DEA与SDS/n-C5H11OH/H2O微乳液的相互作用

以循环伏安法研究了N,N-二乙基苯胺（DEA）与十二烷基硫酸钠（SDS）/正戊醇（n-C5H11OH）/H2O体系O/W和W/O结构微乳液的相互作用.结果表明,DEA在SDS/n-C5H11OH/H2O体系微乳液中有两种定位方式:其一,DEA分子在微乳液液滴膜相中定位于表面活性剂和助表面活性剂的极性基团附近;其二,DEA分子在微乳液液滴膜相中定位于表面活性剂疏水基团一侧.两种定位的分布与微乳液的结构和组成相关.     

柴油/渣油多重乳液延缓铬溶胶交联体系的制备及稳定性研究

多重乳液因为具有独特的"两膜三相"的多隔室结构,使得交联剂和聚合物溶解在不同相中,起到延缓交联的作用,可用于油田采油后期深部调剖堵水作业,以提高原油采收率。本文采用用两步法制备了一种稳定的W/O/W型多重乳状液延缓交联体系,并对其在大庆地层条件下成胶性能进行室内静态评价。通过正交试验得到多重乳化最佳工艺条件:W/O乳液在WSpan80=2.8%,Wresidual=5%,VOil∶VWater=3∶7,T=2.5min条件下制备;W/O/W乳液在VW/O∶VHPAM=7∶3,WTween80=1.5%,R=4000r·min-1,T=3.0min条件下制备。在pH=8时所合成的柴油/渣油多重乳液延缓铬溶胶交联体系成胶时间为480h,冻胶强度为28354m Pa·s。     

聚乙烯吡咯烷酮存在时反相微乳液中水的状态

运用傅立叶变换红外光谱（FTIR）研究不同分子量的聚乙烯吡咯烷酮（PVP）存在时,十二烷基甜菜碱(C12BE)/正庚烷 /正戊醇 /水（Ⅰ）及二（2 乙基）己基磺化琥珀酸钠（AOT）/正庚烷 /水（Ⅱ） 反相微乳液中水的存在状态.采用计算机分峰技术将微乳液中水分子的O－H伸缩振动进行曲线拟合, （Ⅰ）得到三个子峰,分别位于(3560±20)cm－1,(3430±10)cm－1,(3280±10)cm－1附近; （Ⅱ）得到四个子峰,分别位于3618 cm－1, 3550 cm－1, 3446 cm－1和3292 cm－1处.尽管PVP均增溶于W/O型微乳液中表面活性剂分子的极性基团附近,却没有引起长链间自由水的变化.但由于两体系的差异,PVP的存在,导致微乳液（Ⅰ）的本体水减少,结合水增多,却使体系（Ⅱ）的结合水减少,本体水增多.由于W/O型微乳液中水与生物膜中水相似,这些研究有助于理解生物膜界面上的生物化学和生物物理现象.     

辐射冷冻乳液聚合制备多孔聚合物微球

本文研究了常规苯乙烯乳液和苯乙烯细乳液在两种不同冷冻条件下,即液氮冷冻和-20℃冰箱冷冻过程中乳液体系稳定性的变化,以及γ射线辐射引发冷冻乳液中单体聚合得到的聚苯乙烯微球的形貌,并探讨了形貌形成机制.结果表明,乳液在-20℃冰箱中冷冻过程中乳液稳定性破坏,单体出现分层现象.而液氮冷冻可以保持冷冻前的乳液相态结构.γ射线辐射可以引发冻乳液中苯乙烯聚合,聚合过程中体系经历了从O/W乳液向W/O/W多重乳液的转变,最终形成粒径分布较宽,直径为1~20μm的泡孔状多孔PS微球.本工作不仅为低温聚合技术提供了新思路,也为多孔聚合物微球材料的制备提供了新方法.     

高固含量低黏度聚氨酯微乳液的制备及性能研究

以聚(四氢呋喃-co-氧化丙烯)二醇(Ng210)为软段,异佛尔酮二异氰酸酯(IPDI)为硬段,以1,2-二羟基-3-丙磺酸钠(DHPS)和二羟甲基丙酸(DMPA)作为亲水扩链剂,采用自乳化法合成了一系列了高固含量低黏度稳定聚氨酯微乳液,分析了DHPS和DMPA质量配比对乳液性能的影响,结果表明,所得乳液粒径呈多元分布,乳胶粒子呈球形;乳液为假塑性流体,表观黏度小于250mPa.s(剪切速率为25s-1)且随切变速率的变化规律呈现一定的切力变稀特征;随着DHPS/DMPA比值的增大,胶粒平均粒径逐渐减小,多分散性增强;当DHPS/DMPA值为4/10～6/10时,乳液中大小粒子粒径比为6～8,且大乳胶粒子的体积分数约为70%～75%,乳液的固含量均大于70%.另外,乳液具有较好的低温和高温以及贮存稳定性,具有较低的表面张力,相对于常规的聚氨酯乳液,所制备的高固含量聚氨酯乳液胶膜具有更好的力学性能.     

高固含量低黏度丙烯酸酯乳液的制备及在密封胶中的应用

利用过硫酸铵-亚硫酸氢钠氧化还原引发体系制备了固含量为55%的丙烯酸乙酯、丙烯酸异辛酯、丙烯酸、甲基丙烯酸甲酯的共聚物种子乳液;以上述乳液为种子,十二烷基硫酸钠和辛基酚聚氧乙烯醚为乳化剂、碳酸氢钠为缓冲剂,过硫酸钾为引发剂80℃下制备固含量在70%~74%的高固含量、低黏度稳定乳液。种子乳液呈现多元分布、乳胶粒粒径约为150~300nm,增长后高固含量乳液仍保持宽分布、平均粒径大小在350~600nm,黏度在剪切速率20s-1时为600~900mPa·s。此乳液做成的密封胶固化时间短,收缩率小,强度大。     

用混合乳化剂UE20/PVA制备的水包油型生漆乳液的性能

以漆酚基乳化剂(UE20)和聚乙烯醇(PVA)为混合乳化剂制备了水包油(O/W)型生漆乳液(RLE), 研究了UE20与PVA的质量比、混合乳化剂质量分数(wME)、水与天然生漆(RL)的质量比、温度和贮存时间对RLE性能的影响, 并用透射电镜观察了wME对RLE粒子的大小及形态的影响. 结果表明, RLE的黏度随着PVA的增加而增大; 当wME≤6.7%时, RLE表现出假塑性流体的特征, 其黏度随着wME的增大而增大, 乳液的稳定性增强; 而当wME≥10.0%时, RLE则表现出膨胀型流体的特征, 乳液的黏度较低; 随着温度的升高及水的用量增加, RLE粒子间相互作用减弱, 乳液的稳定性降低. 正交实验结果表明, 影响RLE的黏度及稳定性的顺序为wME＞mH2O∶mRL＞mUE20∶mPVA＞乳化温度. 随着wME的增大, RLE粒子的粒径减小, 其形态也由不规则的形状转变为球形粒子.     

阴离子型微乳液的电导行为及其溶液结构

根据电导测量,研究了属于W/O→双连续→O/W一类微乳液的十二烷基硫酸钠(SDS)/正丁醇/辛烷/水体系的溶液结构.并探讨了表面活性剂离子对微乳液导电行为的贡献,以及表面活性剂与助表面活性剂含量、油含量对微乳液溶液结构的影响.微乳液的导电行为在W/O子区域中主要是由于SDS阴离子和在O/W子区域中是由于Na离子的影响.在双连续区(IZ)中SDS阴离子和Na阳离子都能影响导电行为增加表面活性剂含量有助于形成O/W微乳液,而助表面活性剂和油含量都增加有助于于形成W/O微乳液.     

吩噻嗪在十二烷基硫酸钠/苯甲醇/水微乳液中的定位

采用循环伏安法和荧光猝灭法研究了吩噻嗪（PTZ）在十二烷基硫酸钠（SDS）/苯甲醇（BA ）/ 水（H2O）微乳液中的定位.结果表明,吩噻嗪在十二烷基硫酸钠/苯甲醇/水体系微乳液中位于微乳液膜相中靠近表面活性剂极性头基的一侧,PTZ分子中的S原子和N原子均可朝向表面活性剂的极性头基.     

微乳液法制备的PtSn/C催化剂对乙醇的电催化氧化性能

以甲酸钠为还原剂,在水/triton X-100/乙二醇/环己烷的W/O型微乳液中制备PtSn/C催化剂.采用X射线衍射（XRD）分析催化剂的结构,循环伏安法和电化学阻抗谱法测试催化剂对乙醇的催化氧化性能.结果表明,微乳法制备的PtSn/C催化剂部分合金化,与Pt/C相比,PtSn/C对乙醇的电催化氧化活性有明显提高,具有更高的抗CO中毒能力.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。