茂基稀土胺化物的合成及其作为单组份引发剂引发极性单体聚合的研究

综述了近年来我们在茂基稀土胺化物的合成、结构及其催化极性单体,包括甲基丙烯酸甲酯、甲基丙烯酸N,N-二甲氨乙酯、异氰酸苯酯的聚合和ε-己内酯开环聚合的研究结果.讨论了茂基稀土胺化物的结构与催化活性的关系,提出了可能的聚合反应机理.

钯催化的肉桂基碳酸酯化合物与酰腙的烯丙基胺化反应

烯丙基胺结构单元广泛存在于天然产物、药物和功能材料分子中,另外烯丙基胺衍生物也是一类重要的有机合成子.实现了钯催化的肉桂基碳酸酯化合物和酰腙化合物的烯丙基胺化反应,高选择性地生成了线型烯丙基胺类化合物,产率高达99%.该方法具有不需要加碱、条件温和、操作简单、底物适应范围广等优点.

烯胺酮平台构建转化生物质产品Cyrene为增值化合物

发展了在二氢左旋葡萄糖酮(Cyrene,昔兰尼)的酮α-位烯胺化构建烯胺昔兰尼(EC)的方法,有效地构建烯胺Cyrene作为平台合成子为将生物质产品Cyrene转化为增值化学品开辟了广阔的空间.在此研究中,实现了将烯胺昔兰尼向多种不同的手性有机衍生物,包括NH-/N,N-双取代结构的烯胺昔兰尼,氰基烯-和烯基磷修饰的昔兰尼,呋喃稠环结构的昔兰尼以及2,2-二氟二氢呋喃稠合的昔兰尼的转化.

钯催化的芳酰氧基氨基甲酸酯的分子内脱羧烯丙基胺化反应

烯丙基胺化合物是有机合成化学和药物化学的重要化合物之一,其合成方法备受关注.以芳酰氧基氨基甲酸酯为原料通过分子内脱羧一步合成了烯丙基胺化合物,而原料芳酰氧基氨基甲酸酯可由廉价易得的羧酸和羟胺原位制备.反应条件温和,底物普适性好,并且可以实现克级和吲哚的合成.

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

双功能配体促进的钯催化不对称醚化和胺化反应（英文）

研究双亚砜膦配体(BiSO-P)亚砜基团的Bronsted碱性在协同催化反应中的作用.1H NMR研究表明双亚砜膦与醇和胺等质子试剂形成氢键;并将此类配体应用于钯催化的不对称醚化和胺化反应,最高获得99%ee.研究发现氢键的存在能有效提高反应的ee值,配体亚砜基团在反应过程中同时起着Lewis和Bronsted碱的作用.

Thermodynamic study of direct amination of isobutylene to tert-butylamine

On basis of thermodynamic empirical equations, the thermodynamic parameters for the direct amination of isobutylene to tert‐butylamine, an atomically economic and green chemical reaction,were calculated. In particular, the equilibrium conversion of isobutylene under various reactionconditions close to those used in industry was calculated and discussed. Isobutylene amination is atemperature sensitive reaction due to its exothermic nature and isobutylene equilibrium conversiondecreases with temperature. However, kinetically, the amination reaction will be faster at ahigher temperature. Thus, there must be an optimum temperature for the reaction. A high pressureand n(NH3)/n(i‐C4H8) molar ratio promote the transformation of isobutylene to tert‐butylamine.Developing a highly efficient catalyst under mild reaction conditions is preferred for the aminationprocess. The reaction was investigated over a series of acidic zeolites. ZSM‐11 zeolite exhibited thebest performance with 14.2% isobutylene conversion (52.2% of the equilibrium conversion) and >99.0% tert‐butylamine selectivity. The effect of reaction conditions on the performance of the ZSM‐11 catalyst agreed with the thermodynamic results, which provides guidance for further catalyst development and reaction condition optimization.

A shaped binderless ZSM-11 zeolite catalyst for direct amination of isobutene to tert-butylamine

A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.

Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation

A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source.Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites.The special complexing capability of EDTA^(2–)plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process,thus leading to a uniform distribution of Mo in the MFI framework.In addition,a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites.The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H_(2)O_(2)as the oxidant.The composition-optimized catalyst,Mo-MFI-50,efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion(93%)and epoxide selectivity(82%)at 75℃after 9 h of reaction.Moreover,the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.

Single Pt Atoms Supported on Oxidized Graphene as a Promising Catalyst for Hydrolysis of Ammonia Borane

Based on density functional theory calculations,the full hydrolysis of per NH3BH3 molecule to produce three hydrogen molecules on single Pt atoms supported on oxidized graphene(Pt1/Gr-O)is investigated.It is suggested that the first hydrogen molecule is produced by the combination of two hydrogen atoms from two successive B-H bonds breaking.Then one H2O molecule attacks the left*BHNH3 group(*represents adsorbed state)to form*BH(H2O)NH3 and the elongated O-H bond is easily broken to produce*BH(OH)NH3.The second H2O molecule attacks*BH(OH)NH3 to form*BH(OH)(H2O)NH3 and the breaking of O-H bond pointing to the plane of Pt1/Gr-O results in the desorption of BH(OH)2NH3.The second hydrogen molecule is produced from two hydrogen atoms coming from two H2O molecules and Pt1/Gr-O is recovered after the releasing of hydrogen molecule.The third hydrogen molecule is generated by the further hydrolysis of BH(OH)2NH3 in water solution.The rate-limiting step of the whole process is the combination of one H2O molecule and*BHNH3 with an energy barrier of 16.1 kcal/mol.Thus,Pt1/Gr-O is suggested to be a promising catalyst for hydrolysis of NH3BH3 at room temperature.

Synthesis and Characterization of EO/PO Random Copolyethers

Ethylene oxide(EO) and propylene oxide(PO) random copolyethers were synthesized by the sequential addition of the mixture of ethylene oxide and propylene oxide to propylene glycol (initiator) in the presence of potassium hydroxide(KOH), and characterized with infrared spectrum(FTIR) and nuclear magnetism resonance(NMR). The effects of catalyst concentration, reaction temperature, charging rate and EO/PO mixture ratio on the polymerization reaction were investigated. It was revealed that the optimal reaction condition is the ratio of 2.5∶1 000(KOH mass vs. product mass), at 114.6℃ and pressure below 0.4 MPa. The residual KOH was neutralized by phosphoric acid(H 3PO 4). Then the crude copolyether was refined with adsorbents, and the refined copolyether, which contains less than 0.7 μg/ml K+, was obtained as colorless, viscous liquid.

Electrochemical Polymerization of Acrylamide Film on Mild Steel Electrode for Corrosion Protection

Polyacrylamide （PAM） film was electrosynthesized on mild steel by cyclic voltammetry using Ce （IV） salt-oxalic acid as supporting electrolyte. Polymerization was initiated by a free radical that was formed by the fast reaction of oxalic acid and Ce （IV）. The electrolysis of the reaction solution resulted in regeneration of Ce （IV）, which could oxidize oxalic acid to produce radicals. The effect of temperature on the yield of electroinitiated polymerization was performed. The potential sweep rates were changed to achieve the polymer film with different thickness. Protective properties of the PAM film for corrosion of mild steel in 1 M NaCI aqueous solution were investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy （EIS）. The structure of PAM film on mild steel was investigated by using physicochemical methods such as elemental analysis of C, H, N, physical chemical methods and FTIR spectrometer. The influence of scan repetition and scan rate on the formation of polymer film was studied at a current density of 1 mA/cm2. The results of these studies reveal that the corrosion resistance of the PAM-coated mild steel was significantly higher and the corrosion rate was considerably lower than that of uncoated steel. The PAM film was formed with lower sweep rate leading to more positive shift of corrosion potential and greater charge transfer resistance, reflecting higher inhibition for corrosion of the mild steel.

Feature Designed Growth of 3D Flower-like SiO2 Growing on Polyethyleneimine Modified CaCO3 Microparticles

We report on the ability to create complex 3D flower-like SiO2 in vitro via CaCO3 micropar- icles supported by polyethyleneimine mediated biosilicification under experimentally altered chemical influences. The morphology, structure, composition of the product have been inves- tigated with the X-ray photoelectron spectrum, scanning electron microscope, transmission electron microscope, and energy-dispersive spectroscopy. Tile overall morphologies could be controlled to shift from a characteristic network of flower-like silica sphere to a sheet-like structure by adjusting physical adsorption of different amount of polyethyleneimine onto the surface of the CaCO3 microparticles.

Prediction of Swelling Behavior of AT-Isopropylacrylamide Hydrogels in Aqueous Solution of Sodium Chloride

In this paper, a model is presented to correlate and predict the swelling behavior of hydrogels in aqueous solutions of electrolytes. The model is a combination of VERS-model, 'phantom network' theory and 'free-volume' contribution. The VERS-model is used to calculate Gibbs excess energy; 'phantom network' theory to describe the elastic properties of polymer network, and 'free-volume' contribution to account for additional difference in the size of the species. To test the model, a series of N-isopropylacrylamide based hydrogels are synthesized by free radical polymerization in oxygen-free, deionized water at 25℃ under nitrogen atmosphere. Then, the degree of swelling of all investigated gels as well as the partition of the solute between the gel phase and the surrounding coexisting liquid phase are measured in aqueous solution of sodium chloride. The model test demonstrates that the swelling behavior correlated and predicted by the model agrees with the experimental data within the experimental uncertainty. The phase transition appeared in the experiment, and the influences of the total mass fraction of polymerizable materials ζgel as well as the mole fraction of the crosslinking agent yCR on the swelling behavior of IPAAm-gels can also be predicted correctly. All these show the potential of such model for correlation and prediction of the swelling behavior of hydrogels in aqueous solutions of electrolytes.

Enhanced treatment of water with low turbidity:Combined effects of permanganate, PAM and recycled sludge

The effectiveness of enhancing treatment of water with low turbidity through combined effects of permanganate oxidation, PAM aiding coagulation and sludge recycling was investigated through continuous bench scale studies. In comparing with ferric chloride coagulation, only recycling sedimentation sludge was ineffective in enhancing treatment of water with low turbidity. PAM with recycled sludge showed positive effects, and the additional permanganate dosing exhibited the best potential of favoring coagulation, which leaded to much lower effluent turbidity and CODMa. Additionally, it was observed that the optimal permanganate dosage was 0. 4 mg/ L and the higher permanganate dosage exhibited inhibiting effects for pollutants removal. SEM analysis indicated that the floes were loosely formed and the particle diameter was critically low for ferric chloride coagulation process. Comparatively, the addition of PAM and permanganate with recycled sludge facilitated the aggregation of tinny particles onto compact PAM polymer chains, therefore contributing to the formation of compact floes with high particle diameter. The combined employment of recycled sludge, PAM and permanganate showed the best potential of favoring coagulation, mainly through synergistic effects between seeding, polymer bridging and increasing effective collision in mechanism. Additionally, the variation of Fe and Mn concentration after recycling and sedimentating units was studied for the processes, and the main species was also investigated for elements Fe and Mn. Sludge recycling and permanganate addition did not increase Fe and Mn concentration in the sedimented water.

Bio-solubilization of Chinese lignite I:extra-cellular protein analysis

A white rot fungus strain, Trichoderma sp.AH, was isolated from rotten wood in Fushun and used to study the mechanism of lignite bio-solubilization.The results showed that nitric acid pretreated Fushun lignite was solubilized by T.sp.AH and that extracellular proteins from T.sp.AH were correlated with the lignite bio-solubilization results.In the presence of Fushun lignite the extracellular protein concentration from T.sp.AH was 4.5 g/L while the concentration was 3 g/L in the absence of Fushun lignite.Sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE) of the extracellular proteins detected at least four new protein bands after the T.sp.AH had solubilized the lignite.Enzyme color reactions showed that extracellular proteins from T.sp.AH mainly consisted of phenol-oxidases, but that lignin decomposition enzymes such as laccase, peroxidase and manganese peroxidases were not present.

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.

Purification and Biochemical Characterization of N-methyl-Histidylesterase from Camel （Camelus dromedarius） Liver

Camel Liver Esterase （LE） was isolated through five consecutive steps： Extraction with Tris/HCl buffer, pH 8, precipitation with ammonium sulfate, affinity chromatography on Affi-gel-butyric acid and on Affi-gel-oleic acid, and preparative polyacrylamide gel electrophoresis （PAGE）. The Km values were found as： methyl butyrate （8.3 mM）, α-naphthyl acetate （3.65 mM）, 13-naphthyl myristate （66.7 mM）, p-nitrophenyl acetate （0.29 mM）, and phenyl acetate （5.26 mM）. The Ki of LE inhibition by bis（4-nitrophenyl） phosphate was 7.9 p.M, and 58 μM by phenyl-methyl-sulfonyl fluoride. The inhibition by these inhibitors is irreversible. p-Hydroxymercuribenzoate or ethylenediamine-tetra-acetic acid did not inhibit the enzyme. LE showed a dimeric structure with molecular weight of 129 kD. The energy of activation of LE was 15.0, 5.5 and 10.75 Kcal, using the substrates： a-naphthyl acetate, p-nitrophenyl acetate, and methyl butyrate, respectively. The optimal pH for LE was between 8 and 10. The N-terminus was found as aspartic acid. The percentage of glycine residues （13.3%） was the highest whereas the percentage of cysteine residues （0.68%） was the lowest in LE. Amino acid composition shows that LE has -50% of its histidine residues as N-methylhistidines.

The Inhibitory Role of Plant Extracts on Acrylamide Formation in Potato Chips

This paper investigated the efficiency of antioxidant of Thyme and extract of cumin on the reduction of acrylamide in potato chips and summarized the optimal levels of two additives. Seven experimental groups including a control group were organized for both of additives.