氯化聚丙烯的磺化反应

研究了氯化聚丙烯(CPP)采用亚硫酸氢钠作磺化剂的磺化反应,在乳液状态下成功地合成了接枝磺酸基团的CPP。红外光谱(FT-IR)图在1150cm-1处出现一个新的强吸收峰为磺酸基团的伸缩振动吸收峰,核磁共振氢谱(1H-NMR)受接枝的磺酸基团影响,化学位移δ为3.52～3.89及4.07处位移向低场移动,也证明了磺酸基团取代了CPP上部分氯原子,接到CPP分子上。研究了反应时间和亚硫酸氢钠用量对磺化度的影响。磺化反应初期,磺化度增大较快,反应20h后,磺化度变化不明显。当反应时间为24h,mNaHSO3/mCPP=0.6时磺化度达到1.53%。     

正交设计法研究中温煤沥青磺化工艺

以浓硫酸为磺化剂对中温煤沥青进行磺化改性。采用硫酸钡沉淀法测其磺化度。通过考察反应温度、反应时间和磺化比对磺化度的影响并通过正交实验获得最佳工艺参数：反应温度70℃,反应时间5h,磺化比1．8,该条件下合成产物的磺化度达13．28％,水溶物含量为98％。     

球形多孔木质素颗粒的制备及表征

以工业碱木质素为原料,变压油为分散相,添加分散剂十二烷基硫酸钠及交联剂环氧氯丙烷,采用"反相悬浮聚合法"制备出球形多孔木质素珠体.通过单因素及正交试验筛选制备木质素多孔珠体的影响因素并对球形木质素珠体进行了形貌、红外光谱、X衍射分析.结果分析表明,制备木质素珠体的最佳配比为:5g木质素溶于50mL水中,pH值为10～1...     

Synthesis of sodium magnesium iron sulfate rod-likes as NASICON using the precipitation method

Sodium magnesium iron sulfate rod-likes were synthesized using the tailing by the precipitation method. The density of the tailing sample was determined as 3.45 g/cm³ and 85% of the particle sizes are < 300 μm. In the course of synthesis, the tailing dissolved in the sulfuric acid. The solution was participated using sodium hydroxide. The precipitate was calcinated at 500 °C in the furnace without special atmosphere. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed to characterize the prepared product. XRD results showed that sodium magnesium iron sulfate is the desired material. Also, the sample contains a small amount of sodium sulfate. The SEM image proved that the morphology of the sample is rod-like. It was observed that the diameter of the rod-likes was about 100-250 nm.     

链转移剂对高团含量共聚物乳液的影响

分别合成了固含量７０％、６７％左右的ＢＡ／ＭＭＡ／ＨＡＭ、ＢＡ／ＭＭＡ／ＭＡＡ共聚物乳液。发现：链转移剂Ｃ１２Ｈ２３ＳＨ的使用,使乳胶粒粒径变大,乳液粘度变小,聚合物应力松驰时间缩短,未使用链转移剂的胶膜其拉伸为脆性断裂,使用的为韧性断裂。     

Synthesis and characterization of sulfonated poly(ether imide) membranes using thermo-analysis and dialysis process

Polyimides have been investigated as alternative materials to commercial membranes, once these polymers present high thermal, chemical, and mechanical performances. This work has modified poly(ether imide), PEI, by sulfonation reaction using acetyl sulfate as sulfonating agent. Sulfonated PEI (SPEI) films were characterized by infrared spectroscopy, ion exchange capacity (IEC), glass transition temperature (Tg), and proton diffusivity. The influence of degree of sulfonation on IEC, Tg, and proton diffusivity can be observed. SPEI membranes have presented proton diffusivity lower than that obtained with a commercial sulfonated membrane (Nafion). This result was related to low degree of sulfonation and low chain mobility of the obtained SPEI.     

Determination of the dopant weight fraction in polyaniline films using a quartz-crystal microbalance

The electrical conductivity of polyaniline depends on factors such as degree of oxidation, type of protonation, and dopant weight fraction. The last of these factors is connected with the loss of mass during the deprotonation of polyaniline, and can thus conveniently be determined in situ by the use of a quartz microbalance. This is illustrated in the present paper which concerns the determination of the weight fraction of acid in thin polyaniline films prepared by the chemical oxidation of aniline in the aqueous solutions of sulfuric and phosphoric acids. It is illustrated that the deprotonation-reprotonation processes are fast, complete, and reversible. Polyaniline has sulfate counter-ions in 0.1 M sulfuric acid while, in 0.5-1 M sulfuric acid, hydrogen sulfate counter-ions are present. The quartz microbalance involving polyaniline films can be used in the sensing of the acidity.     

Leaching and separation of zinc from the black paste of spent MnO2-Zn dry cell batteries

Spent batteries represent a source of hazardous materials when discarded without appropriate treatment. Investigations on the recovery of zinc from the black paste of spent MnO(2)-Zn cell batteries were carried out. Leaching of zinc and manganese from the black paste of spent batteries using sulfuric or hydrochloric acid solutions was studied. It was found that leaching with sulfuric acid solution is more efficient than with HCl solution. Different parameters affecting the leaching of Zn(II) and Mn(II) with sulfuric acid were further studied. Extraction of Zn(II) and Mn(II) from the leaching sulfate medium by bis(2,4,4-trimethylpentyl) dithiophosphinic acid (CYANEX 301) diluted with kerosene was investigated. The factors affecting the extraction process, separately studied, include the effect of contact time, sulfuric acid concentration, CYANEX 301 concentration, phase ratio as well as temperature. The results indicated that, from sulfate medium, Zn(II) is more extracted than Mn(II). Selective stripping of Zn(II) was obtained using 5M HCl. Application of the method on the leaching sulfate solution of the spent MnO(2)-Zn dry cell black paste show the efficiency of the process, where the extraction and stripping of Zn(II) are 98% and 99%, respectively.     

改性纳米SiO_2/磺化聚苯乙烯-马来酸酐降粘剂的研究

以苯乙烯、马来酸酐为单体,发烟硫酸为磺化剂,正硅酸乙酯为纳米二氧化硅的前驱体合成了改性纳米二氧化硅/磺化苯乙烯-水解马来酸酐降粘剂。研究了引发剂的浓度,磺化剂的加量,乙酸乙酯的加量等因素对产品产率、产品分子量以及性能的影响。用红外光谱、扫描电镜和热分析仪对该纳米复合降粘剂进行了表征分析并对其性能进行了测试。结果表明,该纳米降粘剂具有良好的热稳定性,加入0.5%(质量分数)该降粘剂可使7.5%(质量分数)的淡水基浆在常温下的降粘率达到83.3%,经180℃高温老化16h后的降粘率达到90%。     

Pt/TiO2-NTs复合材料的制备及其甲醇电氧化机理研究

采用水热法合成锐钛矿型TiO2纳米管(TiO2-NTs),并以其为载体制备了Pt/TiO2-NTs复合材料。用TEM、XRD对复合材料的形貌和结构进行了表征,TEM测试表明Pt纳米粒子以簇状形式均匀地分散在TiO2纳米管表面。运用循环伏安法研究了Pt/TiO2-NTs复合材料在不同条件下对硫酸中甲醇的电催化活性,并讨论了甲醇的电氧化机理。结果表明,Pt/TiO2-NTs复合材料具有出色的电催化活性。因此,TiO2-NTs被认为是非常有潜力的燃料电池贵金属催化剂载体材料。     

The influence of crosslinking density on the pore morphology of copolymer beads prepared with a novel pore-forming agent

Macroporous styrene–divinylbenzene (St–DVB) copolymer beads are prepared with a novel pore-forming agent, 1-chlorodecane. Copolymer beads with high specific surface area are obtained although 1-chlorodecane is a typical incompatible solvent of polystyrene. The unexpected behavior of 1-chlorodecane during preparation of copolymer beads is discussed. It is found that the excellent compatibility between the chloro substituents in 1-chlorodecane and phenyl rings in copolymer could be responsible for the unexpected behavior. In addition, the effect of crosslinking density on the pore morphology of the copolymer beads is systematically investigated. The results indicate that the specific surface area, the total pore volume and the average pore diameter of the copolymer beads strongly depend on the crosslinking agent concentration. Overall, the present study provides a novel route to prepare macroporous polymer beads with controllable pore morphology.     

Adsorptive features of poly(glycidyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-hydroxyethyl methacrylate): effect of porogen formulation on heavy metal ion adsorption

Preparation of crosslinked copolymer beads based on glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA), and divinyl benzene for the use of heavy metal adsorption has been investigated. In our study, a series of porous copolymer beads were synthesized by suspension polymerization in the presence of porogens, 1-dodecanol, toluene, and heptane at different dilutions. The effect of the porogens on the surface appearance and the porous structure of copolymer beads was studied by scanning electron microscopy and BET method. Diethylene triamine chelating copolymers were obtained through a reaction between amine groups of diethylene triamine and epoxide pendant groups of GMA. Adsorption isotherm and quantitative analysis for adsorption capacity involving copper, chromium, manganese, cadmium, iron, and zinc ions were investigated using atomic absorption spectrophotometer. The adsorption was a function of types of metal ions, adsorption time, and solution properties including pH and metal concentration. Adsorption equilibrium was achieved in approximately 50 min with a maximum adsorption capacity at pH 5.0. The Langmuir isotherm was found to be well fitted on the adsorption behavior. The maximum metal adsorption capacities in single ion solution in mole basis were in the order Cu(II) > Cr(VI) > Mn(II) > Zn(II) > Cd (II) > Fe(II). It was found that introducing porogen in the polymerization mixture produced the copolymer beads with better adsorption capacity. The maximum Cu(II) adsorption capacity of chelating poly(GMA-co-HEMA) beads were 1.35 mmol/g (85.79 mg/g) measured from the beads prepared in the presence of 1-heptane with 50% dilution. Consecutive adsorption–desorption experiments showed that crosslinked poly(GMA-co-HEMA) micro-beads can be reused almost without any change in the adsorption capacity.     

C-6羧基氧化纤维素醋酸酯的制备和性能

以溶解级木浆作为原料,通过TEMPO（2,2,6,6四甲基哌啶1氧化物自由基）/NaClO/NaClO₂氧化体系对纤维素C-6羟基进行氧化,经过乙酰化处理后制备出C-6位含羧基的氧化纤维素醋酸酯。用红外光谱（IR）、X-射线衍射（XRD）和核磁共振（NMR）等手段表征了产物的结构,用热重分析（TGA）和差示扫描量热法（DSC）测试了产物的热性能。结果表明:所合成氧化纤维素醋酸酯的C-6位羧基取代度为0.15,乙酰基取代度为2.72（其中C 2为0.93、C-3为0.98、C 6为0.81）且取代均匀性较好;用C-6羟基的选择性氧化预处理可实现纤维素的可控酯化;产物能溶于DMSO（二甲基亚砜）;产物的晶型由纤维素Ⅰ型转变成纤维素Ⅱ型。氧化纤维素醋酸酯在185℃发生玻璃化转变,在257℃熔融。乙酰基的接入,使产物的热塑性提高。     

甘蔗渣基氧化石墨烯制备条件的响应曲面法优化设计

以甘蔗渣为基质采用改进Hummers法制备氧化石墨烯(GO),利用响应曲面法优化实验设计对甘蔗渣为基质的GO制备条件进行优化。选取碳粉用量、高锰酸钾用量、浓硫酸用量和超声时间作为4个变量因素,以制备的GO的红外特征吸收峰强度为响应值,利用Design-Expert软件进行数据分析,确定甘蔗渣基GO的最佳条件为:碳粉用量3.39g、高锰酸钾用量4.21g、浓硫酸用量20.68mL、超声时间7.75h。扫描电子显微镜和傅里叶变换红外光谱仪分析表明,在最佳条件下制备的GO具有明显的片层结构,特征峰出现在1500cm^-1、2300cm^-1、2400cm^-1和3500cm^-1处。     

Synthesis of WO(3) nanoparticles using a biopolymer as a template for electrocatalytic hydrogen evolution

Tungsten trioxide nanoparticles were prepared by a simple approach using chitosan biopolymer as a template. These nanoparticles were characterized using x-ray diffraction, Raman spectroscopy, transmission electron microscopy and high resolution transmission electron microscopy. The average size of the WO(3) nanoparticles is 42?nm, and they intercalate a larger amount of hydrogen than tungsten trioxide, which is prepared without chitosan. The materials are tested for their electrocatalytic hydrogen evolution in a sulfuric acid medium, where WO(3) nanoparticles show a fourfold higher activity than bulk tungsten trioxide.     

有序介孔炭分子筛膜的制备与表征

以三嵌段共聚物P123为结构导向剂和有机碳源,正硅酸乙酯为无机前驱体,在微量酸的催化条件下,结合非水体系蒸发诱导自组装技术与溶胶-凝胶工艺,采用浸渍-提拉法制备了介孔炭分子筛膜,研究了陈化温度对介孔炭膜结构的影响。通过透射电镜(TEM)、N2物理吸附-脱附、场发射扫描电镜(FESEM)和热重分析(TGA)对膜体的形貌结构性能进行了表征。结果表明,P123是优良的制膜材料,硫酸的预处理提高了P123的碳转化率,是成膜的关键因素之一。所制备的膜体材料由一定取向的类碳纳米管阵列组成;膜体表面致密、光滑无裂纹,具有孔径均一的对称结构。同时可以通过改变涂膜液的陈化温度来调节炭分子筛膜的孔径大小。     

Cross-linking regulators in one-step synthesis of macronet ion-exchangers

Hydrophillic macronet resins were prepared via a route which includes simultaneous sulphonation and cross-linking of styrene-acrylonitrile copolymer and polystyrene foam. Chlorosulphonic acid was employed as both the sulphonating reagent for the introduction of the sulphonic acid group on styrene units and the medium for the formation of sulphone-type cross-links. Controlled cross-linked structures were achieved by the parallel participation of acetic acid or acetic anhydride as sulphone cross-bridging regulators. The reaction yield, as well as the properties of the formed gels, were studied in respect to the cross-linking regulator concentration and the chlorosulphonic acid flow rate. Both strongly and weakly acidic ion-exchangers on the same substrate were achieved when styrene-acrylonitrile copolymer was used as a raw material. The synthesized macronet ion-exchangers were found to exhibit high swelling abilities and intermediate ion-exchange capacities while scanning electron microscopy (SEM) revealed their morphology.     

Versatile method for synthesis of electrically conductive polypyrrole-polystyrene clay nanocomposites using ATRP and chemical polymerisation methods

A synthetic route for the preparation of a novel solution copolymer derived from styrene (St), pyrrole (Py) and its organoclay nanocomposite with conductive and mechanical properties is demonstrated. The electroactive copolymer of polystyrene-g-polypyrrole (PSt-g-Ppy) nanocomposite was successfully prepared by atom transfer radical polymerisation (ATRP) and chemical polymerisation methods. First, potassium pyrrole was reacted by α-chlorophenyl acetyl chloride to prepare an initiator that can polymerise styrene by ATRP technique. Then, polypyrrole was prepared by chemical polymerisation using FeCl₃ as an oxidant in dichloromethane^,s solvent. Nanocomposites of the copolymer with modified montmorillonite were prepared with a solution intercalation method. The conductivity of the copolymer was measured by the four-point probe method. The structures of the intermediate, copolymer and nanocomposite were investigated by Fourier transform infrared spectroscopy, ¹H-NMR and X-ray diffraction techniques. The molecular weight of the copolymer was determined by gel permeation chromatography. Their thermal behaviour was examined by differential scanning calorimetry and thermogravimetric analyses.     

AA－AM－SAS三元共聚物的合成及其阻垢性能

以水为溶剂，过硫酸盐为引发剂，合成了丙烯酸（ＡＡ）、丙烯酰胺（ＡＭ）和烯丙基磺酸钠（ＳＡＳ）三无共聚物（ＡＡ－ＡＭ－ＳＡＳ）。用ＩＲ、ＮＭＲ和热分析方法时共聚物进行了表征和测定，并对共聚物的阻垢性能进行了测定。结果表明，合成的三元共聚物是一种性能优良的阻垢分散剂。     

Macroporous hydrogels based on 2-hydroxyethyl methacrylate

Crosslinked macroporous hydrogels based on 2-hydroxyethyl methacrylate (HEMA)—[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MOETACl) copolymer, HEMA-MOETACl—methacrylic acid (MA) terpolymer, and on a polyelectrolyte complex of HEMA—MA copolymer with poly(MOETACl) were prepared. All the hydrogels were prepared in the presence of fractionated sodium chloride particles. The hydrogels were characterized by the number of pores and the total volume of all pores in unit volume, the average volume and the average diameter of single pore. Morphology of the hydrogels was investigated by confocal and scanning electron microscopy. The hydrogels based on polyelectrolyte complexes were also characterized by chemical composition. Homogeneous (non-porous) hydrogels with the same composition as macroporous hydrogels were prepared and characterized by their biocompatibility.