系列磺基甜菜碱的合成及表面性能的研究

以N,N-二甲基乙醇胺、酰氯和丙磺内酯为原料,合成了系列磺基甜菜碱型两性表面活性剂;并通过红外光谱对目标产物进行了结构表征,结果表明产物的分子结构与设计的分子结构相符。采用滴体积法对两型表面活性剂的表面性能进行了测定;其中SB9-coo-2-3的临界胶束浓度（cmc）为23.550×10-4mol.L-1,cmc为31.006mN.m-1;SB11-coo-2-3的cmc为9.908×10-4mol.L-1,cmc为27.669mN.m-1;SB13-coo-2-3的cmc为1.968×10-4mol.L-1,cmc为24.932mN.m-1。结果表明,随着烷基链长的增加,系列磺基甜菜碱cmc呈指数下降,cmc逐渐下降,表面活性逐渐增加。     

双头基表面活性剂的合成、表征及其性能

以棕榈酸、四甲基二丙烯三胺和丙烷磺内酯为主要原料合成了一种双头基表面活性剂N,N-双[3-（二甲基磺丙基铵基）-丙基]-N-十六酰胺,红外光谱和质谱分析验证了产物的结构。对产物进行性能测试,结果表明：25℃时,临界胶束浓度cmc为1.78×10?4mol/L,γcmc为50.1mN/m;在浓度大于cmc时,硝基苯在产物胶束相的分配系数lgKmc=3.12;钙皂分散指数LSDR为4%;硬水中的稳定等级为5级。     

基于短碳链氟碳表面活性剂合成及复配性能测试

合成了一种以短碳链全氟丁基磺酰氟为基础的氟碳表面活性剂,并通过IR、19FNMR、1HNMR等对其进行结构表征,证明合成产物为目标产物,并选用称重法测得产物的表面张力为17.05mN/m,cmc为1.12%。通过氟碳-碳氢表面活性剂的复配,极大地降低了其复配体系的表面张力和cmc,为短碳链氟碳表面活性剂在水成膜灭火剂中的应用提供理论支持。     

两性双子表面活性剂的合成及性能研究

以二乙胺盐酸盐、十二烷基二甲基叔胺、环氧氯丙烷和丙磺酸内酯等为原料,合成了一种两性型双子(Gemini)表面活性剂,并采用红外光谱和元素分析对合成产物进行结构表征;采用滴体积法测定合成产物的表面张力曲线;采用电导率法测定并计算了合成产物的胶束化热力学参数。结果表明,合成产物的临界胶束浓度(cmc)和cmc时的表面张力分别为8×10-5mol/L和38.57 m N/m,且随着温度的升高,产物溶液的cmc升高。胶束化过程的ΔHθm为负值,说明胶束化过程是一个放热过程;胶束化过程的ΔSθm为正值,说明胶束化过程是一个熵驱动过程。     

几种新型杯[4]芳烃衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合、一步取代反应合成了对叔丁基杯[4]芳烃的衍生物,两步取代反应合成了对叔丁基杯[4]芳烃的衍生物。用FT-IR,^1HNMR,FAB-MS对产物的结构进行了表征。     

双酰胺型磺基甜菜碱表面活性剂的合成与性能

以辛酸、N,N-二（3-氨丙基）-甲胺和1,3-丙烷磺内酯为主要原料,通过两步反应设计了一种新型双酰胺型磺基甜菜碱表面活性剂。采用红外光谱、质谱、核磁等方法确证产物结构,并对双八酰胺磺基甜菜碱的表面化学眭能、应用性能进行了研究。结果表明,该产品具有较高的表面活性,25±0．2℃时临界胶束浓度cmc为1．02×10^-3mol·L^-1,1cmc为30．13mN·m^-1,且具有良好的润湿洼、抗硬水性以及钙皂分散性。     

杯芳烃的合成及其对二氧化碳的吸附研究

以对叔丁基苯酚和甲醛溶液为原料,在酸碱条件下采用两步法合成杯[4]芳烃和杯[6]芳烃,并对这两种产物进行了结构表征。同时将合成的杯芳烃进行了对二氧化碳的吸附,发现对叔丁基杯[6]芳烃对二氧化碳的吸附百分比为1．516％。     

6,7-甲氧基香豆素冠醚双功能化杯【4】芳烃的合成与表征

以对叔丁基杯[4]芳烃为原料,经碱催化两步合成了26,28-二（6,7-二甲氧基香豆素-4-亚甲基）-5,11,17,23-四叔丁基杯[4]芳烃-25,27-冠-6,产物经IR、^1H NMR表征和元素分析表征,该衍生物为锥形结构并与设计思想一致。     

磺酸盐双子表面活性剂的合成及其性能研究

以间苯二酚和甲醛、亚硫酸氢钠为原料,在100℃通过磺甲基化制得中间体,再与溴代十二烷通过威廉姆森醚化得到阴离子磺酸双子表面活性剂,总收率46.7%。研究了反应时间、反应温度和反应物摩尔比对收率的影响。用红外光谱和元素分析确认了其化学结构。测得其cmc和γcmc分别为0.81 mmol/L、γcmc=28.5 mN/m。对其与其他表面活性剂进行复配,在最佳配比下,有更低的cmc和γcmc。     

杯芳烃的合成及其在聚丙烯中的抗热氧性能研究

以对叔丁基苯酚和甲醛为原料,在碱的催化作用下,合成对了叔丁基杯（４）芳烃、杯（６）、杯（８）芳烃。产物结构经＾１Ｈ－ＮＭＲ鉴定,并用热重法评价了对叔丁基杯（ｎ＝４、６、８）在聚丙烯中的抗热氧性能。结果表明,含对叔丁基杯（ｎ）芳烃（ｎ＝４、６、８）的聚丙烯耐热氧性能明显优于２,６－二叔丁基－４－甲基苯酚 ,而且抗热氧性能为对叔丁基杯（６）芳烃〉对叔丁基杯（４）芳烃〉对叔丁基杯（８）芳烃。     

Adsorption of amino acid derivatives on calixarene carboxylic acid impregnated resins

Macrocyclic host molecules calixarene carboxylic acid derivatives are found to act as powerful extractants for biologically important amino compounds. A series of adsorbents were prepared from a methacrylate-based polymer Amberlite XAD-7 by impregnation with various calixarene derivatives, for adsorptive recovery of amino acid derivatives. The larger macrocycles calix[6]arene and calix[8]arene carboxylic acid derivatives were more effective for adsorption of amino acid derivatives on the impregnated resin than the calix[4]arene derivative. Since adsorption proceeds mainly via electrostatic interaction, the carboxylic acid groups introduced into the calixarene platform were important for adsorption of cationic amino acid derivatives. The adsorption selectivity for amino compounds using adsorbent impregnated with the calix[6]arene carboxylic acid derivative depends simply on the hydrophobicity of the adsorbates.     

杯芳烃／聚丙烯共混体系耐热氧性能的研究

合成了对叔丁基杯[4]、杯[6]、杯[8]芳烃,并用热重法和烘箱老化评价了共混体系的耐热氧性能。结果表明,杯芳烃能明显提高聚丙烯的耐热氧性能,其耐热氧能力为：对叔丁基杯[6]芳烃＞对叔丁基杯[4]＜2,6－二叔丁基－4－甲基苯酚。     

杯[4]芳烃偶氮衍生物的合成及其金属离子萃取性能

杯芳烃作为超分子化学的重要组成部分,近年来得到了快速发展并成为化学家的研究热点。以脱叔丁基-杯[4]芳烃为原料合成了杯[4]芳烃偶氮衍生物,其结构经IR和1H NMR所表征。研究了该主体分子对金属离子的萃取性能,实验结果表明,该主体分子对Mg2＋具有较高的萃取作用。讨论了主客体间配位作用的机制。     

Liquid phase extraction of azo dyes by novel calixarenes bearing phthalonitrile and diiminoisoindoline groups

This paper presents a study on the removal of azo dyes [Methyl Orange (MO) and Trapaeolin 000 (TP)] from aqueous solution using new phthalonitrile and isoindoline substituted calix[n]arene derivatives into the organic phase in order to explore the potential use of these calixarenes as low-cost efficient extractants for removal of these azo dyes from wastewater. The effect of NaCl concentration, contact time, and pH on the extraction of these azo dyes was also investigated for all calixarene derivatives. The stoichiometric ratio between the calixarene derivatives (5 and 6) and selected azo dyes (MO and TP) was estimated through job’s plot.     

Micellar Effects in Olefin Hydroformylation Catalysed by Neutral,Calix[4]arene‐Diphosphite Rhodium Complexes

The combination of calixarene‐derived surfactants and neutral rhodium complexes containing a hemispherical “1,3‐calix‐diphosphite” ligand led to efficient catalysts for the hydroformylation of octene and other olefins in water. While the surfactants allowed the formation of micelles that dissolve both the catalyst and the alkene, thereby resulting in high olefin:rhodium ratios, the diphosphite provided a tight envelope about the catalytic centre able to drive the reaction towards the linear aldehydes. Best results in the hydroformylation of 1‐octene were obtained when using [tetra(p‐sulfonato)]‐(tetra‐n‐butoxy)‐calix[4]arene as surfactant. With this additive remarkable linear to branched aldehyde ratios of up to 62 were obtained, the corresponding activities being higher than those observed when operating in an organic solvent [turnover frequencies (TOFs) up to 630 mol(converted 1‐octene)⋅ mol(Rh)⁻¹⋅h⁻¹].     

Electrochemical oxidation of <Emphasis Type="Italic">p</Emphasis>-sulfonated calix[8]arene

The water-soluble p-sulfonated sodium salt of calix[8]arene (III) was synthesized. The product was characterized by FT-IR, NMR and UV–Vis spectra.Then the electrochemical behaviors of p-sulfonated sodium salt of calix[8]arene in NaAc+HAc (pH = 4) buffer solution was studied. In aqueous solution, p-sulfonated calix[8]arene can be oxidized when the potential is more than 0.7 V vs SCE. It was confirmed that the reaction was a two-electron irreversible electrochemical reaction. The transfer coefficient, α, was measured as 0.7. At 25°, the diffusion coefficient of p-sulfonated calix[8]arene was determined as 8.6 × 10⁻⁷ cm² s⁻¹. The diffusion activation energy of p-sulfonated calix[8]arene was 18.9 kJ mol⁻¹ at pH = 4.     

新型杯[4]芳烃衍生物对Pb~(2+),Cd~(2+)的萃取性质

研究了新型杯[4]芳烃D对Pb2+,Cd2+离子的液-液萃取性质,并将其与自制的杯[4]芳烃A及其衍生物B、C对Pb2+,Cd2+离子的液-液萃取性质进行了比较。结果表明,与化合物A~C相比,D对Pb2+萃取率最高,在实验条件下,可达到42.8%;测试的四种化合物对Cd2+离子的萃取效率均不佳,未经任何修饰的杯[4]芳烃A的萃取效率最高,仅8.5%。推测对Cd2+的萃取为阳离子交换机理。     

Gemini表面活性剂溶液的胶束聚集数研究

以芘为荧光探针、二苯甲酮为猝灭剂,用稳态荧光探针法测定了系列阴离子型Gemini表面活性剂的胶束聚集数（Nm）。以芘的饱和水溶液为溶剂配制表面活性剂溶液,二苯甲酮的适宜浓度取小于1.00 mmol/L时,可以获得满意的实验结果。当表面活性剂溶液浓度为5～10倍cmc时,Nm随表面活性剂浓度增大而线性增大,而随温度的变化略有波动。Cs=CMC时,Nm值为一本征值,定义为临界胶束聚集数[Nm]。[Nm]值可从Nm～Cs实验曲线外延得到。     

Molecular composites obtained by polyaniline synthesis in the presence of p‐octasulfonated calixarene macrocycle

Polyaniline (PANI) molecular composites were synthesized by chemical oxidative polymerization of the aniline and aniline dimer, N‐phenyl‐1,4‐phenylendiamine, in the presence of a macrocycle, calix[8]arene p‐octasulfonic acid (C8S), using ammonium peroxidisulfate as oxidant. The macrocycle has acted both as acid dopant and surfactant to obtain processable PANI‐ES. The PANI/calix[8]arene p‐octasulfonic acid composite was also obtained by a simple doping of PANI emeraldine base form with calix[8]arene sulfonic acid. The structure of materials was confirmed by Fourier transform infrared, UV–vis and nuclear magnetic resonance spectroscopy. All synthesized composite materials are amorphous and soluble in chloroform, dimethylsulfoxide, NMP, showing excellent solution‐processing properties combined with electrical conductivity. Cyclic voltammetry evidenced a good electroactivity for the composite films. Dielectric properties (dielectric constant and dielectric losses) were determined and are comparable with those of other PANI/ionic acid polymer composites. Preliminary studies have evidenced a high dielectric constant (10⁴ at 100 Hz) and electrical conductivity of 6 × 10^?3 S/cm for PANI composites. From sulfur elemental analysis of the PANI/calixarene, it results that the content in macrocycle is ～30% (weight). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrochemical responsive arrays of sulfonatocalixarene groups prepared by free radical polymerization

A styrene based water soluble polymer containing pendant sulfonated calix[4]arene groups has been synthesized by using free radical polymerization combined with post-polymerization sulfonation chemistry. The monomer 25-(4-vinylbenzyl)-26, 27, 28-hydroxy-calix[4]arene (VBC4A) was prepared in 3 steps: (1) reduction of 4-vinyl benzoic acid to the respective alcohol (2) formation of the bromide by the Appel reaction and (3) synthesis of the respective ether by Williamson O-alkylation reaction with calix[4]arene. Polymerization was accomplished by azobisisobutyronitrile (AIBN) initiated free radical polymerization technique to afford P(VBC4A) with Mn value of 7090 g/mol and moderate polydispersity. The resulting P(VBC4A) was subsequently reacted with acetyl sulfate to afforded the sulfonated polymer. The reaction was followed by nuclear magnetic resonance and infrared spectroscopy, and the results suggest that the sulfonation reaction lead to nearly quantitative functionalization of the calixarene functional polymer. Elemental analysis by X-ray photoelectron spectroscopy confirmed these findings on the degree of sulfonated functionalization. Electro-responsive properties of the sulfonated polymer were studied by cyclic voltammetry and isothermal titration calorimetry in phosphate buffer saline solution. A response to electrochemical stimulus is observed where guest molecules of methyl viologen incorporate and dissociate with P(VBSC4A).