293K下K^＋／CO3^2-，HCO3^-、Cl^-、H2O四元体系相图的研究——从农药废水中回收无机盐

用等温法测定了293K下K+/CO32-、HCO3-、Cl-、H2O四元体系的溶解度,根据溶解度数据绘制了相图,相图由KCl、KHCO3、K2CO3·3/2H2O、K2CO3·2KHCO3·3/2H2O四个相区组成.实验结果表明,K2CO3对KCl和KHCO3有强烈的盐析作用.以四元水盐体系相图理论作指导,对吡虫啉农药生产废水进行等温蒸发,分析计算了废水中各种盐的析出顺序及析出量,给出了分离氯化钾和碳酸钾较为理想的蒸发终止点,并提出了合理的工艺流程.     

293K下K~+/CO_3~(2-),HCO_3~-、Cl~-、H_2O四元体系相图的研究——从农药废水中回收无机盐

用等温法测定了293K下K+/CO32-、HCO3-、Cl-、H2O四元体系的溶解度,根据溶解度数据绘制了相图,相图由KCl、KHCO3、K2CO3·3/2H2O、K2CO3·2KHCO3·3/2H2O四个相区组成。实验结果表明,K2CO3对KCl和KHCO3有强烈的盐析作用。以四元水盐体系相图理论作指导,对吡虫啉农药生产废水进行等温蒸发,分析计算了废水中各种盐的析出顺序及析出量,给出了分离氯化钾和碳酸钾较为理想的蒸发终止点,并提出了合理的工艺流程。     

四元体系Li~+,K~+//CO_3~(2-),B_4O_7~(2-)-H_2O273K介稳相平衡研究

针对西藏扎布耶盐湖卤水组成,用等温蒸发平衡法研究了四元体系Li+,K+//CO23-,B4O27--H2O 273 K的相平衡,测定了平衡时各组分的溶解度及平衡液相的密度。四元体系Li+,K+//CO32-,B4O72--H2O273 K时的相图由5条溶解度单变量线、4个结晶区及2个共饱点组成。4个结晶区分别为对应于盐Li2CO3,K2CO3.1.5H2O,K2B4O7.4H2O及Li2B2O4.16H2O。2个共饱点中,一个为Li2CO3,K2CO3.1.5H2O及K2B4O7.4H2O三盐相称共饱点,另一个为Li2CO3,K2B4O7.4H2O和Li2B2O4.16H2O的三盐不相称共饱点。体系属四元水合物相图Ⅰ型,4种原始组分间未形成复盐或固溶体。对于该四元体系273 K和288 K下的介稳相图发现,碳酸锂盐的溶解度呈现较明显的负温度效应,它在273 K下的结晶相区比在288 K下的要小,且析出固相为偏硼酸锂;而碳酸钾、硼酸钾及硼酸锂结晶区则比288 K下的大。     

五元体系Li~+,K~+//CO_3~(2-),SO_4~(2-),B_4O_7~(2-)-H_2O 273K介稳相平衡研究

采用等温蒸发法研究了五元体系Li+、K+//CO32-、SO42-、B4O72-、H2O 273 K介稳相平衡关系,测定了它们在273 K条件下的介稳平衡的溶解度和溶液密度,根据实验数据绘制了相应的该五元体系在273 K条件下Li2CO3饱和的介稳平衡相图(干盐投影图和水含量图)。研究结果表明该五元体系介稳平衡中有复盐K2SO4-Li2SO4生成,其低温273 K时介稳相图中有4个共饱点和9条单变量曲线,6个Li2CO3饱和的结晶区分别为LiBO2-8H2O、K2B4O7-4H2O、K2CO3-3/2H2O、K2SO4、Li2SO4-H2O和复盐K2SO4-Li2SO4。对该五元体系在288 K和273 K时的介稳平衡相图进行了比较和讨论。     

交互四元体系Li+, K+//CO32-, B4O72- -H2O 298K 相关系及平衡液相物化性质的研究

针对西藏扎布耶盐湖卤水组成,用等温溶解平衡法研究了四元体系Li^ ,K^ //CO3^2-,Ba4O7^2-H2O 298K时的溶解度,测定了该体系的物化性质（密度,粘度,pH值,电导率,折光率）,该四元体系298K时的相图由5条溶解度单变量线,4个结晶区及2个共饱点组成,4个结晶区分别对应于盐Li2CO3,K2CO3.3/2H2O,Li2B4O7.3H2O及K2B4O7．4H2O,2个共饱点中,一个为Li2CO3,K2CO3.3/2H2O及K2B4O7．4H2O三盐共饱点,另一个为Li2CO3,Li2CO3,Li2B4O7.3H2O及K2BO7．4H2O的三盐不相称共饱点,体系属四元水合物相图I型,四种原始组份间未形成复盐或固溶体,应用Pitzer电解质溶液理论拟合了Li2CO3,K2CO3,Li2B4O7和K2B4O7的单盐参数及有关的混合离子作用参数,在此基础上计算了该四元体系298K时的溶解度,计算值与实验值基本吻合。     

298K下Na~+,K~+//Cl~ˉ,SO_4~(2ˉ),NO_3~ˉ-H_2O五元体系液固介稳相平衡

研究了298 K下,五元体系Na+,K+//Clˉ,SO42ˉ,NO3ˉ-H2O的液固介稳相平衡。采用等温蒸发法确定了溶液的介稳平衡溶解度。根据实验数据,绘制出了该体系介稳相图中氯化钠介稳饱和区以及氯化钠饱和条件下的介稳相平衡投影相图。相图中,有四个四盐共饱的零变量点、九个三盐共饱的单变量线和六个两盐结晶区:Na2SO4·Na NO3·H2O+Na Cl,3K2SO4·Na2SO4+Na Cl,Na NO3+Na Cl,KNO3+Na Cl,Na2SO4+Na Cl和KCl+Na Cl。该体系在298 K下的介稳相图和稳定平衡相图存在一定的差别,复盐3K2SO4·Na2SO4的结晶区明显缩小。     

10℃下 K+, Ca2+∥Cl-,SO42-,36%NH3-H2O体系相图的研究

为了探讨CaSO4·2H2O和KCl复分解生产K2SO4的工艺及最佳生产条件,特用恒温法研究了10℃K+,Ca2+∥Cl-,SO42-,36%NH3-H2O体系相图.溶剂NH3-H2O中氨的浓度之所以选为36%,目的在于扩大K2SO4及CaSO4·K2SO4·H2O的结晶区;反应温度选为10℃,可降低氨的蒸气压.研究结果表明:在上述条件下,体系中存在K2SO4和CaSO4·K2SO4·H2O、CaSO4·K2SO4·H2O和CaSO4·2H2O的共饱线;存在K2SO4-CaSO4·K2SO4·H2O-KCl以及CaSO4·2H2O-CaSO4·K2SO4·H2O-KCl的三盐共饱点;K2SO4结晶区要比25℃,溶剂NH3-H2O中氨的浓度为25%的同体系相图大得多:K2SO4-CaSO4·K2SO4·H2O-KCl的三盐共饱点更偏向氯化钙一角,因此有利于CaSO4·2H2O和KCl复分解生产K2SO4:最佳工艺条件为2KCl(mol):CaSO4(mol):36%NH3-H2O(kg)=1:0.9023:0.5740,KCl的理论转化率可达90.22%;若想进一步提高KCl的理论转化率,必须加大氨的浓度.     

三元体系K2CO3-KHCO3-H2O289K时相平衡的研究

为利用Engel复盐法制备碳酸钾，本文研究了三元体系K2CO3-KHCO3-H2O在KHCO3在289K时的相平衡，并测定溶液密度，绘制出体系的溶解度图和溶液密度一组成关系图，通过相图研究得出三元体系的共饱点及相关性质，为最终获得生产相图奠定基础。     

KCl-K_2CO_3-H_2O三元水盐体系在298K下相平衡的研究

采用等温溶解平衡法测定了298 K时,KCl-K_2CO_3-H_2O三元水盐体系的固液相平衡关系,测定了平衡液相的溶解度和密度,并绘制了相图。结果表明该体系在298 K时的相图都存在6个区域,即:纯KCl结晶区;纯K_2CO_3结晶区;以KCl为主的固溶体结晶区,以K_2CO_3为主的固溶体结晶区;以KCl为主的固溶体和以K_2CO_3为主的固溶体的共结晶区;不饱和溶液区。     

258.15K下五元体系Na~+,K~+//Cl~-,SO_4~(2-),NO_3~-―H_2O相平衡研究

采用等温溶解平衡法研究了258.15 K下五元体系Na~+,K~+//Cl~-,SO_4~(2-),NO_3~-―H_2O及其子体系Na~+,K~+//Cl~-,NO_3~-―H_2O的相平衡关系。测定了两个体系各盐的溶解度及溶液密度(冰相区除外),并绘制相图。研究结果表明:在258.15 K,氯化钠饱和时,该五元体系平衡干盐相图由四个两盐结晶区、五条单变量溶解度曲线和两个零变量点构成,四个两盐结晶区分别对应于Na Cl×2H_2O+Na NO_3,Na Cl×2H_2O+KNO_3,Na Cl×2H_2O+KCl,Na Cl×2H_2O+Na_2SO_4×10H_2O;与该体系298.15 K下的相图相比,K_3Na(SO_4)2和Na NO_3×Na_2SO_4×H_2O结晶区消失,Na_2SO_4×10H_2O结晶区扩大,相图大为简化;在258.15 K时,上述四元体系的平衡干盐相图由四个单盐结晶区(除冰区外)、五条单变量溶解度曲线和两个零变量点构成,四个单盐结晶区分别对应于Na NO_3、Na Cl×2H_2O、KNO_3和KCl;与该体系在298.15 K下的相图相比,硝酸钾结晶区扩大很多。     

2,3,4,6-四-O-乙酰基-1-巯基-吡喃葡萄糖的合成

以无水α-D-葡萄糖为原料通过四步反应完成2,3,4,6-四-O-乙酰基-1-巯基-吡喃葡萄糖的合成.首先用α-D-葡萄糖和乙酸酐合成1,2,3,4,6-五-O-乙酰基-β-D-吡喃葡萄糖(Ⅰ),再由(Ⅰ)和溴素、冰醋酸制得2,3,4,6-四-O-乙酰-α-D-溴代吡喃葡萄糖(Ⅱ),然后用(Ⅱ)和硫脲制得2-S-(2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基)-2-异硫脲氢溴酸盐(Ⅲ),最后加入氯仿和偏重亚硫酸钠制得最终产物2,3,4,6-四-O-乙酰基-1-巯基-吡喃葡萄糖(Ⅳ).通过FTIR、元素分析、1HNMR、13C-NMR等手段对产物结构进行了表征.     

N,N,N-三甲基-2-羟基-3-硬脂酰氧基丙基氯化铵的合成与表征

以环氧氯丙烷(ECH)和三甲胺(TMA)为原料,在40 kHz超声辅助下合成了季铵盐型活性醚化剂环氧氯丙基三甲基氯化铵(GTA);GTA在超声辅助下与硬脂酸反应,合成了阳离子单酯表面活性剂N,N,N-三甲基-2-羟基-3-硬脂酰氧基丙基氯化铵(CMESA)。通过元素分析,IR等手段对CMESA进行了表征,并考察了反应温度,n(GTA)∶n(硬脂酸),pH和反应时间等因素对产率的影响。结果表明,CMESA的合适合成条件为:超声频率50 kHz,n(GTA)∶n(硬脂酸)=3∶1,反应温度70℃,反应时间4 h,此条件下CMESA的产率为94.90%。     

环保型脲醛胶生产消费现状及发展趋势

阐述了环保型脲醛树脂生产、消费现状及发展趋势.     

O,O-二乙基-O-异螺环-4-烯-3-肟硫代磷酸酯的合成

本文研究了以薯蓣皂素（Diosgenin）为原料合成O，O-二乙基-O-异螺环-4-烯-3-肟硫代磷酸酯的工艺，IR、^1HNMR、MS、熔点测定等手段对合成的化合物结构进行表征，分析其理化性质和波谱特征，确定所合成的化合物为目标化合物。     

Hydrogenation ofcis-9,cis-12-,cis-9,trans-12- andtrans-9,trans-12- Octadecadienoates

The products formed by hydrogenation of methylcis-9,trans-12- andtrans-9,trans-12-octadecadienoates with nickel and platinum catalysts have been compared with those from methyl esters of the naturally occurring all-cis linoleate. Hydrogen uptake is slower for thetrans isomers. Much of the monoene consisted of esters with double bonds at the 9 and 12 positions with their original geometric configurations. Monoenoic esters with double bonds at the 10 and 11 positions were predominatelytrans and apparently formed by conjugation before hydrogenation. Nickel produced more isomerization than platinum but less than previously reported for copper. With both catalysts hydrogenation proceeded both directly and through conjugated intermediates, in contrast to copper in which all hydrogenation is believed to follow conjugation. Presented at the AOCS Meeting, Los Angeles, April 1972. ARS, USDA.     

高反式- 1,4-丁二烯-异戊二烯共聚物

综述了国内外合成高反式－1，4－丁二烯－异戊二烯共聚物的配位催化体系，负离子催化体系，醇（钠）烯催化体系及其共聚物的结构与性能，用核磁共振，红外光谱对其进行了表征，并提出了发展建议。     

(S,S)-2,12-, (S,S)-2,13-, and (S,S)-2,14-diacetoxyheptadecanes: sex pheromone components of red cedar cone midge, Mayetiola thujae

We identified, synthesized, and field-tested the sex pheromone of female red cedar cone midge Mayetiola thujae (Hedlin) (Diptera: Cecidomyiidae), a pest insect in red cedar Thuja plicata seed orchards. Coupled gas chromatographic (GC)-electroantennographic detection analyses of pheromone extract revealed three components (A, B, C) that elicited responses from antennae of males, all of which occurred below the detection threshold of the mass spectrometer and thus had to be identified without spectroscopic data. Taking into account (1) their retention indices (RI) on three GC columns (DB-5, DB-23, and DB-210), (2) intercolumn RI differentials, and (3) the molecular structures of known cecidomyiid pheromones, we synthesized seven candidate pheromone components: 2,10-, 2,11-, 2,12-, 2,13-, 2,14-, 2,15- and 2,16-diacetoxyheptadecanes. Of these, 2,12-, 2,13-, and 2,14-diacetoxyheptadecane had RIs on all columns consistent with those of A, B, and C and elicited strong antennal responses when tested at picogram levels. In field experiments with the twelve stereoselectively synthesized stereoisomers, only the SS-stereoisomers of 2,12-, 2,13-, and 2,14-diacetoxyheptadecane attracted male M. thujae. The three-component SS-stereoisomer blend was more attractive than the 12-component blend of all stereoisomers, suggesting that one or several nonnatural stereoisomers are inhibitory. One-, two-, and three-component lures of the SS-stereoisomers were equally effective in attracting male M. thujae, indicating redundancy in the pheromone. Identification of the M. thujae sex pheromone will allow development of pheromone-based monitoring, and possibly control, of M. thujae populations in T. plicata seed orchards.     

Synthesis ofcis 9, 15-, 8, 15-, and 7, 15-octadecadienoic acid

In connection with the study of autoxidation of someiso-linoleic acids, the 9,15-, 8,15-, and 7,15-octadecadienoic acids have been synthesized by partial hydrogenation of the corresponding diynoic acids. These acids were prepared by coupling ω-iodo-3-alkynes with ω-chloro-1-alkynes by means of sodium amide in liquid ammonia to form ω-chlorohexadiynes, followed by condensation of the corresponding iodine compounds with sodium malonic ester. Part of paper presented by G. J. Henning at the AOCS Meeting, Philadelphia, October 1966.