萃取剂HDEHP在不同稀释剂中的聚合性质

The dimeric property of bis(2 - ethylhexyl) phosphoric acid(HDEHP) in different diluents has been studied. The experimental results show that the dimeric degree of HDEHP increases with the decrease of the polarity of diluents.This kind of effect has been discussed from the point of view of intermolecular interactions between the extractant molecules and the diluent ones. The dimeric constantswere related to the physical constants and experiencial parameters of the diluents.The following expression hasbeen obtained lg K2 =6 .4 5 9- 4 .4 6 4 (ε- 1) /(2 ε+ 1) - 1.96 5 (n D2 - 1) /(n D2 +1) - 3.199α- 5 .6 6β.

聚合物溶液性质对其数模参数测定结果的影响

通过矿化度对聚合物溶液滤过性、流变性的影响实验 ,研究了AMPS聚合物溶液的性质以及矿化度的增加对这种聚合物数模参数测定结果的影响。研究结果表明 ,随着矿化度的增加 ,溶液中的分子形态及颗粒组成发生变化。这是造成AMPS共聚物溶液静吸附。

阴离子型丙烯酸酯类两亲接枝聚合物的合成、溶液性质及其与阳离子表面活性剂的相互作用研究

通过催化链转移聚合(CCTP)技术可以一步得到末端带有可聚合碳碳双键的大分子单体P(MMA-co-t-BMA),并进一步接枝聚合得到阴离子型两亲接枝聚合物。采用滴形分析法、动态光散射以及透射电镜(TEM)系统研究了所得接枝聚合物的水溶液性质(表面张力、聚集体大小及形貌等),详细研究了合成的阴离子两亲聚合物与阳离子表面活性剂CTAB之间的相互作用。

Syntheses and catalytic performances of three coordination polymers with tetracarboxylate ligands

Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.

以6-甲基-2,3,5-吡啶三酸为配体的过渡金属配合物的合成、结构与性质（英文）

以6-甲基-2,3,5-吡啶三酸为配体和过渡金属盐反应,合成出2个新颖的金属配位聚合物{[Cu(Hmptc)(H2O)]·2H2O}n(1)和{Cd(Hmptc)(H2O)}n(2)(H3mptc=6-甲基-2,3,5-吡啶三酸)。配合物1存在具有四边形孔道的二维网状结构。配合物2中的Cd(Ⅱ)中心通过Hmptc2-配体连接成为类似于笼状的二维层状结构,进一步由氢键相互作用连接成三维超分子结构。配合物2存在蓝绿色荧光。

Syntheses,crystal structures,and catalytic properties of three zinc(Ⅱ),cobalt(Ⅱ)and nickel(Ⅱ)coordination polymers constructed from 5⁃(4⁃carboxyphenoxy)nicotinic acid

Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.

Preparation and interface state of phosphate tailing-based geopolymers

The long-term storage of phosphate tailings will occupy a large amount of land,pollute soil and groundwater,thus,it is crucial to achieve the harmless disposal of phosphate tailings.In this study,high-performance geopolymers with compressive strength of 38.8 MPa were prepared by using phosphate tailings as the main raw material,fly ash as the active silicon-aluminum material,and water glass as the alkaline activator.The solid content of phosphate tailings and fly ash was 60% and 40%,respectively,and the water-cement ratio was 0.22.The results of XRD,FTIR,SEM-EDS and XPS show that the reactivity of phosphate tailings with alkaline activator is weak,and the silicon-aluminum material can react with alkaline activator to form zeolite and gel,and encapsulate/cover the phosphate tailings to form a dense phosphate tailings-based geopolymer.During the formation of geopolymers,part of the aluminum-oxygen tetrahedron replaced the silicon-oxygen tetrahedron,causing the polycondensation reaction between geopolymers and increasing the strength of geopolymers.The leaching toxicity test results show that the geopolymer has a good solid sealing effect on heavy metal ions.The preparation of geopolymer from phosphate tailings is an important way to alleviate the storage pressure and realize the resource utilization of phosphate tailings.

Transition metal coordination polymers with flexible dicarboxylate ligand:Synthesis,characterization,and photoluminescence property

Under solvothermal conditions,six new coordination polymers(CPs)[Mn(L)(phen)(H_(2)O)]_(n)(1),[Co(L)(phen)(H_(2)O)]_(n)(2),[Cu(L)(phen)(H_(2)O)]_(n)(3),[Zn_(2)(L)_(2)(phen)2(H_(2)O)]_(n)(4),[Zn(L)(phen)]_(n)(5),and[Cd(L)(phen)2]_(n)(6)were synthesized by reactions of dicarboxylate ligand 2,2'-(1,2-phenylenebis(methylene))bis(sulfanediyl)dinobutyric acid(H_(2)L)and 1,10-phenanthroline(phen)with the corresponding metal salts.Complexes 1-6 have been structurally characterized by single-crystal X-ray diffraction analyses,elemental analysis,IR,thermogravimetric analysis,and powder X-ray diffraction.The structures of 1-6 are 1D chains,which are further connected by hydrogen bonding interac-tions to form 3D supramolecular structures.Among them,1 and 2 are isomorphic with L2-of syn-conformation,while L2-shows anti-conformation in 3-6.In addition,the solid-state photoluminescence property of 4-6 was investigated.

聚偏氟乙烯辐照改性的影响因素研究

辐照改性是诱导高分子材料交联而实现高性能化和功能化的一种简单有效方法,具有节能环保、交联周期短、交联度精准可控等优点。聚偏氟乙烯(PVDF)作为辐照交联型聚合物,辐照改性处理可明显改善其高温力学性能、耐化学药品性、耐蠕变性、耐磨损性等性能,使其在高精尖领域得到实际应用。PVDF辐照改性后的性能受不同因素影响,包括辐照工艺条件和聚合物自身性质两大方面。明确PVDF辐照后的性能与影响因素之间的关系后,通过优化辐照工艺条件和改变聚合物的性质,人们可以制备符合特定性能要求的辐照PVDF产品。

Synthesis and Solution Properties of Hydrophobic Associating Polymers

Acrylamide/2-acrylamido alkane sulfonic acid hydrophobic associating copolymers were synthesized by micellar copolymerization. Effects of hydrophobe content, polymer concentration, salinity and surfactant on rheological behavior of copolymers were investigated and the conformation of polymers in solution was studied by means of environmental scanning electronic microscopy and dynamic light scattering. The experimental results showed that in the dilute regime the hydrophobic parts could interact intramolecularly, while in the regime where the polymer concentration was higher than the critical association concentration, intermolecular hydrophobic association became predominant. Within the limit of the solubility, the critical association concentration of the polymer decreased with the increase of the salinity. The experimental results of the solution conformation indicated the presence of the three-dimensional network structure in deionized water and the size of the mesh in the network varied with the polymer concentration. In NaCl solution, above the critical association concentration, an increase in polymer concentration enhanced the intermolecular association and also enlarged the hydrodynamic radius. It would result in the improvement of the thickening power of polymers.

Biosynthesis and Characterization of Polyhydroxyalkanoate Copolyesters in Ralstonia eutropha PHB-4 Harboring a Low-Substrate-Specificity PHA Synthase PhaC2ps from Pseudomonas stutzeri 1317

A series of polyhydroxyalkanoate(PHA)copolymers consisting of short-chain-length(SCL)and medium-chain-length(MCL)3-hydroxyalkanoate(3HA)monomers were synthesized in the recombinant Ralstonia eutropha PHB - 4 harboring a low-substrate-specificity PHA synthase PhaC2Ps from Pseudomonas stutzeri 1317. These polyesters,whose monomer compositions varied widely in chain length,were purified and characterized by acetone fractionation,nuclear magnetic resonance(NMR),gel-permeation chromatography(GPC),and differential scanning calorimetry(DSC).This was the first time that the physical properties of PHA copolymers polymerized by PhaC2Ps were characterized.The results indicated that the variation in MCL 3HA contents did not have an obvious influence on the molecular weights of these PHA copolymers but was effective in changing their physical properties. The variation in the thermal property of PHA copolymers with 3-hydroxyoctanoate(3HO)content was also inves- tigated in this study.

Structural characteristics and properties of PU-modified TDE-85/MeTHPA epoxy resin

Diglycidy1-4,5-epoxycyclohexane-1,2-dicarboxylate （TDE-85）/methyl tetrahydro-phthalic anhydride （MeTHPA） epoxy resin was modified by polyurethane（PU）, and its structural characteristics and properties were studied by infrared spectrum analysis （IR）, scanning electronic microscopy （SEM）, mechanics testing and thermogravimetric analysis （TG）. The results indicate that epoxy polymeric network Ⅰ and polyurethane polymeric network Ⅱ are formed in the PU-modified TDE-85/MeTHPA epoxy resin. Meanwhile the PU-modified TDE-85/MeTHPA resins have heterogeneous structure. The miscibility between epoxy （EP） and polyurethane （PU） as well as the phase size are dominantly determined by the mass fraction of polyurethane prepolymer （PUP） in the EP/PU blends. With the increase of PUP mass fraction, the tensile strength, impact strength and thermal stability of the PU-modified TDE-85/MeTHPA epoxy resin all firstly exhibit increasing tendency, and decrease after successively reaching their maxima. When the number-average molecular mass of PPG is 1 000 and the mass fraction of PUP is 15%, the tensile strength, impact strength and thermal stability of materials obtained, compared with TDE-85/MeTHPA epoxy resin, are improved obviously.

Viscoelastic Analysis of a Surface Acoustic Wave Gas Sensor Coated by a New Deposition Technique

An analysis of the response of surface acoustic wave sensors coated with polymer film based on new coating deposition （self-assemble and molecularly imprinted technology） is described and the response formulas are hence deduced. Using the real part of shear modulus, the polymer can be classified into three types： glassy film, glassy-rubbery film and rubbery film, Experimental results show that the attenuation response is in better consistence with the simulation than in Martin＇s theory, but the velocity response does not accord with the calculation exactly. Maybe it is influenced by the experimental methods and environment. In addition, simulations of gas sorption for polymer films are performed. As for glassy film, the SAW sensor response increases with increasing fihn thickness, and the relationship between the sensor response and the concentration of gas is pretty linear, while as for glassy-rubbery flint and rubbery film, the relationship between the sensor sensitivity anti concentration of gas is very complicated. The ultimately calculated results indicate that the relationship between the sensor response and frequency is not always linear due to the viscoelastic prooerties of the polymer.

Monte Carlo Simulation of Propylene Polymerization (Ⅰ) Effects of Impurity on Propylene Polymerization

A comprehensive mechanism for propylene polymerization was proposed by considering the effects of main impurities in the material on propylene polymerization. According to the proposed mechanism, Monte Carlo simulation was employed to investigate the polymerization kinetics in order to determine the effects of the main impurities on the polymerization. Significant influences of the main impurities on the rate, number-average degree and controlling capability of hydrogen of the polymerization were analyzed.

Electrochemical Performance of Nickel Hydroxide/Activated Carbon Supercapacitors Using a Modified Polyvinyl Alcohol Based Alkaline Polymer Electrolyte

Polyvinyl alcohol （PVA）-sodium polyacrylate （PAAS）-KOH-H2O alkaline polymer electrolyte film with high ionic conductivity was prepared by a solution-casting method. Polymer Ni（OH）2/activated carbon （AC） hybrid supercapacitors with different electrode active material mass ratios （positive to negative） were fabricated using this alkaline polymer electrolyte, nickel hydroxide positive electrodes, and AC negative electrodes. Galvanostatic charge/ discharge and electrochemical impedance spectroscopy （EIS） methods were used to study the electrochemical performance of the capacitors, such as charge/discharge specific capacitance, rate charge/discharge ability, and charge/discharge cyclic stability. Experimental results showed that with the decreasing of active material mass ratio m（Ni（OH）2）/m（AC）, the charge/discharge specific capacitance increases, but the rate charge/discharge ability and the charge/discharge cyclic stability decrease.

STUDY ON THE SYNTHESIS AND PHYSICOCHEMICAL PROPERTIES OF SUCROSE POLYESTER

Orthogonal test was used to evaluate the effects of synthetic such as temperature （120-140 ℃）, reaction time （4-6） and substrate molar ratio of methyl oleate to sucrose （8：1-12：1） on the percent quantity conversion to sucrose polyester. Sucrose polyester was synthesized by a solvent-free one-stage interesterification. The optimum reaction conditions are as follows： methyl oleate/sucrose =10： 1 （mol/mol）; reaction temperature is 140 ℃; reaction time is 5 hours. The product yield reaches 88.15%, and the degree of esterification （DE） is over 7 in the conditions. Thin layer chromatography （TLC）, column chromatography （CC）, High-performance liquid chromatography （HPLC） were used to analyze the product, the results show that the percent of sucrose polyoleate is over 70% in the product. The physicochemical properties of sucrose polyesters were compared with cooking oil. The results show that the qualities of sucrose polyesters are all up to the triglyceride.

Preparation and properties of PEO/LiClO_4/KH560-SiO_2 composite polymer electrolyte by sol-gel composite-in-situ method

Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.

Nanoscale Tail Aggregation in Ionic Liquids: Roles of Electrostatic and van der Waals Interactions

Nanoscale spatial heterogeneity in ionic liquids is formed by the aggregation of cationic tail groups. The electrostatic interactions between polar groups and the collective van der Waals interactions between nonpolar tail groups both contribute to the formation of tail domains, but the degrees of their contributions were unknown. In this work, by applying a strong external electric field to effectively overpower the electrostatic interactions between polar groups, we have determined that the tail aggregation is majorly attributed to the electrostatic interactions and the van der Waals interactions only have minor influence on the spatial heterogeneity phenomenon of ionic liquids.

Effect of Clay Minerals on the Chemical Characteristics of Soil Humus

Chemical characteristics of humic substances in soils with different mineralogical characteristics and under different utilization patterns in Zhangpu, Fujian Province,together with two pairs of cultiwted soils in North China Plain were studied by chemical analysis,visible and IR spectroscopy and 13C NMR spectrometry.For soils in Zhangpu the HA/FA ratio and both the aromaticity and the degree of hundfication of HA were higher in soils with montmorillonite as the predominant clay mineral than in thO6e with kaolinite as the predominant clay mineral, provided these soils were under the same utilisstion pattern. While for eaCh pair of soils with similar mineralogical characteristics the HA/FA ratio was higher and the C/H ratio and the content of carboxyl group of HA were lower in paddy soil than in upland soil.Among the upland soils(or paddy soils) studied the HA/FA ratio of soil in Zhangpu with kaollnite as the predominant clay mineral was the lowest,and that of soil in Zhangpu with montmorillonite aa the predominant clay mineral was the highest.It was concluded that the presence of moatmorillonite favored the formation and maturation of humic acid.

STUDY ON SIDE REACTION IN THE SYNTHESIS OF HYPERCROSSLINKED POLYMERS

The systematical study about side reactions have revealed the formation mechanism of oxygen-containing groups of hypercrosslinked polymers. Surface chemistry and functionality of the polymers are characterized by Fourier-transform infrared spectroscopy (FT-IR), solid state nuclear magnetic resonance (NMR) and contact angle. The results showed that the ether groups were from chloromethylated reaction, and the alcohol groups arose from partial hydrolysis of chloromethyl groups during the post-crosslinking reaction, and the carbonyl functionality was formed by further oxidation of the alcohol groups. Catalyst and solvent used in the postcrosslinking reaction would greatly influence the surface chemistry of the polymer.