杂双子表面活性剂的合成

α-溴代十四酸甲酯与对甲苯酚经W illiam son醚化、NBS溴化、季铵化、皂化得3个头基分别是羧酸盐和季铵盐的杂双子表面活性剂,其结构经1HNMR,IR和元素分析确认。     

Synthesis and Surface Activity of Heterogemini Imidazolium Surfactants

A series of heterogemini imidazolium surfactants with two-methylene spacer groups ([C_m-2-C_nim]Br_{2, m, n}=8, 10, 12, 14, 16; m≠n) have been synthesized and characterized by 1H NMR and ESI-MS spectroscopy. The effects of various reaction parameters, including stoichiometry, reaction temperature and time, were investigated. In addition, the surface activity study about heterogemini imidazolium surfactants was carried out and the influences of dissymmetric degree on the surface properties were also discussed.     

Synthesis and Interfacial Properties of Imidazoline Surfactants

Quaternary ammonium salts of 2‐undecyl (heptadecyl)‐1‐dithioureido‐ethyl‐imidazoline (SUDEI/SHDEI) have been synthesized, and their interfacial properties are investigated. The effects of temperature, alkyl chain R length, and polarity of solvents on the surface tension are discussed. The results show that surface tension of SUDEI and SHDEI in water solutions decreases with increasing of temperature, and SHDEI shows lower cmc value than SUDEI at constant temperature, indicating that it is easier for SHDEI to form micelles in water. SUDEI and SHDEI show much higher cmc in ethanol‐water (1∶4, v/v) than that in pure water. The molecular structure of SUDEI/SHDEI is composed of lipophilic group R and hydrophilic group comprising active elements S, N and imidazoline ring and the two groups are of similar length, which is similar to that of bi‐block copolymer. Thus, interesting results have been found in the preparation of nanomaterials in the presence of imidazoline surfactants. The corresponding mechanisms are still under investigation.     

新型含硅表面活性剂的合成及性能研究

含有双胺基的三硅氧烷中的伯胺基与D-葡萄糖酸-δ-内酯进行酰胺化,仲胺基与低聚乙二醇甲醚缩水甘油醚、二缩水甘油醚进行烷基化,制备了新型含硅表面活性剂Me₃SiOSiMeR¹OSiMe₃ [R¹=(CH₂)₃NR²(CH₂)₂NHCO(CHOH)₄CH₂OH; R²=H, CH₂CH(OH)CH₂O(CH₂CH₂O)_xCH₃, x=1, 2, 3] (1a, 2a～2c)和(CH₂OCH₂)_y(Me₃SiOSiMeR³OSiMe₃)₂ [R³=(CH₂)₃NR⁴～(CH₂)₂NHCO(CHOH)₄CH₂OH; R⁴=CH₂CH(OH)CH₂OCH₂, y=0, 1, 2] (3a～3c).这些化合物的结构用¹H, ¹³C核磁共振仪和元素分析仪进行鉴定.研究了这些新型含硅表面活性剂的界面性能,在浓度分别为10^-4和10^-5 mol·L^-1时可以将水的表面张力降低至约21 mN·m^-1.     

Effect of Fatty Acid Polyunsaturation on Synthesis and Properties of Emulsion Polymers Based on Plant Oil-Based Acrylic Monomers

This study demonstrated that polymerization behavior of plant oil-based acrylic monomers (POBMs) synthesized in one-step transesterification reaction from naturally rich in oleic acid olive, canola, and high-oleic soybean oils is associated with a varying mass fraction of polyunsaturated fatty acid fragments (linoleic (C18:2) and linolenic (C18:3) acid esters) in plant oil. Using miniemulsion polymerization, a range of stable copolymer latexes was synthesized from 60 wt.% of each POBM and styrene to determine the impact of POBM chemical composition (polyunsaturation) on thermal and mechanical properties of the resulted polymeric materials. The unique composition of each plant oil serves as an experimental tool to determine the effect of polyunsaturated fatty acid fragments on POBM polymerization behavior and thermomechanical properties of crosslinked films made from POBM-based latexes. The obtained results show that increasing polyunsaturation in the copolymers results in an enhanced crosslink density of the latex polymer network which essentially impacts the mechanical properties of the films (both Young’s modulus and toughness). Maximum toughness was observed for crosslinked latex films made from 50 wt.% of each POBM in the monomer feed.     

低聚表面活性剂的合成及性能研究

低聚表面活性剂是指通过连接基将两个以上的传统表面活性剂连接在一起而形成的一类新型表面活性剂。相对于对应的传统表面活性剂,这类表面活性剂具有临界胶束浓度(cmc)低、表面活性高等优点。本文介绍了本研究团队近年针对低聚表面活性剂所开展的研究,包括分子结构不对称的双子表面活性剂、同时具有阳离子和阴离子头基的甜菜碱型双子表面活性剂、三聚和四聚阳离子表面活性剂以及通过原子转移自由基聚合制备的低聚表面活性剂等。     

Cationic Surfactants in Interfacial Synthesis of Linear Aromatic Polyester

Abstract

The polycondensation of terephthaloyl chloride and bisphenol A was used as a model reaction for the production of linear aromatic polyesters in stirred interfacial polymerization. The evaluation of several catalytic and surfactant additives to this system was based upon yields and intrinsic viscosities of the products obtained with both low and high concentrations of cationic surfactants of the quaternary ammonium type, of an anionic surfactant, and of a non-micelle forming quaternary ammonium salt. Although yields were similar in most cases, viscosity differences were marked. The highest intrinsic viscosities, hence highest degrees of polymerization, were found for preparations where cationic surfactant in excess of the critical micelle concentration was employed. Modes of action for such surfactants are suggested. The possibilities include, but are not limited to, solubilization of the product, solubilization of either or both monomers, emulsification of the liquid phases, catalytic phase transfer of one monomer, and micellar catalysis.     

疏水链长对聚氧乙烯失水山梨醇脂肪酸酯界面扩张流变性质的影响

利用悬挂滴方法研究了系列聚氧乙烯失水山梨醇脂肪酸酯(TweenX)在正癸烷-水界面的扩张流变性质. 实验结果表明, 疏水烷基链长较短的Tween20 分子在界面上吸附量较大, 分子排列更紧密, Tween40 和Tween60具有大致相同的“有效截面积”, 导致饱和吸附时界面张力(γ_cmc)比较接近. TweenX浓度大于临界胶束浓度(cmc)时, 由于Tween20 分子排列的更加紧密, 模量和弹性大于Tween40 和Tween60. 当TweenX的疏水烷基链长达到一定长度时, TweenX的界面膜性质受疏水链长的影响减弱, Tween40和Tween60的扩张参数相差不大.     

Surface and Thermodynamic Properties of Nonionic Surfactants Based on Rosin-Maleic Anhydride and Acrylic Acid Adducts

Ester-adduct derivatives of rosin were synthesized by reacting rosin maleic anhydride (RMA) or rosin acrylic acid (RAA) adducts with polyethylene glycol 600 (PEG600), 1000 (PEG1000) or 2000 (PEG2000) and at elevated temperature. These derivatives were evaluated for acid number, FTIR spectroscopy, molecular weight (Mw) and polydispersity. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The surface tension, critical micelle concentration, and surface activities were determined at different temperatures. Surface parameters such as surface excess concentration (Γmax), the area per molecule at interface (Amin) and the effectiveness of surface tension reduction (πCMC) were determined from the adsorption isotherms of the prepared surfactants. Some thermodynamic data for the adsorption process were calculated and are discussed.     

羧酸盐双子表面活性剂的合成及性能

为筛选环境友好的新型双子表面活性剂,以水杨酸为原料设计合成了5个羧酸盐型双子表面活性剂EODPN1-EODPN5[2,2'-(1,2-CH₂CH₂-二-O-)-二-(4-C_nH_2n+1COPhCOONa),n=5,7,9,11和13],并通过核磁共振波谱仪(NMR)和傅里叶变换红外光谱仪(FT-IR)等对目标产物进行了结构表征。 探究了EODPN作为表面活性剂的性能,并利用Gibbs表面吸附方程,通过理论计算得到相关热力学参数,结果表明,目标分子具有优异的表面活性,临界胶束浓度(CMC)值低(最低达0.4 mmol/L),表面张力性能优良(最低达29.74 mN/m),单位面积表面吸附量(Γ)高(最高达3.37×10^-6 mol/m²)。 通过改变疏水基烷基碳链的长度,优化了EODPN的表面活性和自组装能力,筛选出EODPN4为最佳的表面活性剂。 借助EODPN4能与铜离子稳定结合,实现了表面活性剂含量的检测。     

两性孪联表面活性剂的合成及溶液性质

用C10～C16脂肪醇与2-氯-2-氧-1,3,2-二氧磷杂环戊烷低温反应生成环状磷酸酯的中间产物,再用N,N-二甲基十二胺在亲核溶剂中65℃下开环反应合成了4种含N 和磷酸根阴离子的两性孪联表面活性剂C10-C12、C12-C12、C14-C12和C16-C12,其质量收率分别为32%、54%、18%和28%。产物的结构通过1HNMR和元素组成分析,表明两性离子表面活性剂C、H、O、N的分析值与理论计算值偏差不超过0.3%。四种表面活性剂的临界胶束浓度(cmc)在0.0072~0.0125mmol/L之间,临界胶束浓度时表面张力(γcmc)依次为23.90、25.61、27.68和36.08mN/m。其中,C10-C12、C12-C12和C14-C12有较好的界面活性,加入盐可以使表面活性剂与烷烃间的界面张力下降,但下降程度有限,不能达到超低界面张力(10-3mN/m)。     

Synthesis of Some Surfactants Based on Polytriethanolamine and Investigation of Their Surface Active Properties

New modified surfactants were developed by esterification of ethoxylated polytriethanolamine with oleic acid. Triethanolamine was polymerized at three different times 1.30, 2.30, and 3.30 hours to give (P₄, P₆, and P₈) where 4, 6, and 8 refer to the degree of polymerization. The prepared polymer (P₈) was ethoxylated at three different molar ratios of ethylene oxide (40, 100, and 120) and named E(en)P₈. Then the ethoxylated polymers were esterified with oleic acid and abbreviated as E(en)P₈O_m. The surface properties for these surfactants were determined by measuring the surface tension. The structure was confirmed using the elemental analysis, (FTIR, ¹H, ¹³C NMR) spectroscopic.     

新型脂肪酸钐系列四元配合物的合成及其荧光性能

以钐(Sm)为中心离子,二苯甲酰甲烷(DBM)为主配体,脂肪酸[顺丁烯二酸(MA),油酸(OA)和月桂酸(LA)]和邻菲罗啉(phen)[或丙烯腈(AN)]为协同配体,经配合反应合成了一系列新型的脂肪酸钐系列四元配合物——Sm-(DBM)2-MA-phen,Sm-(DBM)2-OA-phen,Sm-(DBM)2-LA-phen,Sm-(DBM)2-MA-(AN)2,Sm-(DBM)2-OA-(AN)2和Sm-(DBM)2-LA-(AN)2,其结构和性能经UV,FL,IR,元素分析和TG表征。结果表明,在350 nm波长激发下,配合物发出以钐的特征发射谱线(644 nm左右)为主的强荧光。协同配体向钐离子传递光能的能力顺序为:AN>phen。     

阴离子孪连表面活性剂的合成及其表/界面活性研究

合成了疏水链长度不同和连接基长度不同的7种系列阴离子孪连表面活性剂,研究了它们的表/界面活性。结果表明,它们有较低的表面张力和临界胶束浓度(CMC),有很好的表面活性。它们的CMC都在10-5~10-6mol/L之间,表面张力在26·5~34mN/m之间。它们有非常好的抗一价、二价盐的能力。除了C16-C2-C16在高于5%的NaCl溶液中会产生析出外,其余孪连表面活性剂都能耐盐20%以上。随着盐浓度的增加,孪连表面活性剂与烷烃间的界面张力逐渐降低,能达到10-3mN/m。与中原油田原油间的界面张力能降低到10-3~10-4mN/m,表明它们可应用于特高矿化度油藏提高采收率。     

Gemini表面活性剂的合成、表征及性能测定——油田化学专业综合实验

介绍一个油田化学专业综合实验,通过该实验可了解Gemini表面活性剂的发展现状,掌握阳离子型Gemini表面活性剂BQAS的合成及纯化方法,了解结构表征的原理和方法,掌握表面性能和缓蚀性能的评价方法。     

Effects of Charged Surfactants on Interfacial Water Structure and Macroscopic Properties of the Air-Water Interface

Surfactants are used to control the macroscopic properties of the air-water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum-frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br⁻ counterions compared to smaller Na⁺ ones, and also due to the flip-flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H⁺ points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole-dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H⁺ point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature.     

表面活性剂对驱油聚合物界面剪切流变性质的影响

利用双锥法研究了表面活性剂十二烷基苯磺酸钠(SDBS)和十六烷基三甲基溴化铵(CTAB)对油田现场用部分水解聚丙烯酰胺(PHPAM)和疏水改性聚丙烯酰胺(HMPAM)溶液的界面剪切流变性质的影响,实验结果表明:HMPAM分子通过疏水作用形成界面网络结构,界面剪切复合模量明显高于PHPAM.SDBS和CTAB通过疏水相互作用与HMPAM分子中的疏水嵌段形成聚集体,破坏界面网络结构,剪切模量随表面活性剂浓度增大明显降低.同时,界面膜从粘性膜向弹性膜转变.低SDBS浓度时,少量SDBS分子与PHPAM形成混合吸附膜,界面膜强度略有升高;SDBS浓度较高时,界面层中PHPAM分子被顶替,吸附膜强度开始减弱.阳离子表面活性剂CTAB通过静电相互作用中和PHPAM分子的负电性,造成聚合物链的部分卷曲,从而降低界面膜强度.弛豫实验结果证实了表面活性剂破坏HMPAM网络结构的机理.     

多取代吡咯基脂肪酸的合成

许多吡咯衍生物具有生理活性,近年来发现1-芳基取代吡咯具有明显的生理效应,作者曾合成了部分多取代吡咯化合物,并研究了其NMR谱。