ESI源质谱表征氯化钙和氯化镁

用ESI源质谱对氯化镁和氯化钙进行了定性的检测，所得谱图更加全面直观地表征了氯化钙和氯化镁在水溶液中的存在形式。     

苯基氯化硫及氯化硫对碳-碳重键的加成反应

芳基氯化硫是一类具有多种反应性能的物质。Kharasch等系统地研究了它们对重键的加成,并提出亲电反应机理^[1]。但在炔烃反应中,只用亲电反应机理不能解释其加成方向。例如,Truce研究苯基氯化硫与苯乙炔在非极性溶剂中的加成,得α-苯硫基-β-氯代苯乙烯^[2]。     

PREPARATION OF HIGHLY BRANCHED POLYETHYLENE WITH ACENAPHTHENEDIIMINE NICKEL CHLORIDE/DIETHYLALUMINUM CHLORIDE CATALYST

The homogeneous catalyst system [ArN = C(Nap)- C(Nap)= Nar]NiCl2 (Nap = 1,8-naphthdiyl, Ar = 2,6-diisopropylphenyl)/AlEt2Cl has been prepared and examined for ethylene polymerization. Polymerization conditions such as cocatalyst, Al/Ni molar ratio and polymerization temperature (Tp) have a great effect on catalytic activity and properties of polyethylenes (PE). The activity of 5.1 × 105g PE/mol Ni. H was obtained by the catalyst, activated with AlEt2Cl at 120 of Al/Ni ratio and 30℃. Especially, Tp had a pronounced influence on branches and molecular weight of PE. Branching degree of PE increased with increasing temperature whereas their molecular weight decreased correspondingly. At Tp lower than about 70℃, the resultant PE was an elastic material. When Tp was higher than 70℃, the product was a viscous oil. The resultant PE was confirmed by 13C-NMR to contain significant amounts of not only methyl but also ethyl, propyl, butyl,amyl, and longer branches (longer than six carbons). According to gel permeation chromatographic measurement, the weightaverage molecular weights of the polymers obtained ranged from 3.6 × 103 to 2.3 × 105.     

二环戊二烯基氯化钕的合成

用NdCl₃·2 THF和环戊二烯的(摩尔比)比为1:1.8在四氢呋喃(THF)溶液中室温反应得到二环戊烯基氯化钕四氢呋喃络化物(C₅H₅)₂NdCl·THF。元素分析,红外光谱和X光电子能谱的数据证实了这一化合物的存在。在抽空加热下脱去THF得到组成符合(C₅H₅)₂NdCl的淡紫色的残余物。     

氯化稀土吡啶络合物

近年来,文献上已报导了许多种稀土离子和含氮配位体合成的络合物[1,2]。但是,这些络合物几乎都是由强碱性的含氮化合物或含有双基、多基的弱碱性或中性含氮配位体组成。与上述配位体相比,吡啶(Py)与稀土离子的络合能力要弱得多。     

气相色谱法测邻氰基苄基氯

采用GC／MS法检测出邻氰堪苄基氯中的杂质组分，并使用萘做内标物进行气相色谱法对邻氰堪苄基氯的定量检测。     

氯乙烯在高聚物中的溶解度

本文进行了氯乙烯在氯相/高聚物 (PVC,EVA,EVA-g-VC) 间相平衡的研究。实验数据用三种数学模型作了处理:Flory-Huggins 经典模型、Prigogine-Flory 自由容积模型和本文作者提出的线性模型。氯乙烯在高聚物中的溶解度按三种模型的计算值与实验结果都符合得很好。而且,结果表明,线性模型具有精确易用的优点,Prigogine-Flory 模型完全适用于 VC/PVC体系,VC在EVA-g-VC接枝共聚树脂中的溶解度服从加和性规律。     

THE CHEMICAL MODIFICATION OF POLYVINYL CHLORIDE

Abstract

Poly (vinyl chloride) (PVC) is commercially one of the most important thermoplastics in the world today. Its growth rate averaged 7% per annum in the 1970s. In 1980 it was the second largest volume thermoplastic used in the United States (the first being low-density polyethylene (LDPE) and was the lowest priced among the five leading plastics: LDPE, PVC, high-density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS).     

BARRIER PROPERTIES OF VINYLIDENE CHLORIDE COPOLYMERS

The permeability coefficients of a series of copolymers of vinylidene chloride (VDC)with methyl acrylate (MA), butyl acrylate (BA) or vinyl chloride (VC) (as comonomer)to oxygen and carbon dioxide have been measured at 1.0 MPa and 30℃, while those towater vapor have been measured at 30℃ and 100% relative humidity All the copolymersare semicrystalline. VDC/MA copolymers have lower melting temperature compared withVDC/BA copolymers, while that melting temperature of VDC/VC copolymer is higherthan that of VDC/acrylate copolymers with the same VDC content. The barrier propertyof the copolymers is predominantly controlled by crystallite, free volume fraction, andcohesive energy The permeability coefficients of VDC/MA copolymers to oxygen, carbondioxide, and water vapor were successfully correlated with the ratio of free volume tocohesive energy.     

甲基磺酰氯合成工艺改进

本文概述了甲基磺酰氯的合成方法，作者对以硫脲为原料的合成工艺进行了深入的研究，改进后的合成工艺使产品产率提高了10％。     

气相色谱法测定三聚氰氯的研究

气相色谱法测定三聚氰氯的研究李秀梅赵树岚＊田锦霞＊孙维星（东北师范大学化学系长春１３００２４）关键词气相色谱法三聚氰氯三聚氰氯（ＣＮＣｌ）３是活性染料的重要中间体及合成树脂、橡胶、塑料等的防老剂，也常用于除草剂、增白剂、药物、炸药等的生产中。传统的分...     

三苄基氯化锡及其衍生物的合成

三苄基氯化锡最初用格氏法制得。Keiti等曾报道由锡和苄基氯直接制备,这时溶剂对反应的影响很大:用水作溶剂时得到三苄基锡;用甲苯作溶剂时得到二苄基二氯化锡;用正丁醇作溶剂时三苄基氯化锡的产率只有61％。在反应体系中加入KI、KBr或H_3PO_4等催化剂,三苄基氯化锡的产率也只有60％。本文用DMF作溶剂,AlCl_3-I_2作催化剂,并首次在反应体系中加入镁、锌、铝和钠等使副产物氯化亚锡还原成活性很高的金属锡,后者再与等基氯反应,可使三苄基氯化锡的产率提高到91.3％。文中还报导三种尚     

SILVER CHLORIDE MICROCRYSTALS SUSPENSIONS IN MICROEMULSION MEDIA

A study of the precipitation of silver chloride in a micro-emulsion medium is presented. Measurements of turbidity, X-ray diffraction and small angle scattering show, the rapid formation of small crystals, about 60 °A in diameter wliich show no further growth and aggregate only slowly ; the stabilization of these solid particle suspensions, of steric or electrostatic origin, is increased by six orders of magnitude in comparison with aqueous colloidal solutions     

亚硫酰氯阴极还原的半对数极化曲线

目前正在广泛研究的鲤/亚硫酰氯(Li/SOCl_2)电池是迄今为止比能量最高的一种新型化学电源。提高电池的性能和可靠性与电池反应的化学和电化学性质直接有关。但是,SOCl_2的还原过程相当复杂,对其反应机理迄今尚无明确的结论。由于SOCl_2还原时伴随着LiCl的沉积,当用常规电极测量时难以得到稳态极化曲线,因而至今未见报道SOCl_2还原反应的半对数极化曲线。微电极的单位表面上极限液相传质速度较高,且测量时较易得到稳态电流。因此,采用微电极方法可在一定程度上避开上述困难,研究SOCl_2还原反应的机理。     

羟基四氮茚在氯化银乳剂中的增感作用

自Birr发现三氮茚和四氮茚类化合物^[1]及其用作卤化银感光剂的稳定剂以来,它们一直受到广泛的关注^[2]。     

三氯化铝催化硫的同位素交换

研究了³⁵S与>C=S、→P=S、→C—S—S—C←、→C—SH等类型硫化物用三氯化铝催化的交换反应.二硫化碳、硫代磷酰氯、乙基硫代膦酰二氯、苯基硫代膦酰二氯等用此法交换,均得到良好的化学产率与放射产率.二硫化碳或硫代磷酰氯与三氯化铝、硫共热,显示三个顺磁共振峰,因此初步推测交换反应为自由基反应.含有R—O—P键的→P=S类化合物与三氯化铝发生副反应,故未能很好交换.二乙基化二硫的交换率颇低,乙硫醇则无交换.     

REACTION OF SULFUR CHLORIDE WITH ACETOPHENONE. II

Abstract

In a previous paper,¹ we reported the formation of a resinous material (1) from the reaction of sulfur chloride with acetophenone which, upon treatment with DMF, yielded phenylglyoxylthiodimethylamide (4). We now report two additional resinous materials (5, 6), resulting from bromination of sodium phenacylthiosulfate (3) and diphenacyl disulfide (7) respectively, both of which not only resemble resinous 1 in appearance, but also yield 4 upon treatment with DMF in aqueous alkali.

Resinous 1, 5, and 6 appear to have the same common basic structure and differ only in the number of sulfur atoms bonded between the common units. Cleavage at the sulfur-sulfur bonds and elimination of hydrogen halide then yields identical oxothioamides from 1, 5, or 6. The latter appears to be a general reaction, and several oxothioamides were prepared by this synthetic method from 1, 5, and 6 and various amides and amines.     

PA6/CaCl_2复合物的络合机理研究

通过负离子淤浆聚合制备了高相对黏度的聚酰胺6(PA6)粉末料,将其加入氯化钙甲酸溶液中制备不同的PA6/CaCl2单位链节摩尔比络合溶液.采用X射线光电子能谱(XPS)、红外分析方法研究了PA6/CaCl2复合物的络合机理.结果表明,复合物中钙原子与聚酰胺6分子链上的羰基氧原子发生配位作用,破坏了PA6本身的氢键,释放出自由NH,而氯离子则与NH形成氢键.同时通过电导率测试推测氯化钙与酰胺键之间的配合形式为四配位或者六配位.