Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

油基钻井液的推广及循环利用

针对普通水基钻井液在钻进中强、强水敏性油藏时会造成储层污染、产量降低的问题,指出了油基钻井液在钻进该类油藏时的优势和其成本高、对生态环境有污染的缺点。为了大面积推广应用油基钻井液,重点介绍了油基钻井液的特性和稳定性影响因素,并通过室内评价证明了油基钻井液在油层保护中的良好效果,着重阐述了油基钻井液在王庄油田的现场应用情况,并探讨了油基钻井液的循环利用技术。研究结果表明,油基钻井液不仅具有良好的油层保护效果,而且具有较好的社会经济效益。     

非水解溶胶-凝胶法低温合成硅酸锆

以工业纯ZrCl4、 Si(OC2H5)4为前驱体,通过非水解溶胶-凝胶法合成了硅酸锆.采用DTA-TG和XRD等测试手段研究了凝胶热处理过程中的物相变化.结果表明:当前驱体溶胶中未引入矿化剂时,硅酸锆的合成温度高达1450℃;相比之下,溶胶中引入矿化剂LiF后在600℃下便开始出现了ZrSiO4衍射峰,在700℃合成的硅酸锆不仅合成率高,而且晶体发育好,实现了低温合成硅酸锆的目标.     

Photocatalytic degradation of 2,2‐bis(4‐hydroxy‐3‐methylphenyl) propane (BPP) based on molecular recognition interaction

BACKGROUND: Endocrine disruptors in the aquatic environment and their potential adverse effects are currently issues of concern. One of these endocrine disruptors is 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane (BPP). In this work the molecular recognition interaction of BPP with β‐cyclodextrin (β‐CD) was studied using IR spectroscopy and steady state fluorescence spectroscopy, and the photocatalytic degradation behaviour of BPP based on molecular recognition interaction was investigated in a TiO₂/UV–visible (λ_max = 365 nm) system. This might provide a new method for the treatment of some organic pollutants in wastewater. RESULTS: β‐CD reacts with BPP to form a 1:1 inclusion complex, the formation constant of which is 4.94 × 10³ L mol^?1. The photodegradation rate constant of BPP after molecular recognition by β‐CD showed a 1.42‐fold increase in the TiO₂/UV–visible (λ_max = 365 nm) system. The photodegradation of BPP depended on the concentration of β‐CD, the pH value, the gaseous medium and the initial concentration of BPP. The photodegradation efficiency of BPP with molecular recognition was higher than that without molecular recognition. After 100 min of irradiation the mineralisation efficiency of BPP after molecular recognition by β‐CD reached 94.8%, whereas the mineralisation efficiency of BPP before molecular recognition by β‐CD was only 40.6%. CONCLUSION: The photocatalytic degradation of BPP after molecular recognition by β‐CD can be enhanced in the TiO₂/UV‐visible (λ_max = 365 nm) system. This enhancement is dependent on the enhancement of the adsorption of BPP, the moderate inclusion depth of BPP in the β‐CD cavity and the increase in the frontier electron density of BPP after molecular recognition. Copyright © 2008 Society of Chemical Industry     

Recovery of pyruvic acid with weakly basic polymeric sorbents

BACKGROUND: Carboxylic acids are among the most important substances that can be manufactured from biomass. However, the recovery of carboxylic acids from fermentation broths presents a challenging separation problem. To avoid the production of waste salts and net consumption of chemicals in the calcium carboxylate salt process, the use of reversible chemical complexation with polymeric sorbents and extractants is attractive for carboxylic acid recovery. Pyruvic acid is widely used in the manufacture of medicines, pesticides and foodstuffs and can be produced by fermentation. Since the acidity of pyruvic acid (pK_a = 2.49) is stronger than that of normal carboxylic acids, and as few reports on the recovery of pyruvic acid are available, the sorption of pyruvic acid from aqueous solution on two types of weakly basic polymeric sorbent, tertiary amine D301R and primary amine D392, was investigated over a wide pH range and at various salt (MgSO₄) concentrations. RESULTS: Overloading adsorption of pyruvic acid on both weakly basic polymeric sorbents occurred, with the overloading of D392 being greater than that of D301R. The adsorption of pyruvic acid on both sorbents was greatly affected by the solution pH and the salt concentration in the aqueous phase. An overloading model was able to predict the experimental uptake data very well. CONCLUSION: Solution pH is one of the most important operating conditions, and both polymeric sorbents D392 and D301R can be used to recover pyruvic acid from dilute aqueous solution with high efficiency at a solution pH around 2. The uptake by D392 is greater than that by D301R owing to steric hindrance of the tertiary amine. Copyright © 2008 Society of Chemical Industry     

Electromagnetic properties of ferroelectric-ferrite ceramic composites

The NiFe₂O₄ and Pb(Zr_0.52Ti_0.48)O₃ ceramic composites are prepared by conventional solid state reaction method. The microstructural and morphological properties of the composites are studied by X-ray diffraction analysis and scanning electron microscopy. Results indicate that the ferrite and piezoelectric phases can co-exist in the composites. The relationship between the dielectric constant and frequency (40 Hz–40 MHz) as well as temperature is also investigated. It is noted that the transition temperature of the composites is about 380 °C. A double electric hysteresis loop is observed in our composites. The magnetic properties are relatively weak according to the magnetic hysteresis loop. With increase in the content of the ferrite phase, the permeability increases. The electromagnetic properties of the as-prepared composites are tunable according to the content of the NiFe₂O₄ phase.     

One‐step production of 2,3‐butanediol from starch by secretory over‐expression of amylase in Klebsiella pneumoniae

BACKGROUND: 2,3‐Butanediol (2,3‐BD) is a valuable chemical that can be biosynthesized from many kinds of substrates. For commercial biological production of 2,3‐BD, it is desirable to use cheap substrate without pretreatment, such as starch. However, there have been few reports on the production of 2,3‐BD directly from starch. RESULTS: In this work, gene malS coding for α‐amylase (EC 3.2.1.1) precursor was inserted into plasmid pUC18K, and secretory over‐expression of α‐amylase was achieved by engineered Klebsiella pneumoniae. The extracellular recombinant amylase accelerated the hydrolyzation of starch, and one‐step production of 2,3‐BD from starch was carried out by engineered K. pneumoniae. A 2,3‐BD concentration of 3.8 g L^?1 and yield of 0.19 g 2,3‐BD g^?1 starch were obtained after 24 h fermentation. CONCLUSION: The one‐step production of 2,3‐BD from starch was achieved by secretory over‐expression of amylase in K. pneumoniae. This would simplify the process and reduce the production cost considerably by enabling use of starch with minimal pretreatment. Copyright © 2008 Society of Chemical Industry