脱水KFI沸石中钾离子分布的模拟退火研究

基于四个固定的参量设值：阳离子位能差ＥＭ２－ＥＭ１＝２５．５０ｋＪ／ｍｏｌ、ＥＭ３－ＥＭ１＝－１０．７３ｋＪ／ｍｏｌ和最近邻阳离子对互作用能Ｗ１２＝４５．６ｋＪ／ｍｏｌ、Ｗ１４＝０．５６ｋＪ／ｍｏｌ以及一个温度依赖的参量ＥＭ４－ＥＭ１＝２．６８（Ｔ／３２３）２．５ｋＪ／ｍｏｌ，以能量极小原则，通过模拟退火优化途径研究了ＫＫＦＩ（Ｋ２２．４Ａｌ２２．４Ｓｉ７３．６Ｏ１９２）沸石分子筛中钾离子在四个结晶学不等价可交换阳离子位（Ｍ１－４）上分布的温度依赖。理论预测的阳离子位占据率Ｐｉ（ｉ＝１～４）在Ｔ＝３２３～９２３Ｋ温域与高温ＸＲＤ实验分析数据相符。     

CX2（X=H,FCl）与甲基异丙基醚C—H键插入反应的理论研究

用从头计算方法在ＭＰ２／６－３１Ｇ（ｄ）水平上研究了ＣＸ２（Ｘ＝Ｈ,ＦＣＩ）与甲工异丙基醚的Ｃ－Ｈ键插入反应。ＣＣＩ２与甲基异丙基醚两个淡同的α－Ｃ的Ｃ＝Ｈ键插入势垒分别为１１７．２ｋＪ／ｍｏｌ（甲基）和２０．６ｋＪ／ｍｏｌ（异丙基）。ＣＦ２与异丙基α－Ｃ的Ｃ－Ｈ键上插入势垒为１２０．０Ｋｊ／ＭＬ,在插 Ｃ－Ｈ键时会引起Ｃ－Ｏ键的断裂。ＣＨ２的插入是不需要势垒。对ＣＸ２与二甲醚、甲乙醚、甲基异丙基     

卡宾与醚C——H键插入反应的理论研究（Ⅱ）：——二氯卡宾？…

用量子化学从头算方法在ＭＰ２／６－３１Ｇ（ｄ）水平上研究了单重态的ＣＸ２（Ｘ＝Ｆ,Ｃｌ）与二甲醚中Ｃ－－Ｈ键的插入反应。两个体系的插入反应都是自发的,插入过程是ＣＸ２的亲电－新核过程。ＣＸ２与二甲醇的插入势垒分别为１２５．９ＫＪ／ｍｏｌ（经零点能校正后为１３２．２ＫＪ／ｍｏｌ,Ｘ＝Ｃｌ）和２５５．３ＫＪ／ｍｏｌ（经零点能校正后为２５７．６ＫＪ／ｍｏｌ,Ｘ＝Ｆ）。ＣＦ２的插入反应实际上难以发生。     

壳多糖与丙烯酸丁酯的乳液接枝共聚研究

以十二烷基苯磺酸钠为乳化剂，过硫酸钾－亚硫酸氢钠为引发剂，研究了壳多糖与丙烯酸丁醋的乳液共聚合，结果表明当［Ｋ２Ｓ２Ｏ８］＝［ＮａＨＳＯ３］＝２．５７×１０－３ｍｏｌ·１－１，［ＢＡ］＝０．６８ｍｏｌ．１－１，［Ｃｈｉｔｏｓａｎ］＝１９．２ｇ·ｌ－１，在７０℃下反应５小时，共聚反应的接技率和接枝效率均较高．用红外光谱，差热分析，Ｘ射线衍射，扫描电镜对接技共聚物进行了表征，此外测试了共聚物胶乳成膜的机械性能，表明用丙烯酸丁酯对壳多糖进行接枝改性，可提高壳多糖的韧性，扩大其应用范围．     

溶液组分对铝阳极氧化多孔膜界面电性能的影响

采用电渗法研究了电解质溶液组分对铝阳极氧化多孔膜层界面电性能的影响。结果表明，多孔膜分别经含Ｆ＾－，ＰＯ＾３－４，ＳｉＯ＾２－３或单宁酸溶液浸泡处理后，膜在０．０１ｍｏｌ／ＬＫＣｌ溶液中等电点由原来的ｐＨＩＥＰ＝９．２０分别移至ｐＨＩＥＰ＝３．４０，４．３０，３．３０display structure     

硼掺杂多晶金刚石薄膜电极的电化学特性

用循环伏安法和恒电位法研究了硼掺杂多晶金刚石薄膜电极（ＤＦＥ）的若干电化学特性。电极面积４×４ｍｍ＾２。在０．１ｍｏｌ／Ｌ ＫＣｌ，ＮａＮＯ３，ＮａＯＨ和ＫＨ２ＰＯ４＋Ｎａ２ＨＰＯ４（ｐＨ＝６．８６）电解质溶液中电势窗口均为－５００￣＋８００ｍＶ；而在０．１ｍｏｌ／Ｌ ＨＣｌ和Ｈ２ＳＯ４溶液中电势窗口为－２００￣＋１１００ｍＶ．Ｋ３Ｆｅ（ＣＮ）６的氧化峰电位为＋５００ｍＶ，与Ｐｔ电极测量相同；校正     

析相光度法测定铜（Ⅱ）的研究

本文研究了Ｃｕ（Ⅱ）－ＰＥＧ（聚乙二醇－２０００）－Ｚｉｎｃｏｎ（锌试剂）－（ＮＨ４）２ＳＯ４体系的析相光度法并应用于测定Ｃｕ（Ⅱ）。最宜酸度为ｐＨ５．５～８．５（ＫＨ２ＰＯ４－Ｋ２ＨＰＯ４）缓冲溶液）其络合物的最大吸收位于６１０ｎｍ，表观摩尔吸光系数为４．０×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，Ｃｕ（Ⅱ）浓度在０～１．５ｍｇ／Ｌ范围内服从比尔定律，铜与Ｚｉｎｃｏｎ形式组成为１：２的稳定的蓝色络     

超价化合物NLi4^n＋和OLi4^n＋电子结构和性质

以６－３１Ｇ＾＊基组利用ＨＦ、ＭＰ２和ＤＦＴ方法优化了超价化合物ＮＬｉ４＾ｎ＋和ＯＬｉ４＾ｎ－的几何构型。研究结果表明，ＭＰ２和ＤＦＴ法计算出的ＯＬｉ４分子解离出Ｌｉ和Ｌｉ２的反应能与已有的实验值吻合，对于ＮＬｉ４分子，得到其解离出Ｌｉ和Ｌｉ２的反应能分别为１９１．７８和５１５．３７ｋＪ／ｍｏｌ（ＭＰ２值）。并预测了ＯＬｉ４＾ｎ＋和ＮＬｉ４＾ｎ＋分子的基振动频率。     

聚乙二醇辛基苯基醚—铁（Ⅱ）—过氧化氢化学发光体系研究及应用

本报道了聚乙二醇辛基苯基醚（ＯＰ）－Ｆｅ（Ⅱ）－Ｈ２Ｏ２化学发光体系，建立了高等反悔一测定微量铁的化学发光新方法，检出限为７．６×１０＾－８ｍｏｌ／Ｌ，线性响应的浓度范围为１．０×１０＾－７－１．０×１０＾－３ｍｏｌ／Ｌ，该法所受金属离子孤干扰小，用于实际水样及铜精矿样品的全铁的测定，结果令满意。     

混合微乳液火焰原子吸收法同时测定奶粉中钙和镁

１引言用原子吸收光谱法（ＡＡＳ）测定生物样品中微量元素前常需对样品进行灰化或消化处理，操作繁琐、易产生误差且污染环境。有人曾用聚乙二醇辛基苯基醚（ＯＰ乳化剂）溶液对奶粉进行抽取，通过火焰原子吸收光谱法（ＦＡＡＳ）测定静置分层后的液相中的钙，省去了费事的前处理，但增加了测定操作难度。本文根据微乳液体系的热力学稳定性，高增溶性及优越的传质、吸附性能建立了一种混合微乳液体系同时测定奶粉中钙镁的空气－乙炔ＦＡＡＳ法，克服了生物样品前处理的诸多不便，且可不加分离地进行快速测定。２实验部分２．１仪器与试剂３…     

Incorporation of nonionic emulsifiers inside particles in emulsion polymerization: mechanism and methods of suppression

Emulsion polymerizations of styrene were carried out using two kinds of polyoxyethylene lauryl ether nonionic emulsifiers having different hydrophilic-lipophilic balances (HLB): Emulgen 109P (HLB 13.6); and Emulgen 150 (HLB 18.3). In both cases, incorporation of emulsifier inside polystyrene (PS) particles was clearly observed, as previously reported for the emulsion polymerization of styrene and methacrylic acid using polyoxyethylene nonyl phenyl ether (Emulgen 911, HLB 13.7) nonionic emulsifier. The generality of the incorporation phenomenon of nonionic emulsifier inside polymer particles in emulsion polymerization was clarified. In the case of Emulgen 109P, which is more hydrophobic than Emulgen 150, about 30% of the total amount was incorporated inside the PS particles, higher than for Emulgen 150 (15%). The difference seemed to be ascribed to the difference in the affinities between the nonionic emulsifiers and styrene, which cause the incorporation of emulsifier. On the basis of this idea, suppression of the incorporation was achieved by decreasing the polymerization temperature and the monomer-feed rate. This strongly supports the proposed incorporation mechanism.     

Synthesis and Characterization of Hydrogel Nanoparticles Through Inverse Microemulsion Polymerization of 2-Acrylamido-2-methyl-1-propanesulfonic Acid

Nanosized hydrogel particles prepared through inverse microemulsion polymerization of 2-acrylamido-2-methyl-1-propanesulfonic acid, using the combination of an oil soluble emulsifier (SPAN80) with a water soluble emulsifier (TWEEN 80), and precise determination of HLB range related to the formation of stable single phase microemulsions.

The effect of crosslink density, water phase to oil phase ratio, and the hydrophilic-lipophilic balance (HLB) value on polymerization rate, particle size, and swelling ratio were investigated. It found that polymerization rate and particle size are strongly dependent on the water phase to oil phase ratio. Hydrogel samples prepared using oil soluble and water soluble initiators and the results showed that the initiator type had a great influence on monomer conversion and particle size. Effect of pH on equilibrium swelling of hydrogels was studied by dynamic light scattering and hydrogels showed pH-independent swelling behavior in a broad range of pH values. We also reported and discussed the crosslink density distribution in nanogels prepared by inverse microemulsion polymerization.     

Inclusion of nonionic emulsifier inside polymer particles produced by emulsion polymerization

A general emulsion copolymerization of styrene and methacrylic acid was carried out with polyoxyethylene nonyl phenyl ether nonionic emulsifier. Surprisingly, about 75% of the nonionic emulsifier was included inside forming particles.     

Polymerization of acrylamide in nonionic microemulsions: Characterization of the microlatices and polymers formed

Free radical polymerization of acrylamide was carried out in nonionic microemulsions of water, an isoparaffinic oil, Isopar M and a blend of nonionic emulsifiers: a sorbitan sesquioleate and a polyoxyethylene sorbitol hexaoleate (HLB of the mixture: 9.3). The size and the stability of the latex particles formed after polymerization were studied as a function of monomer, emulsifier and electrolyte concentration. High emulsifier and high monomer contents favor obtaining high molecular weight polyacrylamides. It is shown that both the number of polymer chains contained in each latex particle and the size of the particles are essentially controlled by the acrylamide/emulsifier weight ratio.     

Styrene and methylmethacrylate oil-in-water microemulsions

 A simple procedure for the preparation of styrene-in-water and methylmethacrylate (o/w) micro-emulsions was established. This consisted of the preparation of a w/o emulsion using a low HLB number surfactant (Synperonic NP4, nonyl phenyl with 4 mol ethylene oxide) and a small amount of an anionic surfactant (Aerosol OT, diethyl hexyl sulphosuccinate, or sodium dodecyl benzene sulphonate). The w/o emulsion was then titrated with an aqueous solution of a high HLB number surfactant (Synperonic NP15, nonyl phenyl with 15 mol ethylene oxide). The droplet size and poly-dispersity were determined using photon correlation spectroscopy (PCS). The temperature range within which a microemulsion remained stable decreased with increase in the concentration of styrene or methylmethacrylate and this could be explained in terms of the phase diagram of the microemulsion system. Conductivity measurements as a function of temperature showed that the systems are oil-in-water microemulsions. Received: 20 December 1996 Accepted: 5 March 1997     

A Study on the Vinyl Acetate-co-Butyl Acrylate Latexes in the Presence of N-Methylol Acrylamide and Mixed Type Emulsifiers

Summary: The properties of copolymer latexes depend on the copolymer composition, polymer morphology, initiator, polymerization medium and colloidal characteristics of copolymer particles. Poly(vinyl acetate-co-butyl acrylate) latexes with N-metylol acrylamide were prepared by applying semicontinuous emulsion polymerization. The systems studied were (a) the mixture of anionic sodium lauryl sulfate ether (SELES) with nonionic 30 moles ethoxylated nonyl phenol (NP 30) (50:50), (b) the mixture of anionic sodium lauryl sulfate ether (SELES) with nonionic 30 moles ethoxylated nonyl phenol (NP 30) (70:30), and (c) anionic sodium lauryl sulfate ether (SELES) (100%). The effects of the emulsifier and emulsifier composition on the physicochemical properties of obtained vinyl acetate-co-butyl acrylate latex properties in the presence of N-methylol acrylamide initiated by ammonium persulfate were investigated.     

The dissolution of ionized water-insoluble carboxylated polymer particles in the nonionic emulsifier solution

It was found that 276 nm-sized styrene-butyl acrylate-methacrylic acid terpolymer (P(S-BA-MAA)) (50.4/40.9/8.7, molar ratio) particles produced by emulsifier-free emulsion polymerization dissolved in a polyoxyethylene nonylphenylether nonionic emulsifier aqueous solution at pH values above 11 and above 25°C resulted in polymer microemulsion. The weight-average diameter of P(S-BA-MAA) microparticles in the solution was 31 nm, which was measured by dynamic light scattering spectroscopy. Such a dissolution of the particles was not observed in the absence of the emulsifier.Part CXLI of the series Studies on Suspension and Emulsion.     

壬基酚聚氧乙烯醚聚合度对水煤浆浆体性质的影响

研究了壬基酚聚氧乙烯醚型添加剂的聚合度对变质程度不同的8种煤所制得的水煤浆浆体性质的影响规律。结果表明，壬基酚聚氧乙烯醚添加剂的聚合度对于8种煤所制得的水煤浆的成浆性、流变性以及静态稳定性均有一定的影响，存在一最佳范围。研究还发现，用壬基酚聚氧乙烯醚型添加剂制备水煤浆时，该添加剂的作用与煤的分析基水分质量分数、丝质组分质量分数以及孔体积之间存在着相关性。     

Effect of two Kinds of Imidazolium Ionic Liquids on the Microemulsion Polymerization of Methyl methylacrylate

Summary: In this paper, the microemulsion polymerization of methyl methylacrylate (MMA) was carried out with single and gemini ionic liquids as emulsifier including 1-N-tetradecyl-3-methylimidazolium bromide (C₁₄MIM · Br) and 1, 4-Bis (3-tetradecylimidazolium-1-yl) butane bromide (C₁₄MIM-4-C₁₄MIM · 2Br) respectively, and they were all have typical microemulsion polymerization characters of MMA, but the process of polymerization directly depends on the structure of the imidazolium ionic liquids. The structure and concentration of ionic liquids have effects on the resulted latex particle sizes of PMMA, and much smaller size latexes of PMMA could be gotten with C₁₄MIM · Br as emulsifier than C₁₄MIM-4-C₁₄MIM · 2Br in polymerization. On the other hand, the structure of emulsifier has the effects on the molecular weight (MW) and molecular weight distribution (MWD) of PMMA, so the resulting PMMA prepared from microemulsion polymerization with C₁₄MIM · Br as emulsifier has higher MW but narrower MWD than that of PMMA with the same dosage of C₁₄MIM-4-C₁₄MIM · 2Br as emulsifier.     

油酸单乙醇酰胺聚氧乙烯醚微乳液体系的研究

以油酸单乙醇酰胺聚氧乙烯醚作为乳化剂制备水包油型微乳液.通过拟三元相图、粒径大小及粒径分布确定较优配方:复配表面活性剂(由油酸单乙醇酰胺聚氧乙烯醚和吐温20组成)的亲水亲油平衡值(HLB值)为15,助表面活性剂为正丁醇,复配表面活性剂与助表面活性剂的质量比(Km值)为1,混合表面活性剂与正辛烷的质量比(S/O值)=1∶...