氟表面活性剂的工业合成及应用

讨论了氟表面活性剂3种较为成熟工业合成方法,即电解氟化法、氟烯烃调聚法和氟烯烃齐聚法等,比较了3个方法的优缺及各自有待解决的问题.介绍了氟表面活性剂的特殊性能及目前在一些领域的特殊应用.认为我国研制氟表面活性剂在性能、种类、价格及应用领域上与国外相比尚有较大差距;应充分利用自身市场优势.抓住机遇.提高合成技术、工艺,降低成本.     

氟系表面活性剂

<正> 氟系表面活性剂具有烷烃系、硅系表面活性剂没有的优点是人所众知的。现在,各种氟系表面活性剂正在工业上逐渐应用,它不是简单地代替烷烃系表面活性剂,由于它具有各种特性,其应用领域将迅速扩大。 一、氟系表面活性剂的特性 氟系表面活性剂与烷烃系表面活性剂一样,从亲水性的构造分类可分为:阴离子型、阳离子型、非离子型及两性型,其化学结构与烷烃的亲水基化学结构几乎相同,它的特性主要取决于氟碳键。     

含氟表面活性剂的技术及市场应用

氟表面活性剂为特种表面活性剂产品中最重要的一类品种，主要应用于技术要求较高的特种场合或一般普通表面活性剂难以胜任的、应用效果较差的领域。同时又可以作为普通表面活性剂增效用的特殊添加剂，通过添加极少量的氟表面活性剂后的普通表面活性剂产品，即可极大地改善普通表面活性剂的性能，有时还能达到意想不到的效果。但是由于氟表面活性剂的商品价格要比普通表面活性剂高，对氟表面活性剂的推广应用形成一定的局限性，这是唯一的缺点。     

单晶硅表面微结构调节技术的改进

提出改变碱液腐蚀单晶硅表面特性的一个简单方法,即在碱液中加入活性剂改变碱液在硅表面的润湿性能从而改变其腐蚀特性。分别采用普通碱液、四甲基氢氧化铵（tetramethylammonium hydroxide,TMAH）溶液和加入阴离子有机氟表面活性剂的普通碱液腐蚀硅表面。结果发现：普通碱液和TMAH腐蚀液腐蚀的硅表面的金字塔大小差异大、有许多蜂窝状的小金字塔,反射率较高;用加入阴离子有机氟表面活性剂的普通碱液腐蚀的单晶硅表面,能形成比较规则的金字塔,金字塔尺寸为4～6μm、均匀性好、覆盖率高、表面反射率下降到12．65％。有机氟表面活性剂能提高硅在碱中腐蚀速率,有效调控单晶硅金字塔形貌、大小与分布,为精确调控单晶硅表面微结构提供了可能。     

氟碳表面活性剂及其应用

一、特点及用途氟碳表面活性剂为一类性能独特的表面活性剂,正在不断显示其重要性。其结构可用通式:R_f～X表示,R_f表示含氟(全氟或多氟)碳链;X表示极性基团。这类化合物的特点是:(1).表面活性高:普通碳氢表面活性剂只能使水溶液表面张力降至30达因/厘米左右,而氟     

特种表面活性剂和功能性表面活性剂(ⅩⅦ)——氟硅表面活性剂的合成及应用

综述了氟硅表面活性剂的主要合成方法,如硅氢加成法、自由基聚合法及缩聚法;介绍了氟硅表面活性剂在橡胶、涂料、润滑剂及其他精细化学品等方面的应用及性能,最后对氟硅表面活性剂的发展进行了展望.     

化学驱用特种表面活性剂的文献综述

随着油田开采程度的深入,普通表面活性剂由于其固有的弱点已不能满足在高温高盐条件下提高采收率的要求,于是把目光转向了新型耐温抗盐表面活性剂——特种表面活性剂。化学驱用特种表面活性剂主要包括G em in i型表面活性剂、氟表面活性剂、生物表面活性剂和非离子-阴离子复合型表面活性剂。本文将就特种表面活性剂的研制开发、特性及应用作较详细介绍。     

造纸化学品氟表面活性剂性能介绍

普通表面活性剂分子中碳氢链中的氢原子部分或全部用氟原子取代，就成为氟表面活性剂，从而具有许多普通表面活性剂不具有或者更优的性能，引起了人们普遍的重视，显示出越来越强的生命力，广泛应用于消防、化工、农药、选矿、造纸、皮革、纺织等各个领域。     

氟表面活性剂的合成及油田应用的最新进展（待续）

<正>与碳氢表面活性剂相比,氟表面活性剂降低表面张力的效率更高,且具有高热稳定性并能改善表面性能。然而,氟表面活性剂的亲水性不如碳氢表面活性剂。这一点限制了氟表面活性剂在更大范围内的应用。例如,Yoshino等合成了含有2条氟烷基链的阴离子型氟表面活性剂（图9）,     

氟硅表面活性剂的制备方法与应用探讨

介绍了氟硅表面活性剂的结构和性能,叙述了氟硅表面活性剂的合成工艺及其应用研究进展。认为氟硅表面活性剂有效结合了含氟表面活性剂和有机硅表面活性剂的性能优点,具有非常良好的应用前景,国内相关行业的科研工作者应加强与其他类型表面活性剂的复配增效研究,开发出高效环保、成本低廉、容易降解的多种用途的氟硅表面活性剂;积极开展有机金属化合物法、官能团反应法等先进技术制备氟硅表面活性剂的研究,缩小与欧美、日本等发达国家的差距。     

Synergistic effect of organoclay fillers based on fluorinated surfmers for preparation of polystyrene nanocomposites

Novel fluorinated reactive surfactants were used for the organic modification of monmorillonite clays. These organoclays were used for the preparation of polystyrene?clay nanocomposites by in‐situ free radical polymerization. Reference systems based on hydrocarbon homologous surfmer and nonpolymerizable surfactants were also used to deduce the effect of the fluorine moiety and the polymerizable function on the morphology and thermal stability of the prepared nanocomposites. Different structural parameters of the surfactants were investigated and modulated for the clay modification including: the nature of surfactant (surfmer/classical surfactant, fluorinated, or hydrocarbonated), the length of the fluorinated chain as well as the length of the hydrocarbon spacers linking the ammonium head to the fluorine chain or the polymerizable acrylic function. Wide angle‐X‐ray scattering (WAXD), thermogravimetric analysis (TGA), and electronic microcopies (TEM and SEM) were used to establish a structure‐morphology, thermal properties relationships, and to highlight the key parameters governing the exfoliation process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42347.     

Properties and applications of amphoteric surfactant: A concise review

Amphoteric surfactants have long hydrophobic hydrocarbon chain and hydrophilic positive as well as negative charged center connected with each other by a spacer group. Thus, this type of surfactant maintains overall charged neutrality. The properties of amphoteric surfactants depend primarily on the length of the hydrophobic hydrocarbon chain, the number of methylene segments in the spacer, the positive and negative charged groups, and their relative position. The ionic activity of amphoteric surfactants is influenced according to the pH value of the solvent. They display cationic behavior below the isoelectric points and anionic behavior at a higher pH. They take the shape of zwitterions in the area of the isoelectric point. In fact, amphoteric surfactants can be parted into pH-sensitive and pH-insensitive surfactants. The pH-insensitive surfactants stay as zwitterionic form irrespective of the pH of the solution. This surfactant has some unique features because of its precise molecular structure as follows: high water solubility, high surface activities, a wide isoelectric range, low critical micelle concentration (CMC), high foam stability, low toxicity, low irritating, excellent biodegradability, bioactivity, interface change, and so on. Because of these special characteristics, amphoteric surfactants have been immensely interested in many applications in the scientific community, including cosmetics, chromatography, enhanced oil recovery, electrochemistry, nanoscience, polymer chemistry, and waste water treatment. This review aims to study about amphoteric surfactants, which have only one hydrophobic hydrocarbon tail and two oppositely charged hydrophilic headgroups connected with each other by a spacer group and its properties, applications in various academics and industrial fields.     

含氟季铵盐表面活性剂的合成与应用研究进展

含氟季铵盐表面活性剂是一类具有高表面活性、高耐热稳定性、高化学稳定性和憎水、憎油等特殊性能的新型表面活性剂。本文系统综述了含氟季铵盐表面活性剂的合成路线和方法,并按照其不同的分子结构特点进行了分类比较,着重介绍了含二烯丙基、羟基、双子、胺基等一些特定功能基团的含氟季铵盐表面活性剂的合成和特性,并阐述了其在相转移催化剂、超临界CO2助剂、金属腐蚀抑制剂、泡沫灭火剂、织物整理剂、抗菌剂等方面的应用。最后,分析了含氟季铵盐表面活性剂目前存在的问题及对其发展趋势进行了展望。     

Fluorocarbon-hydrocarbon interactions in interfacial and micellar systems

The interactions of fluorocarbons and hydrocarbons in liquid mixtures are known to be highly nonideal. Recent research has indicated that the unusual characteristics of such interactions have a significant influence on the behavior of many interfacial and micellar systems in which such interactions occur. Results from several different studies are presented. These involve (a) properties of partially fluorinated surfactants and lipids, including comments on the use of fluorine substituted groups as spectroscopic probes; (b) surface tensions of nonideal mixtures of liquid fluorocarbons and hydrocarbons and their interfacial tensions against water; (c) adsorptions of fluorocarbon and hydrocarbon surfactants to air/water, hexane/water, and perfluorohexane/water interfaces and a comparison of relative affinities; (d) formation of mixed micelles of fluorocarbon and hydrocarbon surfactants and evidence of partial miscibility of micelles; (e) comparison of adsorption of fluorocarbon and hydrocarbon surfactants to graphon; and (f) comparison of wetting of hydrocarbon-like solids by aqueous solutions of fluorocarbon and hydrocarbon surfactants.     

结构可控含氟共聚物的合成及其应用研究新进展

近年来,含氟聚合物以其优异的耐热性、耐氧化性、耐候性、耐腐蚀性以及低介电常数、低表面能等特点,在疏水材料、抗污材料、表面活性剂、造影剂等领域具有广泛的应用前景,受到研究者的密切关注,各种拓扑结构的含氟共聚物被设计合成出来并在相关领域得到应用。本文首先简要介绍了含氟聚合物的性质和研究现状,然后详细叙述了可逆加成-断裂链转移聚合（RAFT）、原子转移自由基聚合（ATRP）、碘转移自由基聚合（ITP）、单电子转移活性聚合（SET-LRP）、氮氧稳定自由基聚合（NMP）以及活性阴离子聚合（LAP）等聚合方法在结构可控含氟共聚物合成中的研究新进展,并对其聚合机理、优缺点以及所得共聚物的性质和应用进行了总结,最后对结构可控含氟共聚物的设计、合成及实际应用前景进行了展望,提出发展绿色环保功能性含氟聚合物将是未来的主要研究热点。     

全氟辛烷磺酸/全氟辛酸替代物——新型含氟表面活性剂的研究进展

全氟辛烷磺酸/全氟辛酸(PFOA/PFOS)由于存在有争议的环境污染和生物蓄积等问题,已经成为全世界关注的焦点之一,寻找能够替代PFOA/PFOS的新型含氟表面活性剂具有重要的意义.本文综述了可能替代PFOA/PFOS新型含氟表面活性剂的合成路线和方法,并按照分子结构进行了分类,着重介绍了以下4类:①端基为CF₃O或(CF₃)₂N系列表面活性剂;②短氟链系列表面活性剂;③基于VDF或TFP系列表面活性剂;④全氟聚醚系列表面活性剂;同时对4类新型替代物的表面活性、生物降解性及在乳液聚合中的应用进行了归纳总结.目前PFOA/PFOS替代物的研究趋势,主要朝着降低含氟表面活性剂中氟元素比例、含减少氟链“有效长度”及插入N、O等杂原子等方向发展,使得新型含氟表活性剂更易降解、更环保、更安全.     

New fluorinated thermoplastic elastomers

New fluorinated thermoplastic elastomers (FTE) with perfluoropolyether (PFPE) blocks have been synthesized by reacting a fluorinated macrodiol with aromatic diisocyanates in the presence of a solvent, followed by subsequent chain extension with low molecular weight aliphatic or aromatic diols. Tensile properties measurements and dynamical-mechanical analysis (DMA) have been carried out and the relationship between chemical structure and final properties has been determined. These new thermoplastic fluorinated polyurethanes show an elastomeric behavior over a wide temperature range (between −75 and 100°C), thanks to their multiphase morphology consisting of a continuous fluorinated phase with a very low T_g (−120°C) and a dispersed high melting hydrogenated hard phase, as verified by a calorimetric and dynamic-mechanical analysis. At the same time, some of the outstanding properties of fluorinated oligomers, such as chemical inertness and low surface tension, are retained in the final polymers. Thanks to these characteristics this new class of polymeric materials provides new opportunities for the application of thermoprocessable elastomers in advanced technological fields. © 1996 John Wiley & Sons, Inc.     

Synthesis and Properties of pH-Dependent Gemini Surfactants Containing Multiple Carboxyl Groups

A series of Gemini surfactants N,N″-dialkyl-N,N′,N″-tripropionate diethylenetriamine (referred as DTPDT-n, where n is the length of the hydrocarbon chain, n = 10, 12, 14) were synthesized, which have three carboxylic head-groups and two hydrophobic alkane chains. The products were characterized by means of nuclear magnetic resonance and mass spectrometry. The physicochemical properties of DTPDT-n surfactants with different hydrocarbon chain lengths were studied such as isoelectric point, surface activities, emulsifying properties, and foam properties. It is showed that these compounds exhibit pH-dependent protonation-deprotonation behavior. The isoelectric points of DTPDT-n surfactants are between 3.40 and 10.90. The critical micellar concentration (cmc) of all three surfactants are lower than the corresponding monomeric surfactants (single head group, single-chain), especially DTPDT-14, whose cmc can reach 2.29 × 10⁻⁵ mol/L. With an increase in the length of the alkyl chain, the solubility of the surfactants decreases and the surface tension of the three surfactants at cmc increases. In consideration of pH, all of three surfactants appear better emulsifying capacity and foaming property under weak alkaline conditions. DTPDT-14 has the best performance of emulsifying capacity among the three surfactants. DTPDT-10 has excellent foaming ability and foam stability.     

氟表面活性剂在油田领域的应用

概述了氟表面活性剂在油田钻井、采油和集输领域的应用。氟表面活性剂具有高表面活性、高热稳定性、高化学稳定性和憎水憎油性等特点,被广泛用作油田钻井中的降滤失剂、助排剂;油田采油中的驱油添加剂、原油破乳剂、酸液缓蚀剂;油田集输中的稠油降黏剂、原油降凝剂、原油蒸发抑制剂、燃油增效剂、油罐防腐剂;也可作为油田污水杀菌剂。开发新型氟表面活性剂类油田化学品具有一定的经济和社会效益。引用文献23篇。     

特种表面活性剂和功能性表面活性剂(ⅩⅩ)——含氟双子表面活性剂的合成

按照结构特点对阳离子型、阴离子型、两性离子型和非离子型含氟双子表面活性剂的合成方法和合成路线进行了归纳。含氟双子表面活性剂是一种特殊表面活性剂,氟原子取代了表面活性剂碳氢链中的氢原子,而使其具有更高的表面活性。展望了含氟双子表面活性剂的发展前景。