不对称S-烷基硫(二硫)代磷(膦)酸酯的新合成方法研究

70年代以前开发的有机磷杀虫剂品种中大多含有两个低烷氧基,因此具有对称结构(1)。而70年代以后,出现了一类含烷硫基和不对称磷原子的化合物(2),通常把它称为S烷基不对称磷酸酯类杀虫剂。这类杀虫剂的代表性品种有速丙磷(Heterophos)、丙溴磷(Pro-fenofos)、硫醚磷(Diphenprophos)、吡唑硫磷(Pyraclofos)、丙硫磷(Prothiofos)和甲丙硫磷     

外文杂志摘要

玉米螟抗性和敏感群体中3种Cry1A毒素作用，甲磺草胺对花生田的除草效果和安全性，异噁草酮对加拿大番茄一年生阔叶杂草的防除效果，家蝇对吡唑硫磷（pyraclofos）的代谢抗性机制     

4,5-二氢吡唑-5-硫酮类的合成和构效关系

许多种吡唑类化合物被研究用于农田并开发为农药。虽然,关于4,4-二取代的4,5-二氢吡唑-5-酮作为农药的报道不少,而相应的吡唑-5-硫酮类则尚未报道,仅有日本鸣门研究中心的Isao Tada等作了介绍。他们合成了一系列以吡唑硫酮为母体的新颖衍生物,主要筛选了4,5-二氢吡唑-5-硫酮类(DHPs)对某些螨类的防治活性,诸如棉红蜘蛛、神洲叶螨、桔红螨和榆全爪螨等,4,5-二氢吡唑-5-酮对它们则几无活性。鉴此,Isao Tada等合成了4,5-二氢吡唑-5-硫酮类化合物(图1),并评估了它们对棉红蜘蛛的杀螨活性。同时,根据化合物的物化参数和诸如疏水指数等容量因素,探讨了它们的构效关系。本文仅就其合成、杀螨活性和构效关系作一概述。     

"创制农药"的市场推广

随着中国农药工业的不断发展和壮大,国家对创制农药的大力扶持和鼓励,部分农药厂家技术实力的不断增强,中国自主知识产权的新农药也在不断涌现,诞生了如氟吗啉、噻菌铜(龙克菌)、噻森铜、噻唑锌、氯胺磷、硝虫硫磷、单嘧磺隆、单嘧磺酯、氯噻啉、申嗪霉素、长川霉素、丙酯草醚、异丙酯草醚、双甲胺草醚、倍速菊酯、呋喃虫酰肼、吡唑硫磷、壬菌铜、水合霉素、杀虫安、噻菌茂、金核霉素等新结构的农药成分.     

具有农药活性的吡唑衍生物研究进展

吡唑类衍生物因其具有广泛的生物活性受到人们的广泛关注。针对具有(3-氯-2-吡啶基)吡唑酰胺、吡唑磺酰(脲)或酰基(硫)脲、吡唑肟醚(酯)或醛腙、吡唑并嘧啶以及膦酸酯等结构的几类吡唑衍生物在农药研究中的进展,按照其不同的结构类型进行了分类综述,对其发展趋势及前景进行了展望。     

新型硫色满酮类化合物的合成及体外抗真菌活性

设计合成9种新型硫色满酮吡唑类化合物,并对其抗真菌活性进行初步评价。首先以取代苯硫酚为起始原料,合成中间体3-次苄基硫色满酮;利用苯甲酰肼与3-次苄基硫色满酮在酸性条件反应生成目标化合物。化合物结构通过核磁共振氢谱、质谱等技术进行确认,抗真菌活性实验表明,9种化合物对部分供试真菌有好的活性。硫色满酮吡唑类化合物在体外的抗真菌活性有待进一步研究。     

新型含吡唑基1,2,4-三唑席夫碱的合成

以5-苯基-3-吡唑甲酰肼(1)为原料,经5-苯基-3-吡唑甲酰肼二硫代甲酸钾(2)与水合肼发生闭环反应制得4-氨基-5-(5-苯基吡唑-3-基)-1,2,4-三唑-3-硫酮(3);化合物3与芳香醛经缩合反应得到6种4-(芳基次甲亚胺基)-5-(5-苯基吡唑-3-基)-1,2,4-三唑-3-硫酮衍生物4a～4f。用IR,~1H NMR,元素分析等对所合成的目标产物结构进行了表征;目标产物存在Z/E异构体,室温下以E式异构体形式为主。     

7种药剂防治水稻3代三化螟药效试验

对90%杀虫单可湿性粉剂、48%乐斯本乳油、5%锐劲特胶悬剂、20%三唑磷乳油、30%吡唑磷乳油(稻欣)、20.2%阿维唑磷乳油(稻卫)、50%敌毒乳油(赛利)等7种药剂进行了防治水稻3代三化螟的药效试验,结果表明,在常规用药量情况下,以锐劲特药效最好;吡唑磷、阿维唑磷、三唑磷药效次之。建议在1~2龄幼虫盛发期施药为宜。     

双硫磷的合成

介绍了一种以三氯硫磷作为原料的双硫磷的合成方法,得到了高品质的双硫磷产品.     

氟虫腈的催化氧化合成研究

氟虫腈是一高效、广谱的吡唑类杀虫剂,以5-氨基-3-氰基-1-(2,6-二氯-4-三氟甲基苯基)-吡唑为原料,经硫氰化、缩合、催化氧化合成了氟虫腈。     

注流孔结构对中间包流场影响的物理模拟

针对某钢厂十流中间包紊流抑制器注流孔结构不合理引起流场分布差、各流铸坯质量不均的问题,运用相似原理,使用相似比为1:3的物理模型进行水模型实验,设计不同的注流孔结构研究流体在中间包的平均停留时间曲线及流场显示特征,明晰注流孔结构对中间包流场的影响规律,优化紊流抑制器注流孔结构,达到中间包流场优化及浸入式水口各流一致性提高的目标。结果表明,长距离多流中间包在无堰坝结构条件下,紊流抑制器的注流孔内径尺寸、数量及开孔方向对中间包流场都有影响,注流孔内径的影响最为显著,数量次之。设计的最佳注流孔内径由原型的53 mm缩小至30 mm,死区比例由54.05%降至34.69%,F曲线最大标准差由0.0154降低至0.0035,中间包流场得到改善,各流一致性显著提高。当注流孔数量由1个增加至3个,死区比例由34.69%增大至46.05%,F曲线最大标准差由0.0035增大到0.0062,注流孔数目越多,流场死区比例反而越大,各水口流场的一致性越差。对长距离多流中间包,建议主要通过适当改变注流孔内径及减少孔数来改善中间包流场,提高各流一致性。     

Influence of capillary condensation on heat and mass transfer in the grain of a Fischer-Tropsch synthesis catalyst

A mathematical model of heat and mass transfer processes in the grain of the Fischer-Tropsch synthesis catalyst is presented that takes into account the effect of the capillary condensation of the products of the synthesis in the pores of the catalyst. The influence of capillary condensation on the processes of the diffusion transfer of heat and mass in the catalyst grain is analyzed using the proposed model. Dependences of the efficiency factor of the grain on the pressure and temperature of the process and the partial pressure of various components of a mixture are presented. The possibility of determining the optimum pressure and temperature of carrying out the process for the catalyst of a certain structure is shown.     

含缩水甘油基／氨基丙烯酸酯共聚物乳液的聚合稳定性

研究了乳胶粒组成对含有缩水甘油基,羧基和胺基的丙烯酸酯多层核壳型乳液聚合稳定性的影响规律,探讨了聚合过程的凝聚机理。研究表明：官能团间的交联凝聚作用和水溶性聚合物的架桥凝聚作用是本体系凝聚物形成的主要原因。     

An increase in thermodynamic efficiency and compactness of contact apparatuses via spatially organized structure of the active material bed

The possibility of filling the hollow input (diffuser) and output (confuser) sections of contact apparatuses by an active material is analyzed. The equation determining the distribution function of the sizes of material particles along the axis of a conelike apparatus, which provides the minimum volume of the bed of particles at the specified values of the total surface area of the interfacial contact in the bed and total flow resistance of the bed, is derived. It is shown that the change in the conventional shape of the apparatus to a construction in the form of a junction of two truncated cones filled with the active material allows one to decrease the total volume of the apparatus by 30%. The dependence of the thermodynamic efficiency and compactness of the regenerative facility on the particle size of the active material bed is numerically analyzed. The existence of a critical particle size which determines the minimum necessary volume of the bed providing high thermodynamic efficiency of the process is shown.     

Manifestation of the Urbach rule in the fundamental electronic absorption spectra of halide salt melts: I. Tails of the absorption edge of alkali metal halide melts

The long-wavelength tails of the fundamental electronic absorption spectra of alkali metal halide melts have been investigated. The obtained values of the absorption characteristics of the alkali metal halide melts have confirmed the assumption that, over a wide temperature range (600–900°C), the exponential tail of the absorption coefficient of these disordered systems is associated with the presence of the spectrum of fluctuating electronic levels extended to the band gap in the melts under investigation. The fulfillment of the Urbach rule is the limiting case of the general exponential dependence of the optical absorption coefficient in the ultraviolet region of the fundamental absorption edge. In the studied series of melts of alkali metal halide salts, the absorption coefficient in the region of tails of the spectral curves of the halide systems decreases from LiCl to CsCl and from LiCl to LiI. An analysis of the results obtained from the investigation of alkali metal halides has revealed an interrelation between the main parameters of the Urbach rule and between these parameters and the temperature coefficient of the band gap.     

玻璃纤维增强制件注射成型过程的模具磨损原因及规律

玻璃纤维增强聚醚酰亚胺（PEI）薄壁制件注射成型过程中,易对模具型芯产生磨损,从而严重影响制件成型品质。以某型号手机听筒薄壁制件为例,根据生产实践分析了型芯表面的微观磨损特性,采用数值计算方法研究了型腔近壁面的熔体流动行为以及型芯表面材料的冲蚀破坏形式与磨损规律。结果表明,注塑过程中型芯表面材料发生冲蚀磨损形成月牙形凹槽,型腔近壁面上的熔体流速决定了月牙形凹槽的形貌和尺寸,玻璃纤维粒子的入射角和倾角决定了型芯表面材料的冲蚀破坏形式,冲蚀磨损量随着玻璃纤维粒子侧倾角的增大不断增加,随着入射速度的增大呈指数型增加。     

The electrochemistry of alloys

The features of the dissolution of the components of alloys forming solid solutions were examined. It was shown on the example of the anodic dissolution of alpha-brass that the process of the selective dissolution of zinc observed in the initial period is limited by the stage of its non-stationary diffusion from the bulk of the alloy and is subsequently replaced by uniform dissolution. During prolonged corrosion of brass, secondary selective dissolution is observed, which is due to the re-deposition of copper.It was established that intensive preferential dissolution of iron from Fe-Cr alloys takes place in the passive region and leads to the enrichment of the passivating chromium film. The results obtained from an investigation of the dissolution of the components of Fe-Cr-Mo alloys in the active region permit the conclusion that the favourable effect of small additions of molybdenum on the corrosion stability of alloys is due to the fact that this element, in view of its great inclination to passivation, blocks the most active centres of the surface in the process of its dissolution.In order to establish the mechanism of the active dissolution of Fe-Cr, alloys, the effect of the potential and pH of sulphate solutions on the partial dissolution rates of iron and chrome from these alloys in the active state was established. It was shown that the Tafel slopes and the order of magnitude of the reaction for the H⁺ ions for both components were the same and close to the corresponding values for pure iron (at low concentrations of chromium in the alloy) or for pure chromium (when the chrome content in the alloys was 13% or more). A mechanism was suggested for the active dissolution of alloys that explained the discovered regularities.     

Mathematical description of the synthesis of butadiene rubber with allowance for the branching of a polymer under conditions of the separate supply of a reaction mixture to the reactors of a cascade

Mathematical modeling of the synthesis of butadiene rubber on a neodymium-based catalytic system under conditions of the separate supply of a reaction mixture to the apparatuses of a cascade is performed. Expressions are derived for calculating the characteristics of the branching of the polymer with allowance for the additional supply of the reaction mixture to the second apparatus of the cascade. An analysis of the influence of the flow rate of an additional stream of the reaction mixture to the second apparatus of the cascade and operating parameters on the molecular weight characteristics and branching of the polymer is performed.     

水泥预粉磨装备及技术发展现状的分析

重视预粉磨装备及技术的发展,就是重视水泥联合(半终)粉磨工艺系统的粉磨效果。联合(半终)粉磨系统中充分利用了料床预粉磨段粗处理的技术特性,同时发挥了管磨机段独有的磨细与整形功能,真正实现了“分段粉磨”过程中两段之间的优势互补。预粉磨段主机的吸收功耗越大,管磨机段主电机电耗降低越多,系统的总节电效果越显著。随着预粉磨段主电机功率与管磨机主电机装机功率比值的增加,预粉磨段处理能力进一步增大,投入的功耗越多,整个粉磨系统电耗降低的幅度也更大。在水泥粉磨生产线改造过程中,将高压力多辊外循环立磨用于预粉磨段,是降低粉磨电耗的发展方向之一。辊压机联合(半终)水泥粉磨系统中辊压机的吸收功耗至少应≥9.0 kWh/t,高值可以达到12.0 kWh/t,在此范围内越高越好。辊压机联合(半终)粉磨系统中,辊压机运行常常表现为不够平稳、时有偏辊现象发生、液压系统压力输出不稳定、操作不灵敏、液压系统现场“跑冒滴漏”严重、控制关键元器件购置困难等。建议采用辊压机SPC控制系统进行改造,以确保辊压机应保持稳定和较高的工作压力,确保良好的挤压做功能力,确保有更多的细粉产出,有利于系统高效低耗运行。     

Die differentielle Doppelschichtkapazität an der Phasengrenze Quecksilberanorganischer Elektrolyt—II. Das Kapazitätsminimum

In the negative range of charge, the differential double-layer capacitance at the interface of mercury and an inorganic electrolyte solution shows a characteristic minimum. This minimum is independent of the nature of the ion, of the concentration of electrolyte and of the temperature. However, the solvent strongly influences the capacitance of the minimum. The metal charge at which the minimum occurs is uninfluenced only by the temperature. Changes of the concentration of the electrolyte as well as of the nature of the anion are able to cause a shift of the minimum.