国外过氧化氢在化学合成中应用研究进展

介绍了近期国外过氧化氢在部分化学品合成中应用研究新进展 ,产品包括过碳酸钠、过碳酰胺、4Na2 SO4·2H2 O2 ·NaCl加合物、叔胺氧化物、水合肼、二羟基苯、季铵盐过氧化氢和甲乙酮肟。内容涉及产品质量 (纯度、安定性、溶解速率、外观等 )、产品收率、催化剂、工艺过程等方面改进。主要介绍专利技术。     

Crystallography and equilibrium solubility for ammonium and potassium orthophosphites and hypophosphites

The composition and solubility properties of eight ammonium and potassium orthophosphites and hypophosphites were determined to evaluate the potential of these classes of materials for increasing the plant nutrient content of liquid fertilizers. Phase relationships for the systems (NH₄)₂O-P₂O₃-H₂O, K₂O-P₂O₃-H₂O, (NH₄)₂O-P₂O-H₂O, and K₂O-P₂O-H₂O were determined along with the crystallographic properties (X-ray and optical) of the solid phases. Toxicity and phosphite response was tested in greenhouse experiments for the compounds.     

铝电解电容器用新型宽温高压工作电解液

采用异癸二酸铵为主溶质,乙二醇和γ-丁内酯为复合溶剂,制备新型宽温(-40~105℃)、高压(400 V)铝电解电容器工作电解液,并检测了该电解液和用该电解液生产的电解电容器的性能。测试结果表明,该工作电解液25℃时电导率达到1.6 mS/cm,闪火电压为480 V,-40℃下未见晶体析出;CD 110/400 V铝电解电容器试样的漏电流≤10μA,损耗0.03,容量变化率只有-3%。经过105℃高温贮存250 h后各项电气性能不仅优于国家标准,而且能达到严格的企业标准。     

Heat-release mechanism in ammonium dinitramide flame

To verify the adequacy of various models of heat release in ammonium dinitramide flame to real processes, chemical processes in products of thermal decomposition at a pressure of 10 torr and in ammonium dinitramide [ADN; NH₄N(NO₂)₂] flame at a pressure of 0.4 to 60 atm are numerically simulated. The calculations are performed on the basis of a detailed kinetic mechanism and boundary conditions correlated with experimental data, thermodynamic properties, and chemical composition of ADN. The kinetic mechanism includes submechanisms that describe high-temperature chemical processes in NH₃/N₂O/NO/NO₂/HNO₂/HNO₃ and NH₃/HN(NO₂)₂ mixtures, and the global stages of aerosol decomposition. Based on calculated and experimental data, the role of dinitraminic acid HN(NO₂)₂, aerosols, and ADN vapor in heat release in the ADN flame zone adjacent to the burning surface is estimated. The calculations predict that the main source of heat release in the cold flame zone at p ≥ 3 atm is dinitraminic acid incoming through the channel of dissociative evaporation ADN_liq → NH₃ + HN(NO₂)₂ from the burning surface. In the high-temperature flame zone, heat release is caused by the reaction that occurs in the NH₃/N₂O/NO/NO₂/HNO₂/HNO₃ mixture. At moderate pressures, the high-temperature and low-temperature zones are separated by an induction zone. The stage governing production of the OH radical, which plays an important role in combustion, in the induction zone is the reaction HNO₃ + M → OH + NO₂ + M. Because of a high activation energy of the stage, small temperature perturbations in the induction zone at low pressures lead to a finite change in the stand-off distance between the high-temperature flame zone and the burning surface. Therefore, small temperature perturbations in the induction zone, which are caused by admixtures in the sample or by heat transfer between the reacting gas and the ambient medium, may be responsible for disagreement between various experimental data and between experimental and calculated data on the stand-off distance between the high-temperature flame zone and the burning surface. In numerical calculations, the position of the high-temperature zone is effectively controlled by varying rate constants of elementary stages within admissible limits. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 64–76, September–October, 2007.     

Mussoorrie rock phosphate-pyrite mixture as phosphate fertilizer

Mussoorrie rock phosphate (MRP), MRP + pyrite (25% by weight), diammonium phosphate (DAP), ammonium polyphosphate (APP) and nitrophosphate (NP) were compared in a field experiment as fertilizers for wheat. At 20 kg P ha^–1, MRP was only 6 per cent as effective as DAP. However, when it was mixed with pyrite, the efficiency of MRP increased to 64 per cent at 20 kg P ha^–1 compared with 97 per cent at 40 kg P ha^–1. The P requirement for a targeted yield for 4.5 t ha^–1 decreased from 39.4 kg P ha^–1 as MRP to 23.7 kg P ha^–1 as MRP + pyrite. Of the other P fertilizers studied, NP was as effective as DAP, whereas APP was 9 to 37 per cent more effective than DAP. However, the P requirement as DAP, NP and APP for a targeted yield of 4.5 t ha^–1 was similar (11 ± 0.5 kg P ha^–1).     

聚磷酸铵的研究进展

聚磷酸铵(APP)是一种重要的无机阻燃剂，是膨胀型阻燃剂的主要成分之一。介绍了Ⅰ-型和Ⅱ-型聚磷酸铵的结构、性质，着重讨论了Ⅰ-型和Ⅱ-型聚磷酸铵的合成方法、改性途径的研究新进展，以及Ⅰ-型聚磷酸铵到Ⅱ-型聚磷酸铵的转化机理、转化方法。研究目的在于制备难溶于水的聚磷酸铵。     

配位离子液体［3（CH3CH2）4N+Cl-·（NH2）2CO］的合成及表征

采用尿素和氯化四乙基铵为原料，合成了一种新型的配位离子液体，并通过红外和X－射线粉末衍射对其结构进行了表征。结果表明，尿素和氯化四乙基铵发生反应，使得原来尿素羰基峰由1690.72cm－1转移到了1619.10cm－1。由X－射线粉末衍射图可以看出，在2θ = 30.37°处有新的衍射峰。通过差热－热重分析，配位离子液体在室温到250℃可以稳定存在，与其他有机溶剂相比具有良好的稳定性。     

弱酸性铵盐与碱性锌酸盐双缸套镀锌工艺及低铬钝化

总结了弱酸性链盐镀锌和碱性锌酸盐镀锌的优缺点，并综合两者的优点，提出了一种弱酸性铵盐与碱性锌酸盐双缸套镀锌工艺。钝化膜的性能得到了改善。     

提高硫酸生产用钒催化剂性能的技术措施与效果

针对国产的硫酸生产用钒催化剂普遍存在的反应活性欠稳定、颗粒强度偏低、催化剂床层阻力偏大等问题，采取了对载体硅藻土进行共再浆水选处理、煅烧处理、热浓硫酸处理;晨添加剂中加入稀有元素，提高钾钒比，优化中和条件；采用专利技术成型，成品采用立式煅烧等技术措施，提高了钒催化剂的性能。改进后的钒催化剂不易粉化，低温型钒催化剂的活性明显提高，起燃温度可降至350℃，390℃以下的活性明显优于宽温型的，宽温型钒催化剂在390－450℃的活性更为优异。     

2,4-D/CMC接枝物纳米粒子的制备与缓释性能研究

以羧甲基纤维素钠（CMC）为基材，甲基丙烯酸甲酯（MMA）和二甲基二烯丙基氯化铵（DMDAAC）为改性单体，通过乳液聚合制备了CMC-g-P(MMA-DMDAAC)共聚物，采用自组装方法负载2,4-二氯苯氧乙酸（2,4-D）得到2,4-D/CMC-g-P(MMA-DMDAAC)纳米药物缓释体系。利用傅里叶红外光谱（FTIR）、差示扫描量热法（DSC）、热重分析（TGA）、扫描电镜（SEM）、粒度分析仪对其结构和形貌进行表征，并探究其载药性能和缓释性能。结果表明，2,4-D/CMC-g-P(MMA-DMDAAC)载药粒子呈笼状结构，粒度分布为160～425 nm；其载药率随着CMC∶MMA∶DMDAAC的摩尔比增大而提高，最高可达40.8%；其药物累计释放率随CMC∶MMA∶DMDAAC的摩尔比增大而降低，其释放行为符合Weibull模型，遵循Fick扩散机理。