丁基（三甲基硅基亚甲基）锡二芳香酸酯的合成与结构表征

采用丁基(三甲基硅基亚甲基)二氯化锡和芳香酸,在三乙胺存在下,以1:2的物质的量比进行反应,合成了9个新的混合含硅二烃基锡化合物--标题化合物.通过IR、1HNMR和13CNMR对它们的结构进行了表征.生物活性测定的初步结果表明,目标化合物Bu(Me3SiCH2)Sn(OCOC6H4NO2-p)2对肺腺癌细胞A549有较好的体外抗癌活性.     

二丁基(三甲基硅基亚甲基)锡芳香酸酯的合成、结构及生物活性

合成了9个二丁基(三甲硅基亚甲基)锡芳香酸酯,通过IR、NMR和MS对目标化合物的结构进行了表征.生物活性测定的初步结果表明,该类化合物具有较好的杀螨活性和一定的杀菌活性.     

含硅二烃基锡二吡啶羧酸酯的合成与结构表征

采用含硅二烃基锡氧化物和相应的吡啶甲酸,合成了7个新的含硅二烃基锡配合物--标题化合物;通过IR、1HNMR、13CNMR和元素分析对它们的结构进行表征.生物活性测定的初步结果表明,目标化合物环已基(三甲基硅基亚甲基)锡二(2-吡啶羧酸酯)Cy(Me3SiCH2)Sn(OCOC5H4N-o)2对肺癌细胞A549和肠癌细...     

苯基-二[(三甲基硅基)亚甲基]锡芳香酸酯合成及杀螨活性

合成了两个含硅混合三烃基锡芳香酸酯：苯基-二【（三甲基硅基）亚甲基】锡苯甲酸酯、苯基-二【（三甲基硅基）亚甲基】锡对硝基苯甲酸酯，利用IR、^1H NMR、^13C NMR和元素分析表征了其结构，并进行杀螨活性测定，发现这两个化合物在200mg／L时杀螨率均超过96％，具有较强的杀螨活性。     

含硅烃基氯化锡的合成及其结构表征

用四（烃硅基亚甲基）锡和四氯化锡按不同的物质的量比进行反应,合成了相应的三烃基一氯化锡、二烃基二氯化锡和一烃基三氯化锡。讨论了影响反应的主要因素,并使用高效液相色谱对反应的进程进行跟踪检测。通过^1HNMR和元素分析,确定了这些化合物的结构。生物活性试验的初步结果显示,含硅二烃基二氯化锡对肺癌细胞SPC-A-1具有较好的体外抗癌活性。     

阳离子单体及其聚合物的合成表征

合成了阳离子单体甲基丙烯酰氧乙基二甲基丁基溴化铵(DMB),将DMB与丙烯酰胺(AM)共聚制备了阳离子聚丙烯酰胺,并用IR,NMR对其结构进行了表征。     

MT型硅氧烷低聚物及含MT结构的聚硅氧烷(一)

概述了MT型硅氧烷低聚物和含MT结构的聚硅氧烷的结构、物理常数,介绍了几种典型的MT型硅氧烷低聚物[甲基三(三甲基硅氧基)硅烷、乙烯基三(三甲基硅氧基)硅烷、甲基三(乙烯基二甲基硅氧基)硅烷、3-甲基丙烯酰氧丙基三(三甲基硅氧基)硅烷、3-甲基丙烯酰氧丙基三(二甲基硅氧基)硅烷、甲基三(二甲基硅氧基)硅烷、苯基三(二甲基硅氧基)硅烷、1,3-二苯基四(二甲基硅氧基)二硅氧烷]的特性、应用领域、合成方法及应用实例。     

甲基丙烯酰胺丙基二甲基胺的合成

以甲基丙烯酸甲酯和N,N-二甲基丙二胺为原料,二丁基二月桂酸锡为催化剂,对苯二酚为阻聚剂合成了甲基丙烯酰胺丙基二甲基胺(DMAPMA)。确定了合成的最佳工艺为:n(甲基丙烯酸甲酯)∶n(N,N-二甲基丙二胺)=3∶1,催化剂用量为反应液总质量的2.0%,阻聚剂用量为反应液总质量的0.1%,反应温度为体系回流温度,反应时间为3h,在此条件下,产率达96%以上,二丁基二月桂酸锡可重复使用。     

新型季铵盐的杀菌活性研究

对4种新型季铵盐甲基丙烯酰氧乙基二甲基苄基氯化铵(DMAEMA-BC)、甲基丙烯酰氧乙基二甲基丁基溴化铵(DMAEMA-BB)、甲基丙烯酰氧乙基二甲基十二烷基溴化铵(DMAEMA-DB)和甲基丙烯酰氧乙基二甲基十六烷基溴化铵(DMAEMA-HB),采用最小杀菌浓度(MBC)法和抑菌圈直径法对大肠杆菌和金黄色葡萄球菌的杀菌活性分别进行了表征.MBC法研究结果发现,DMAEMA-HB和DMAEMA-DB的MBC值为12 ug/mL-24 ug/mL,但DMAEMA-Bc和DMAEMA-BB的MBC值大于50 000 ug/mL,其杀菌活性大小顺序为:DMAEMA-HB≥DMAEMA-DB>DMAEMA-BC≥DMAEMA-BB.通过抑菌圈直径法测定4种季铵盐的杀菌活性,顺序为:DMAEMA-DB>DMAEMA-BC>DMAEMA-HB>DMAEMA-BB.造成两种方法测试结果差异主要是因为通过抑菌圈直径法测定的杀菌活性,不仅与季铵盐的结构有关,还与季铵盐在琼脂上的扩散能力有关.     

戊唑醇中间体2-[2-(4-氯苯基)乙基]-2-(1,1-二甲基乙基)-环氧乙烷合成工艺的改进

[目的]研究一种合成2-[2-(4-氯苯基)乙基]-2-(1,1-二甲基乙基)-环氧乙烷过程中替代二甲基硫醚的方法。[方法]用难挥发的甲基硫醚代替二甲基硫醚合成硫鎓盐,然后与1-(4-氯苯基)-4,4-二甲基-3-戊酮反应合成目标化合物,并对反应条件进行优化。[结果]用正辛基甲基硫醚合成2-[2-(4-氯苯基)乙基]-2-(1,1-二甲基乙基)-环氧乙烷,收率达90.5%,操作过程气味小。[结论]用正辛基甲基硫醚替代二甲基硫醚进行硫叶立德反应,可以克服反应过程的恶臭气味,具有工业化应用前景。     

Water extraction of additives from PVC pipe

Information contributing to the safety considerations of PVC potable water pipe is presented on the extraction of various materials other than vinyl chloride monomer. The water extraction data covers methyl-, butyl- and octyl-tin stabilizers and shows a significant decrease in tin extraction level as the chain length increases. Other metallic ingredients such as titanium, calcium and magnesium are studied as well. In all cases the extraction values are at low levels. It is important to consider that the static conditions and the duration of testing time is far in excess of normal residence time of water in PVC piping systems.     

Electrochemical dissolution of tin in methanesulphonic acid solutions

High-rate electroplating of tin on a moving steel strip is generally carried out in cells with dimensionally stable anodes. To obtain a matt tin deposit a concentrated acidic tin methanesulphonate solution containing a small concentration of sulphuric acid is used. The concentrated tin methanesulphonate solution is prepared by dissolution of tin particles with oxygen in a special column. To describe this dissolution process electrode reactions (namely, reduction of oxygen, hydrogen peroxide and hydrogen ions on a tin electrode and oxidation of tin) were studied using electrochemical techniques. It was concluded that on tin, oxygen is almost entirely reduced to water and that H₂O₂ cannot corrode tin directly, but its decomposition products, for instance oxygen, can. The exchange current density and the charge transfer coefficient for the investigated electrode reactions are estimated. The dissolution of tin by oxygen is determined by the kinetic parameters of the oxygen reduction reaction and by the mass transfer of (i) dissolved oxygen to and (ii) Sn²⁺ ions from the tin electrode surface. Hydrogen evolution can be neglected during the dissolution of tin in the presence of oxygen. Moreover, it was found that the rate of tin corrosion increases with (i) increasing H⁺ concentration, (ii) oxygen concentration, (iii) convection intensity and (iv) temperature. It is likely that the tin surface is not covered with oxygen during corrosion in pure methanesulphonic acid solutions, but an oxide layer may be present on the tin surface during oxygen corrosion in pure sulphuric acid solutions. This oxide layer may hinder the oxygen corrosion of tin.     

四辛基锡中锡(Ⅱ)的测定

研究了四辛基锡中锡(Ⅱ)含量的测定方法。试样经浓硫酸高温碳化,以金属铝还原锡(Ⅳ)为锡(Ⅱ),铁粉消除溶解氧的影响,淀粉为指示剂,碘酸钾标准滴定溶液滴定锡(Ⅱ)。该方法的标准偏差为0.179,回收率在98.46%~100.70%之间,试样中共存的其它元素均不干扰测定。     

Preparation of Stabilized Nanosized Tin Oxide Particles by Hydrothermal Treatment

Stable colloidal suspensions of tin oxide (content 0.9–6.1 wt%) were synthesized by subjecting conventionally prepared tin oxide gels to hydrothermal treatment with an ammonia solution (pH 10.5) at 200°C for 3 h in an autoclave. Based on X-ray diffractometry analyses, the tin oxide crystallites after hydrothermal treatment were resistant to thermal growth at elevated temperatures, and this feature became more conspicuous as the tin oxide content of the colloidal suspension decreased. For the powder derived from a 1.8 wt% colloidal suspension, for example, the mean sizes of the tin oxide crystallites were 7.5 and 13 nm after calcination at 600° and 900°C, respectively, in comparison with corresponding values of 13.5 and 29 nm for the untreated gel-derived powder. Thin film spin-coated from the same suspension had good uniformity, packed with tin oxide grains (crystallites) of a mean size of 6 nm after calcination at 600°C. Optical determination of the tin oxide sol particle size, as well as gravimetric analysis of the dehydration from the powder samples, were conducted to determine effects of hydrothermal treatment.     

降温速率对浮法硼硅酸盐玻璃下表面渗锡的影响

研究锡槽中降温速率对浮法硼硅酸盐玻璃下表面渗锡的影响.采用不同降温速率制备浮法硼硅酸盐玻璃,用电子探针测试浮法硼硅酸盐玻璃在1 250～650℃温度范围内不同降温速率情况下表面渗锡分布情况.研究结果表明:浮法成形过程中硼硅酸盐玻璃渗锡的深度可达到40.0μm左右,并且在1 050℃以上的高温段锡离子以深度方向扩散为主,在1 050℃以下的低温阶段锡离子主要在玻璃的近表面富集.随着时间的延长浮法硼硅酸盐玻璃近表面的渗锡量增加,而深度大于7.0μm以上的内部的渗锡量不会由于时间的延长而累加,只与温度有关.在浮法成形过程中渗锡曲线会在1 050℃左右,距玻璃表面15.0μm处出现卫星峰,但最终在低温时该卫星峰会由于逆扩散而消失.     

原板的电化学酸洗对镀锡板表面形貌及孔隙率的影响

研究了电化学酸洗对镀锡板孔隙率的影响。采用X射线荧光光谱仪(XRF)、扫描电子显微镜(SEM)、金相显微镜、原子力显微镜(AFM)等对原板表面成分、形貌以及锡的电沉积层形貌进行了表征,并测试了镀锡板的孔隙率。结果表明:随着酸洗时间的延长,原板表面富集的锰元素含量减少,铁晶粒暴露程度增大,电沉积的锡晶粒逐渐细化,镀锡板孔隙率降低。     

有机锡热稳定剂对CPE脱氯化氢热降解性的影响

采用刚果红法研究有机锡热稳定剂对氯化聚乙烯(CPE)脱氯化氢热降解性的影响。结果表明，硫醇锡复合热稳定剂T-137和T-395A抑制CPE脱氯化氢的效果优于非硫醇锡热稳定剂二月桂酸二丁基锡；环氧大豆油能协同二月桂酸二丁基锡减慢CPE脱氯化氢速度；热稳定剂用量小于3份时，二月桂酸二丁基锡／二盐基亚磷酸铅和二月桂酸二丁基锡／硬脂酸钡并用体系(并用比1：1)抑制CPE脱氯化氢的效果较二月桂酸二丁基锡差，热稳定剂用量为3份时则较好。     

Synergistic effects of benzalacetone and benzophenone on the electrocrystallization of tin from acid stannous sulphate solutions

The synergistic effects of two kinds of aromatic ketones (benzalacetone (BA), benzophenone(BP)) and N,N-bis(polyoxyethylene)octadecylamines (POOA) on the surface morphology and the crystal orientation of electrodeposited tin from acid stannous sulphate solutions have been studied by electrochemical methods, scanning electron microscopy and X-ray diffractometry. BA itself had no effect on the reduction of tin (II) ions, but the reduction product of BA had a strong inhibitory effect on the reduction of tin (II) ions. However, the inhibitory effect of BP was stronger than that of the reduction product of BP. POOA induced a uniform deposition of tin over the whole surface, but the crystal grain size and the surface roughness of electrodeposited tin were relatively large. On the other hand, fine-grained and smooth electrodeposited tin, which had a preferred orientation with the (10 0) plane parallel to the surface, were obtained from acid stannous sulphate solutions containing POOA, BA and BP due to the synergistic effects of the three kinds of adsorbed species. It was found that BA has a levelling action and BP has a grain refinement action.     

Effects of chromate treatments on environmental stability of lead/tin alloy joints bonded with an ethylene–acrylic acid copolymer. I. Characterization of chromated surfaces and fractured joint surfaces

Chromated lead, tin, and lead/tin alloy surfaces have been characterized by x-ray photoelectron spectroscopy (ESCA) and ion microanalyzer (IMA). Also the locus of failure in dry conditions of these metal joints bonded with an ethylene–acrylic acid (EAA) copolymer has been estimated from analysis of the fractured surfaces by ESCA, IMA, and scanning electron microscopy (SEM). Cathodically chromated tin and lead/tin surfaces are almost completely covered with a corrosion-protective chromium oxide film, although immersion-chromated tin and lead/tin surfaces have considerable amounts of tin and lead oxides. In chromated tin joints having a chromate film of less than 100Å, bond failure occurs cohesively in the EAA copolymer. On the other hand, chromated tin joints having a chromate film of more than 100Å give the failure mainly at the chromate film–tin oxide interface and partly in the tin oxide.     

Reactivity of Brönsted acid ionic liquids as dual solvent and catalyst for Fischer esterifications

Several water-stable ionic liquids with different acidity and affinity were synthesized and applied as both solvents and acid catalysts for Fischer esterification of ethanol reacting with four aliphatic carboxylic acids (acetic acid, n-hexanoic acid, lauric acid, and stearic acid). Among the studied ionic liquids, [(n-bu-SO₃H) MIM][HSO₄] (3-butyl-1-(butyl-4-sulfonyl) imidazolium sulfate) and [(n-bu-SO₃H) MIM][p-TSO] (3-butyl-1-(butyl-4-sulfonyl) imidazolium toluenesulfonate) show higher reactivity for the production of ethyl esters. The catalytic activities of these ionic liquids are strongly dependent on the acidity of their anions and cations, as well as their hydrophilicity and affinity with the reactants. Water refluxing through the condenser may be another important reason for obtaining high conversion of esterification, indicating a water-sequester process is still needed in order to obtain a higher yield of ester in the ionic liquid catalyzed esterification system. Kinetics studies show the conversions of the acids increase with reaction temperature and time, and reach equilibrium within about two hours. The apparent activation energies are 39.1±2.0, 49.7±2.5, 51.4±2.5 and 59.3±3.0 kJ·mol⁻¹ for the formation of ethyl acetate, ethyl n-hexanoate, ethyl laurate and ethyl stearate, respectively.