颗粒乳化剂的研究及应用

近年来,颗粒乳化剂因其在食品、采油、化妆品、医药、催化以及功能纳米材料制备等领域具有潜在应用前景而备受关注。本文综述了近来颗粒乳化剂的研究进展,归纳了颗粒乳化剂的种类,包括:无机纳米粒子、表面改性或杂化的无机粒子、有机纳米粒子以及特殊的颗粒乳化剂Janus粒子;并对颗粒乳化剂能够在油水界面稳定吸附的热力学机理和动力学行为进行了阐述,颗粒乳化剂在油水界面接触角以及粒径大小是其在界面稳定吸附的关键参数,而颗粒在油水界面的排布方式则主要受粒子之间相互作用的影响。重点介绍了颗粒乳化剂的热点应用,包括:(1)利用颗粒乳化剂制备Pickering乳液,以及通过对颗粒乳化剂的功能化,使得Pickering乳液具备环境响应性(即pH、盐浓度、温度、紫外光、磁场敏感响应性);(2)以颗粒乳化剂为构筑基元、以Pickering乳液为模板制备Janus颗粒、Colloidosome、具有多级结构的粒子或膜,以及多孔结构材料;(3) Janus粒子在催化领域的应用。     

乳化沥青及其乳化剂的发展与应用

概述了国内外乳化沥青及其乳化剂在建筑防水、道路维修养护等领域的应用概况,着重论述了乳化剂的分类、选择方法以及乳化剂复配体系的应用情况。根据我国的现状,指出了乳化沥青的高性能化、沥青乳化剂多样化将是主要的发展方向。     

基于定量构效关系设计自乳化系统

将定量构效关系引入到自乳化系统中, 采用HF/6-31G^*方法优化分子结构, 在此基础上计算出组分的量子化学参数, 考察组分含量、立体效应、疏水效应、静电效应对自乳化体系的微乳区域面积和粒径的影响, 通过多元线性回归建立了分子结构参数和组分比例与体系的微乳区域面积/粒径间的定量函数模型, 并对模型外的组分组成的测试集进行了预测. 研究结果表明: 乳化剂与助乳化剂的用量比是影响自乳化体系相行为的主要因素, 油相和助乳化剂含量增大, 粒径增加, 乳化剂含量增大, 粒径减小; 而组分间的相互作用力对系统性质影响较小. 除以肉豆蔻酸异丙酯(IPM)为油相建立的模型外, 其余模型均具有较好的预测效果, 利用这些规律可为自乳化系统的组分筛选提供理论指导, 提高实验效率.     

环氧树脂水基分散体系的相反转乳化

以聚乙二醇－邻苯二甲酸酐－环氧树脂Ｅ－４４多元嵌段共聚体为乳化剂,将环氧树脂Ｅ－４乳化成水包油的稳定水基乳液。用乳液体系电导率和粘度的变化表征了相反转乳化过程。研究了乳化剂浓度、三元多嵌段共聚体中亲水嵌段分子量和乳化温度对相反转乳化过程的影响。实验结果表明,体系在较高乳化剂浓度（９．１％）下为完全相反转,在低乳化剂浓度（４．１％）下为不完全相反转。相反转时水与环氧树脂Ｅ－４４的重量比值随乳化剂浓度     

乳化剂分子亲水组分含量对相反转乳化过程的影响

高分子树脂水基分散体系 ,因其结构的可灵活调节性 ,在许多方面得到应用 ,又因其不含有机溶剂 ,能完全满足环境保护和生态的要求而备受关注 [1～ 3] .相反转乳化技术是制备高分子水基体系的新方法 ,它适用于制备包括加聚物和缩聚物的大多数高分子水基体系 ,大大拓宽了水基体系的范围 [4 ] .杨振忠等[5] 利用自己合成的高分子非离子型乳化剂将环氧树脂乳化成微粒尺寸小且分布窄的水基分散体系 ,对相反转机理和相反转技术进行了深入研究 .研究表明 ,乳化剂浓度和乳化温度对相反转后水基微粒尺寸和形态有重要影响 ,高乳化剂浓度和较低的乳化温…     

影响环氧树脂E-44相反转乳化的因素

研究了乳化剂的HLB值、乳化剂浓度、乳化温度、搅拌强度对环氧树脂E-44相反转乳化中临界含水量Rf值与乳状液稳定性的影响,探讨了环氧树脂E-44相反转机理。实验结果表明环氧树脂E-44从W/O向O/W相反转的发生与乳化剂的HLB值与浓度、乳化温度、搅拌强度等因素都有关,其Rf值随着乳化条件的不同是动态变化的。     

转相乳化制备高分子蜡乳液及其在水性涂料中的应用

本文采用转相乳化法以脂肪醇聚氧乙烯醚(MOA-15)、丙二醇嵌段聚醚(L31)、月桂酸聚氧乙烯酯(LAE-4)为复合乳化剂对高分子蜡进行乳化,通过正交实验法得出了乳化高分子蜡的较佳工艺条件为:复合乳化剂的HLB值9,乳化剂用量8%,乳化温度80℃。通过动态激光光散射分析仪测试了蜡乳液的粒径分布,蜡乳液粒径为317.6nm。通过动态流变研究了高分子蜡乳液的模量与动态频率的关系,测试结果表明,蜡乳液体系具有较佳的黏弹性。将蜡乳液与水性树脂复配,研究了不同蜡乳液含量对水性涂料涂膜性能的影响。随着蜡乳液含量从0增加至4%时,涂膜的磨耗量从29.2mg降至13.9mg,吸水率从34.1%降至20.5%,涂膜光泽度不断增加。     

不完全相反转乳化过程分散相水滴形态发展研究

相反转乳化技术是制备高分子树脂水基分散体系的新方法[1～4].相反转指多组分体系(如油/水/乳化剂)中的连续相在一定条件下相互转化的过程,如在油/水/乳化剂体系中,其连续相由水相向油相(或从油相变为水相)的转变.在连续相转变区,体系的界面张力最低,因而分散相的尺寸最小.同理,可利用相反转技术直接将高分子树脂乳化为尺寸很小的水基微粒,即制备高分子树脂的水基分散体系.由于高分子树脂的粘弹性及相反转过程的复杂性,对高分子树脂的相反转乳化过程的机理研究较少.杨振忠[5]等通过调节高分子非离子型乳化剂浓度,可以有效地控制相反转完善程…     

非离子型水性环氧乳液的制备工艺及性能研究

采用实验室自制的非离子型高分子乳化剂通过相反转法对环氧树脂E-20进行乳化分散来制备水性环氧乳液,对环氧树脂乳化的工艺条件进行了优化研究,并对不同条件的乳液进行了综合性能的分析。具体工艺条件包括:环氧树脂乳液体系中各物料的比例关系,乳化时体系的温度和搅拌速度。结果表明,乳化剂含量为12.5%,助溶剂含量为11.5%,乳化温度为30℃,搅拌速度为300r/min时,乳液的稳定性及漆膜的综合性能(包括漆膜的力学性能和抗腐蚀性能)佳。     

生物质快速热解油水相溶液超声乳化特性

使用生物油水相溶液与0# 柴油乳化,筛选了四种常用乳化剂和一种助乳化剂进行复配乳化实验,考察了复配乳化剂型号、乳化剂用量、超声作用时间对乳化效果的影响。结果表明,六种乳化液超过30d不破乳,与0# 柴油相比,密度和热值相差不大,含水量3%以下,黏度增大约40%,pH值降低一半。因素分析法表明,水相溶液与柴油质量比和不同的水相溶液对乳化效果影响较大。探讨了乳化机理,认为生物油水相溶液中水、醛、酸、酮等极性组分化合物稳定地被乳化剂包裹在W/O型乳化液液滴中,生物油水相溶液中少量的乙酸乙酯、芳香类化合物等则增溶于非离子乳化剂胶束中。热力学分析表明,超声乳化作用比静置作用具有更大的熵增,乳化液更趋于稳定平衡状态。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.