二甲基硫醚的光解特性

本文对二甲基硫醚（ＤＭＳ）在有氧、无氧及有Ｈ２Ｏ２存在的情况下紫外光辐照，然后在２０ｍ长光程 籍富里叶红外光谱仪测定光解产物的吸光谱，实验表明在无氧的情况下ＤＭＳ的Ｃ－Ｓ键断裂，并生成ＣＨ３ＳＳＣＨ３及Ｃ２Ｈ６，在有氧存在下生成ＨＣＨＯ及ＣＨ３ＳＯ３Ｈ〈在有Ｈ２Ｏ２存在下生成ＣＨ３ＳＳＣＨ３，本文讨论了的可能机理，合理地解释光解产物的生成。     

直接法合成甲基（氢）二氯硅烷新工艺研究

本文通过催化作用原理研究，提出了以Ｓｉ、ＣＨ３Ｃｌ为原料?直接法合成ＣＨ３ＳｉＨＣｌ２的新工艺。采用ＣｕＣｌ－Ｎｉ－Ｚｎ催化体系不但能使ＣＨ３Ｃｌ适量分解产物ＨＣｌ与Ｓｉ、ＣＨ３Ｃｌ反应并有效地转化为目的产物ＣＨ３ＳｉＨＣｌ２，由小试和φ４００ｍｍ流化床中试所得的混合单体中，ＣＨ３ＳｉＨＣｌ２含量〉１５％，（ＣＨ３）２ＳｉＣｌ２〉５０％，为工业化生产有机硅含氢单体开辟了新的途径。     

直接法合成甲基（氢）二氯硅烷新工艺研究

本文通过催化作用原理研究，提出了以Ｓｉ、ＣＨ＿３Ｃｌ为原料，直接法合成ＣＨ＿３ＳｉＨＣｌ＿２的新工艺．采用ＣｕＣｌ－Ｎｉ－Ｚｎ催化体系不但能使ＣＨ＿３Ｃｌ适量分解产生ＨＣｌ．而且还能促进ＨＣｌ与Ｓｉ、ＣＨ＿３Ｃｌ反应并有效地转化为目的产物ＣＨ＿３ＳｉＨＣｌ＿２，由小试和４００ｍｍ流化床中试所得的混合单体中，ＣＨ＿３ＳｉＨＣｌ＿２含量＞１５％，（ＣＨ＿３）＿２ＳｉＣｌ＿２＞５０％，为工业化生产有机硅含氢单体开辟了新的途径。     

苯基三甲氧基硅烷制备工艺

由苯基三氯硅烷（ＰｈＳｉＣｌ３）和甲醇（ＣＨ３ＯＨ）醇解制备苯基三甲氧基硅烷[Ｐ ｈＳｉ（ＯＣＨ３）３]过程中，采取及时驱除氯化氢（ＨＣｌ）的方法，控制副反应发生 ，可提高ＰｈＳｉ（ＯＣＨ３）３的质量，收率达８０％以上。     

二甲基硫醚（CH_3－S－CH_3）

二甲基硫醚（ＣＨ＿３－Ｓ－ＣＨ＿３）此品系无色易挥发液体，溶于乙醚和乙醇，不溶于水。其密度约０．８４５，熔点－８３℃，沸点３７．５℃。生产二甲基硫醚的工艺路线主要有两条：１．ＣＨ＿３Ｏ与Ｈ＿２Ｓ合成法：２．ＣＨ＿３ＯＮ与ＣＳ＿２合成法：４ＣＨ＿３ＯＨ...     

含硫酸和亚砜基团的高分子载体三氯化钕配合物的合成及其催化活性

合成了含－ＣＨ２ＳＨ和－ＣＨ２ＳＯＣＨ３功能团的高分子载体氯化稀土配合物Ｐ—ＣＨ２ＳＨＮｄＣｌ３和Ｐ－ＣＨ２ＳＯＣＨ３·ＮＤＣｌ３．Ｐ－ＣＨ２ＳＨ·ＮＤＣｌ３对丁二烯聚合没有催化活性，Ｐ－ＣＨ２ＳＯＣＨ３·ＮｄＣｌ３对丁二烯聚合有催化活性．其催化体系有很高的定向效应，聚丁二烯顺－１，４结构含量在９５％以上。     

竹红菌素在DMF—H2O混合体系中的电化学研究

本文研究了竹红菌素ＨＡ，ＨＢ以及１３－ＳＯ３Ｎａ－ＤＤＨＡ在ＤＭＦ－Ｈ２Ｏ（体积分数ψ＝１）混合体系中的电化学氧化还原性质，结果表明，它们都为两步单电子还原过程，反应机理为：油 ＨＡ，ＨＢ：ＨＡ（ＨＢ）＋ｅ＋Ｈ＾＋－ＨＡ（ＨＢＨ）＋ｅ－ＨＡＨ，水溶性１３－ＳＯ３Ｎａ－ＤＤＨＡ：（第一步）１３－ＳＯ３Ｎａ－ＤＤＨＡ＋ｅ－１３－ＳＯ３ＮａＤＤＨＡ，（质子化）１３－ＳＯ３Ｎａ－ＤＤＨＡ＋Ｈ＾＋－１３－Ｓ     

苯基三甲氧基硅烷制备工艺

由苯基三氯硅烷（ＰｈＳｉＣｌ＿３）和甲醇（ＣＨ＿３ＯＨ）醇解制备苯基三甲氧基硅烷［ＰｈＳｉ（ＯＣＨ＿３）＿３〕过程中，采取及时驱除氯化氢（ＨＣｌ）的方法，控制副反应发生，可提高ＰｈＳｉ（ＯＣＨ＿３）＿３的质量，收率达８０％以上。     

3—甲氧基—4—羟基扁桃酸的合成

３－甲氧基－４－羟基扁桃酸是制备香料、医药等的重要中间体，如大量用于生产香兰素和广谱抗菌药ＴＭＰ。通过愈创木酚与乙醛酸在碱性条件下进行缩合反应是较先进的合成方法，反应方程式如下：ＯＨＯＣＨ３＋ＣＨＯＣＯＯＨＯＨ－→ＣＨ（ＯＨ）ＣＯＯＨＯＨＯＣＨ３据文...     

嘧啶氧(硫)苯甲酸类除草剂的创制经纬

嘧啶氧 (硫 )苯甲酸类除草剂也称嘧啶水杨酸类除草剂是由日本组合化学公司发现的。其研制的过程是随机筛选与模拟合成的结合。发现史如下 :ⅢＨＯＮＮＣＨ３ＣＯ２ＣＨ３ⅣＣＯ２ＣＨ３ＮＮ ＨⅤＣＯ２ＲＸＹⅡＮＯ２ＣＯ２ＣＨ３ＯＣＦ３ＣｌⅠＯＣｌＣＦ３ＯＮＮＯＣＨ３ＯＣＨ３ＣＯ２ＲＲ＝ｌｏｗｅｒａｌｋｙｌ，ＨＸ＝ｅｌｅｃｔｒｏｎ－ｗｉｔｈｄｒａｗｉｎｇｇｒｏｕｐＮＮＮＮⅧＡｃｔｉｖｅＣｌＣＯ２ＣＨ３ＯＯＣＨ３Ｗｅａｋｌｙａｃｔｉｖｅ ⅦⅥｌｎａｃｔｉｖｅＯＣＨ３ＯＣＯ２ＣＨ３ ＣｌＯＣＦ３ＯＣＦ３ＣＯ２ＣＨ３Ｏ…     

三氟甲烷和氯化氢气体在不同溶剂中的溶解度

测定了三氟甲烷和氯化氢气体在烷烃、氯代烃、醇、酮、醚、酯等几种有机溶剂中的溶解度,比较了这两种气体在不同溶剂中的溶解度差别,讨论了采用溶剂吸收法对其混合气体进行分离的可能性.结果表明,醇类溶剂如甲醇、正丁醇和甘油对氯化氢具有较高溶解度,在较高的温度下又容易解吸,而且对低压下三氟甲烷的溶解度极低,尤其是甘油基本上不溶解三氟甲烷,使之有可能作为水吸收剂的替代溶剂用于氯化氢和三氟甲烷的分离,以大大降低吸收液对设备的腐蚀性.     

二溴苯三元物系固液平衡测定与正规溶液模型

采用差示扫描量热法,通过对一系列"拟二元"物系固液平衡数据的测定,得到了邻二溴苯、间二溴苯和对二溴苯三元物系的固液平衡数据.实验结果表明本物系为简单低共熔型,其低共熔摩尔分数组成和温度分别为:邻二溴苯(x1) 间二溴苯(x2) 对二溴苯(x3),x1=0.4259,x2=0.5345,x3=0.0396,Tcu=238.5 K.文中绘制出了其相应的低共熔三元固液平衡相图,并采用正规溶液模型,利用二元溶液的三个相互作用参数对实验数据进行了关联,温度均方根偏差仅为1.32 K,说明正规溶液模型适用于上述弱极性异构体三元物系固液平衡的计算.     

Dialysis of aqueous solutions of nitric acid and ferric nitrate

The separation of an HNO₃ + Fe(NO₃)₃ mixture using an anion-exchange membrane Neosepta-AFN has been investigated in a two-compartment dialysis cell with stirrers. The experiments have proved that this membrane is a very good separator for this mixture, because nitric acid permeates well through the membrane and ferric nitrate is efficiently rejected. The separation is very efficient at high acid concentrations or low content of the salt in the mixture to be dialyzed.     

Synthesis of diphenylamine derivatives on Pd/C catalyst

2-Methyl-3’-hydroxydiphenylamine was synthesized from the mixture of 3-aminophenol, 3-nitrophenol, and 2-methylcyclohexanone in the presence of Pd/C catalyst. The optimum composition of the reaction mixture was determined for maximum yield of the diphenylamine derivative: with the molar ratio of 3-aminophenol: 3-nitrophenol fixed at 1 mmol: 2 mmol, the relative molar amounts of 2-methylcyclohexanone were varied between 3 and 96. At the optimum composition the amounts of Pd/C catalyst were varied threefold in order to investigate the effect of Pd on the product yield. The results obtained from the reaction mixture containing 1 mmol of 3-aminophenol were satisfactorily reproduced for the reaction mixture containing more than 10 mmol of 3-aminophenol. The formation of this diphenylamine derivative could be interpreted using the mechanism for the catalytic synthesis of 2-methyl-4-methoxydiphenylamine which we had optimized previously.     

含硫废水中提取造纸浆料用亚硫酸钠混合物

氨基苯甲醚、氨基苯乙醚生产中产生的含硫废水，采用浓缩方法得到了亚硫酸钠混合物，该混合物可用于造纸浆料。浓缩法处理含硫废水不仅简单可行，而且具有明显的经济和环境效益，硫化物回收率达到１００％ 。     

Initiation of multifuel mixtures with bifurcation structures

The theory of a strong explosion is used as a basis for the development of an experimental technique for determining the source energy that ensures initiation of the combustible mixture. The technique is tested in experiments aimed at determining the critical energies of spherical detonation initiation E*₃ with the use of an electric discharge for a stoichiometric acetylene–oxygen mixture and also for two-fuel mixtures (acetylene–nitrous oxide–oxygen) possessing bifurcation properties of cellular structures. The critical energy E*₃ for the stoichiometric two-fuel mixture in terms of both fuels with a bifurcation structure is several-fold lower than the value of E*₃ for the monofuel mixture whose cell size at a given pressure is determined by the large scale of bifurcation cells. This result testifies that the value of E*₃ decreases with increasing number of “hot points,” which are numerous regions of collisions of large-scale and small-scale transverse waves in the mixture with bifurcation properties.     

甲醇-氨-空气多元爆炸性混合气体的爆炸特性与应用

对甲醇-氨-空气多元爆炸性混合气体的爆炸特性与爆炸形态进行了系统的研究,结果表明：甲醇-氨-空气(甲醇∶氨=1∶1.1)爆炸性混合气体的浓度爆炸极限为12.85%～45.25%;该爆炸性混合气体爆炸只有冷焰与爆燃2种形态,不会出现强烈的爆轰现象;氮气与水蒸气对甲醇-氨-空气爆炸性混合气体爆炸具有一定的惰化作用;氨对甲醇-空气爆炸性混合气体爆炸具有明显的阻尼效应,随着甲醇/氨的比值降低,其爆炸危险度、爆炸最高压力以及压力上升速率均会降低。用于指导甲醇氨氧化的工业生产的技术改造,具有抑爆效果好、防爆措施有力、生产能力大幅度增加、经济效益明显等特点。     

纳米LaCoO3对RDX基混合炸药的热分解特性和感度的影响

用DSC和DTA研究了LaCoO3对含AP的RDX基混合炸药热分解特性的影响。结果表明,纳米LaCoO3对含有AP的RDX基爆炸混合物的热分解具有一定的催化作用;纳米LaCoO3使RDX基混合炸药的撞击感度和热感度降低,摩擦感度增大。     

Ternary nucleation: kinetics and application to water–ammonia–hydrochloric acid system

The ternary nucleation of an ideal mixture of three alcohols and a non-ideal mixture of water, ammonia and hydrochloric acid, which is relevant in atmosphere, have been investigated theoretically. In the ideal mixture of three alcohols, the nucleation rates obtained using simplified kinetic approach are compared with the nucleation rates given by a detailed kinetic model. The simplified model is seen to underestimate nucleation rates by 2–3 orders of magnitude. This is mainly due to the crude estimate for the Zeldovich factor in the simplified model. We have proposed a modification to the simplified model. The improved model gives order-of-magnitude estimates for the nucleation rates. The ternary nucleation of water–ammonia–hydrochloric acid is studied with the improved model. The results have been compared with binary nucleation of water and ammonium chloride. The results show that water–ammonia–hydrochloric acid mixture is effectively a two-component system.     

Conditions of self-ignition upon pulsed high-pressure injection of combustible gases into a bounded space

The temperature of a fuel-air mixture in the vicinity of a contact discontinuity formed in the process of exhaustion of a combustible gas (hydrogen, methane, and propane) into air after the shock-tube membrane breakdown is quantitatively evaluated. It is shown that conditions necessary for self-ignition of such a mixture are reached only when the shock wave reflected from the tube bottom passes through the mixture. An increase in the initial pressure of air in the tube exerts a dramatic adverse effect on the probability of self-ignition of the mixture. In addition, the calculation shows that favorable conditions for self-ignition of a methane- and propane-air mixtures, even after the secondary compression of the mixture behind the reflected-wave front, are observed only for a comparatively high pressure of the combustible gas prior to its exhaustion into the tube and simultaneously for a low initial pressure of air in the tube. The calculation results are in good agreement with available experimental data for a hydrogen-air mixture. Translated fromFizika Goreniya i Vzryva, Vol. 36, No. 3, pp. 3–10, May–June, 2000. This work was supported by the Russian Foundation for Fundamental Research (Grant No. 97-01-00506).