of 2 with magnesium allyl bromide, were converted to the conjugate polyenes 6 under the above conditions either in the presence or in the absence of the nucleophile.The mechanism was discussed according to the effects of different dialkylthio groups to the carbon cation intermediates 12, 13 and 14.
    Studies on the Electronic Spectra of 1,4-Bis (substituted phenylethynyl)-benzene and Trans,Trans-Bis(β-substituted phenylethenyl)benzene
    HUAN Zhen-Wei, PAN Yin-Ming, TANG Jian-Sheng, CHEN Lan, LI Hua, GAO Zhen-Heng
    1993, 14(11):  1543-1546. 
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    The Ultra-Violet absorption spectra and the fluoresence emission spectra of 1,4-bis (substituted phenylethynyl) benzene (Ⅰ) and trans, trans 1, 4-bis (substituted phenylethenyl) benzene (Ⅰ) were determined.The excited energies of phenylacetylene, diphenylacetylene, Ⅱ, styrene, stilbene, and Ⅱ were computed using CNDO/S-CIand HMOmethods.The influences of the structures of the compounds on spectra were discussed.
    Synthesis and Structure of Tetrahydroimidazo[2,1-a]- 2,3-diphenyl-1, 4-diazo-3-cyclohexene
    LIN Zhen-Guang, ZHUANG Hong-Hui, LU Can-Zhong
    1993, 14(11):  1547-1550. 
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    The title compound was prepared by the condensation of benzile and diethylenetri-amine, which was characterized by IR, MS, 13C NMRand UV.The crystal structure was determined by X-ray diffraction analysis.C18H19N3, Mr=277.39, space group P21/n, cell parameters: a=0.9442(2) nm, b=1.4344(4) nm, c=1.1824(3) nm, β=112.94(2)°, Z=4, Dc=1.25 g · cm-3.The structure was solved by direct method.Refinements of full-matrix least-squares converged to a final R=0.05.The compound is a non-planar molecule, in which the parent structure has two rings, a six-member and a five-member with conformations of chair and half-chair forms respectively.The dihedral angle between two substituted phenyl planes is 73.5°.
    A Novel Oligopeptide from Aster Tataricus
    SHAO Yu, CHENG Dong-Liang, CUI Yu-Xin
    1993, 14(11):  1551-1552. 
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    Anew oligopeptide, asterin Cwas isolated from the roots of A.tataricus and its structure was elucidated as △2.4 Pro-Abu-Ser-isoPhe-Thr-OMe on the basis of IR, UV, 1H NMR, 13C NMR, FABMS, 1H-1H COSY, 13C-1H COSY, COLOC, NOESY, chemical and enzymatic methods.
    The Solvent Effect of Epichlorohydrin Ring-Opening Reaction Catalysized by Zeolite
    LIU Fu-An, LI Yao-Xian, LIU Zai-Qon
    1993, 14(11):  1553-1555. 
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    This paper reports the kinetics of ring-opening reaction of epichlorohydrin with propi-onic acid catalyzed by HZSM-5 exchanged with Fe(Ⅲ).The reaction of epichlorohydrin with propionic acid is the first-order.The rate equation is v=k[epichlorohydrin] when the amount of Fe-ZSM-5 is fixed.The influence of benzene, toluene ο-chlorotoluene, m-chlorotoluene, p-chlorotoluene or o-nitrotoluene as solvent on the rate of the reaction is also investigated.Through the mathematical treatment, the relationship between lnk and dielectric constant ε is found to be Ink=2.80[(ε - 1)/(2ε + 1)] - 9.63 (except o-nitrotoluene)
    Proteinase Fluorogenic Substrates Containing 7-Amino-4- methylcoumarin
    ZHANG Ruo-Heng, JIA Shao-Juan, XU Xiao-Jie, TANG You-Qi, YANG Guang-Wei, NI Yi-Sheng
    1993, 14(11):  1556-1559. 
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    The fluorogenic substrates have been used for the highly sensitive determination of chymotrypsin.The sensitivity is due to the fact that the leaving group, some fluorogenic amine, is highly fluororesent.In the present communication, we wish to report the design, synthesis and kinetic study of a series peptide amide substrates containing 7-amino-4-methylcoumarin.By calculating the enzyme's kcat and Km values for the substrates, the influence of amino acid sequence on the specificity of substrates was studied.Therefore, the best fluorogenic substrates for chymotrypsin, Suc-Ala-Ala-Phe-MCand Sue-Ala-Pro-Phe-MC, were found.
    The Theoretical Calculation of Vibrational Force Fields and Spectral Frequencies of H3+O and H3+O(H2O)n(n=1,2,3) Ions
    SUN Ze-Min, LI Jin-Shan, YAN Guo-Sen
    1993, 14(11):  1560-1564. 
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    The paper calculates theoretically the vibrational force fields of H3+O(H2O)n(n=0-3) ions with the model potential function method of polyatomic molecule and predicts these ions' vibrational frequencies.The results of H3+ Oand H9+O4 ions' vibrational frequencies are better than those of the ab initio gradient method's.This thesis gives first threoretical values of stretching vibration frequencies of H5+O2 and H7+O3.
    Studies on Photoelectrochemistry and Auger Electron Spectra for Inhibitor of Copper in 3% NaCl
    YANG Mai-Zhi, GUO Qin-Lin, CAI Sheng-Min, TONG Ru-Ting, HAO Yan-Zhong, REN Ju-Jie, DI Jing, ZHOU Guo-Ding
    1993, 14(11):  1565-1568. 
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    Measuring the open circuit photovoltage, as a in-situ, non-destructive and sensible method, was used to investigate the corrosion of copper in the 3% NaCl solution and the inhibition efficiency of TTAwith different concentrations.Auger electron spectra (AES) technique was also used in this paper.The experiment result exhibits that TTAwill accelerate the corrosion of copper by Cl- when the concentration of TTAis smaller than 1, 5× 10-5 wt%, and that TTAcan inhibit the corrosion of copper by Cl- when the concentration of TTAis bigger than 1. 5× 10-5 wt%.With increasing the concentration of TTA, the TTAprotecting film will be denser and thicker.When TTAis more concentrative than5× 10-5 wt%, the thickness of the protecting film will not increase.
    Studies on Mass Transfer at Gas-Evolving Electrode
    CHEN Yan-Xi, SHEN Man-Li, LIU Jin-Yu, ZHOU Xian-Mao
    1993, 14(11):  1569-1572. 
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    Mass transfer at a gas evolving electrode was estimated by using a redox system of indicator ions.It was found that the absolute values of the slopes of 1gδ/1gi are 0.287 for hydrogen and 0.583 for oxygen generation in Ni/KOHsystem.The bubble size and velocity of bubble rise were measured by means of laser diffraction method and LDA.The data were used to examine the models of the mass transfer at gas evolving electrode (Hydrodynamic model and penetration model).It is concluded that the mechanism of enhance mass transfer from gas-evolving effects is not single.
    Oxidative Coupling of Methane over Li-Ni-La-O Catalysts
    LIU Bao-Chun, YUAN Song-Yue, WANG Lian-Chi, YU Zuo-Long
    1993, 14(11):  1573-1577. 
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    The oxidative coupling of methane was studied over the Li-Ni-La-Omixed oxide cata-lysts.The effects of the catalyst composition and the reaction conditions on the activited of catalysts were examined.Ahigher C2 yield of 25.8% was obtained at 780℃ and 15000 h-1.The surface and bulk structures of the catalysts were characterized by means of XRD, IR, XPS, SEM.The results clearly indicate that in the series of catalysts LiLa1-xNixO2, when 0.1≤ x≤0.95 the catalyst was composed of two phases La2Ni1-yLiyO4-λ and LiNiO2 When x<0.3, LiLaO2 phase appeared.Among them La2Ni1-yLiyO4X possessed much higher catalytic activity for methane-oxidative coupling.The increase of the content of active site Li+-O--Ni2+ was the main factor for increasing the catalytic activity of methane-oxidative coupling.The synergeatic effect of different phases in the catalysts is also supposed.
    Vapor Liquid Equilibrium of Amino Acids in Methanol-Water Mixed Solvents
    LIU Wen-Bin, WANG Cai-Lan, WANG Jian-Ji, LU Jin-Suo
    1993, 14(11):  1578-1582. 
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    The isothermal vapor liquid equilibrium data of glycine, DL-alanine and L-valine in methanol-water mixed solvents at 333 Kand 338 Khave been measured with the improved Rose still.Alinear relationship was found between the pressure and the concentration of amino acids when the binary relative composition is fixed.The extensive linear theory for the salted solution which has been established was further extended to the systems containing the non-volatile components.The linear formula has been obtained from the law of the thermodynamics.The influence laws of amino acids on the structure and property of the mixed solvent have been investigated.
    UV Pulsed Laser Photolysis of Matrix Isolated Mn2(CO)10 at Low Temperature
    ZHOU Ming-Fei, WANG Wu-Min, YU Min, ZHENG Qi-Ke
    1993, 14(11):  1583-1587. 
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    The photolysis of Mn2(CO)10 isolated in Ar and Xe matrices at 10 Khas been studied with 280 nm and 355 nm UVpulsed laser and Fourier-transformed infrared spectroscopy.The changes in the IRspectra of the Mn2(CO)10 after photolysis and its dependence on the matrices, irradiation time, laser wavelength and the concentration COdoped in the matrix have been examined.The experimental results show that in solid argon matrix the primary product of the dissociation of Mn2(CO)10 is Mn2(CO)9, and in solid xenon matrix, Mn(CO)5 is also observed.The dissociation yield in the xenon matrix is higher than that in argon matrix.Due to the matrix cage effect, the photofragments can recombine, the yield of Mn2(CO)9 is related to the COconcentration in matrix, whereas that of Mn(CO)5 is independent on COconcentration.Based on the COdependence of the absorption intensities of the IRband of the reaction products, the conclusion that in xenon matrix the absorption at 2056.3, 2030.9, 1998.8, 1974.5 and 1764.1 cm-1 are the vibrational bands of Mn2(CO)9 and 1991.9 cm-1 is that of Mn(CO)5 has been reached.The 280 nm pulsed laser is more effective on photolyzing Mn2(CO)10 and generating Mn2(CO)9 than 335nm pulsed alser.
    Reductibility and Catalytic Properties of Different Fe(Ⅲ) Species in Zeolite Y
    GAO Zi, XU Jin-Suo
    1993, 14(11):  1588-1592. 
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    Yzeolites containing Fe(Ⅲ) in framework sites, as the counterions and as the oxide dispersed on zeolite surface were prepared.The reductibility of the zeolite samples was studied by TPRmethod.Below 800℃, the Fe(Ⅲ) cations were reduced to Fe(Ⅲ), the dispersed α-Fe2O3 was reduced to low valent iron oxide, but the framework Fe(Ⅲ) ions were unchanged.Unlike pure α-Fe2O3, none of the Fe(Ⅲ) species in the zeolite could be reduced to Fe metal.The dehydration and dehydrogenation of isopropanol on the zeolites were used as the probe reactions for measuring the relative acidity and basicity of the samples.It has been verified that the adjustment of the acidity and basicity of zeolites through incorporation of Fe(Ⅲ) ions into the various sites of the zeolite structure is realizable.The dehydrogenation and cracking of ethylbenzene were chosen as the probe reactions to measure the dehydrogenation activity of the different types of Fe(Ⅲ) ions incorporated into the zeolite.Cracking of ethylbenzene can become the major reaction due to the synergism of the metal ions and the strong acid sites on the zeolites.Elimination of the strong acid sites and addition of new basic sites on the zeolite surface through incorporation of Fe(Ⅲ) species can enhance the dehydrogenation selectivity considerably.
    Studies on Membrane Catalysts (Ⅲ) --Preparation of Acetaldebyde by Dehydrogenation of Ethanol in a Membrane Reactor
    CAO Zhao, DENG Jing-Fa
    1993, 14(11):  1593-1596. 
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    Dehydrogenation of ethanol to acetaldehyde was carried out in a membrane reactor/incorporating an inorganic alumina membrane, which was prepared by the sol-gel method.The characterization showed that the distribution of pore size was 3-5 nm, while permeability and separation factor were all in good accordance with Knudsen values.The effects of reaction temperature, space velocity, sweep ratio on the conversion of ethanol were investigated in membrane reactor and the results were compared with those obtained by using the conventional reactor.It is shown that in the membrane reactor, the yield of acetaldehyde was higher than that in the conventional reactor and furthermore, the yield of acetaldehyde was also increased by 5%-10% in comparison with that of the corresponding equilibrium conversion.It meant that the shift of the equilibrium of reaction was caused by separation hydrogen from the reaction zone.
    Studies of Olefin Alkylation over Pt-SO42-/ZrO2 Solid Superacid catalyst
    CUI Sheng-Fan, XU Zheng, CHEN Hong-Wei, GUO Can-Xiong, QIAN Zai-Hu
    1993, 14(11):  1597-1599. 
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    The alkylation of isobutane with 1-butene over Pt-SO42-/ZrO2 catalysts prepared with different methods is studied.The results show that Pt-SO42-/ZrO2 catalysts have a high reaction activity and selectivity for alkylation, and the reaction conditions are the same as for SO42-/ZrO2 catalyst.The addition and the adding methods of Pt did not affect the catalytic property, the crystal forms and stucture, and strength of the superacids according to the results of FTIR, XRD, XPSand acid strength measurement.When the alkylation reaction of isobutane with 1-butene takes place in hydrogen, the coke yield over the catalysts added with Pt is decreased and the life of the catalysts is extended.
    Oligomerization Reaction of 1-Butenes (Ⅸ) --The Discussion of Oligomerization Reaction Mechanism in System of the Nickel Carboxylate and Ethyl aluminum Chloride
    CAO Zhan-Xian, ZHOU Ke-Yan
    1993, 14(11):  1600-1604. 
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    The butenes are oligomerized with Ziegler-Natta catalysts composed of (CH3COO)2Ni, (CH3(CH2)3CH(C2H5)COO)2Ni, (C2H5)2AlCl and (C2H5)1.5AlCl1.5 repective-ly.The components in butene dimers are analysed.The course of the formation of active species is discussed.The reaction mechanism of butene oligomerization is deduced.
    Cationic Photopolymerization of Cyclohexene Oxide Initiated with Iron-arene Complex
    CHEN Xu-Dong, CHEN Yong-Lie, LIANG Zhao-Xi
    1993, 14(11):  1605-1608. 
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    The kinetics of photoinitiated polymerization of cyclohexene oxide (CHO) was studied by using Differential Scanning Calorimeter (DSC).The photoinitiator is a cyclopentadienyl Cumene iron hexafluorophosphate.It is shown that CHOpolymerization is the first order reaction, the activation energy for CHOis -9.87 kJ/mol.Temperature has a marked influence on the polymerization process of CHO.The maximum Hof CHOwas obtained at 40℃, but the maximum of reaction rate was obtained at 27℃.Hand reaction rate drop sharply at elevated temperatures.The initiation mechanism was disclosed by these observations.
    Effect of Pressure on Conductivity in Epoxy Resin-Polyethylene Glycal Interpenetrating Polymer Networks Containing Lithium Perchlorate
    LI Guang-Yuan, WANG Xiao-Yan, WANG Xiu-Fang, HU Chun-Pu, YING Sheng-Kang
    1993, 14(11):  1609-1613. 
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    Ionic conductivity of epoxy resin-polyethylene glycal (PE0400) interpenetrating polymer networks (IPN) containing lithium perchlorate between 25-70℃ under pressure from 0 to 40 MPa was investigated.The conductivity maximum exists near 4-5 MPa on conductivity versus pressure curve for these amorphous films.Over 5 MPa the conductivity decreased with increasing pressure.The effect of pressure on the activation volume is determined.For pressure dependence of conductivity and activation volume a microscopic explanation was obtained by considering the crystal picture of ionic transport passages according to crystal chemistry.
    Studies on Polymer Chain Dimension in Solution (Ⅲ) --A New Method for Prediction of Second Virial Coefficient of Polymer Solution
    QIAN Jin-Wen, QI Guo-Rong, FENG Lin-Xian
    1993, 14(11):  1614-1618. 
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    Amethod for prediction of second virial coefficient (A2) from intrinsic viscosity and Mark-Houwink equation or molecular weight has been proposed.The A2 values of 295 samples from 30 kinds of polymer/solvent systems (21 polymers and 12 solvents) calculated by this method are in quite good accordance with experimental results.And also, the model presented here is the best one for obtaining A2, compared with other theories and model.
    Studies on the New Complexing Adsorbents (Ⅲ) --Synthesis and Characterization of Complexing Adsorbents Containing Polyamine and Nickel (Ⅱ) as Template
    HE Bing-Lin, WANG Bu-Sen, DING Ze-Ren, LI Wen-Lan, GUO Zhen-Liang
    1993, 14(11):  1619-1622. 
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    Aseries of complexing polymeric adsorbents made of crosslinked polyamine and nickel (Ⅱ) acting as template ion were synthesized through the polycondensation of epichlorohydrin and tetraethylenepentamine in oil disperse system.The characterization of the sorption for Cu (Ⅱ),Ni(Ⅱ),Zn(Ⅱ) and Co(Ⅱ) metal ions was studied.The results show that the sorption capacities of the kinds of complexing adsorbents for Cu (Ⅱ), Ni (Ⅱ), Zn (Ⅱ), Co (Ⅱ) are 239.60, 231.30, 131.83, 81.23 mg/g resin, respectively.The sorption capacities are in following sequence: Cu(Ⅱ)≈Ni(Ⅱ)>Zn(Ⅱ)>Co(Ⅱ).
    Studies on Electrochemical Polymerization of Naphthalene in BF3-Ethyl Ether Solution
    SHI Gao-Quan, XUE Qi, LI Cun, MA Wan-Li, JIN Shi
    1993, 14(11):  1623-1624. 
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    1,4-polynaphthalene was produced by electropolymerization of naphthalene in BF3-ethyl ether solution.This polymer shows a plane orientation well on the electrode surface.
    A Study on Polymer Blends via Modified Nonradiative Energy Transfer Fluorescence
    QIU Xing-Ping, JIANG Ming
    1993, 14(11):  1625-1626. 
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    In this paper, a modified nonradiative energy transfer method (M-NRET) was used for the study on miscibility of polymer blend.Differing from the conventional NRET, it takes the advantage of labeling one polymer component with both fluorescence donor and acceptor instead of labeling all the components of the blend.This method has been found to be more sensitive to the degree of chain interpenetration in the miscible blends at the molecular level and especially, to be effective to monitor the miscibility-complexation transition of the blends.
    Determination for Characters of Ultra High Molecular Weight Polystyrene
    YANG Di-Lun, JIN Jing, Qi Chen-Ze, LIU You-Cheng
    1993, 14(11):  1627-1628. 
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    Ultra high molecular weight polystyrene with Mw=68.3 × 104-266 × 104, D=2.9-7.2 was synthesized.The electrical, thermal, mechanical characters and rheologic behaviour were determined.The impact strength of the products was found to be 17.9-38.4 J/m, bending strength 86.8-110.5 MPa, hot resistance 93-98℃, transparency 89% and flowviscosity activation energy 67.7 kJ/mol.
    The Molecular Weight Distribution Function of Aα Type Polycondensates and the Interpretation for Gel Molecules
    ZHENG Fu-An, LIU Feng-Qi, TANG Xin-Yi
    1993, 14(11):  1629-1631. 
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    This paper deduced the molecular distribution of Aα type polycondensates with more simple molecular tree model and proposed a new criterion of gel point basing on the real degree of polymerization of the biggest molecular in the reaction system.