可聚合阳离子含氟表面活性剂的合成与性能

该文以全氟烷基乙基醇(PFEA)为原料,设计合成了3种不同含氟链段长度的可聚合阳离子含氟表面活性剂——N-(乙酸全氟烷基乙基酯)-N-(乙醇丙烯酸酯)二甲基溴化铵(PFDM),通过核磁共振氢谱(1HNMR)对其结构进行了表征。利用Zeta电位测定、表面张力测定等手段考察了不同含氟链段长度对PFDM表面活性的影响,并证明了PFDM的可聚合性。结果表明,随含氟链段的增长,PFDM在水介质中形成胶束的胶束聚集数逐渐增大,CMC呈指数下降,表面活性逐渐增强,且具有良好的可聚合性。     

碳氟表面活性剂在有机液体中的表面活性

从不同的碳氟链（ 包括四氟乙烯五聚体衍生物、全氟丙烯环氧齐聚体衍生物以及全氟烷基衍生物等） 出发, 制备了多种碳氟化合物。通过表面张力测定,研究了碳氟化合物在甲苯、正己烷、正癸烷、环己烷等烃类化合物以及在氯仿、硝基甲烷、二甲亚砜、正丁醇等极性化合物中的表面活性。探讨了表面活性剂结构对其表面活性的影响。     

二烷基乙氧基硫酸钠阴离子双子表面活性剂的合成及其表面活性

为研究阴离子双子表面活性剂结构与表面活性的关系,以不同碳链的脂肪醇、环氧氯丙烷、不同的二醇等为原料,通过三步反应合成出一种间隔基为乙氧基的阴离子双子表面活性剂二烷基硫酸钠,得到不同长度碳链和间隔基的4种双子表面活性剂,同时对部分合成条件进行了优化,确定了烷基单缩水甘油醚所用催化剂为苄基三乙基氯化铵以及烷基低聚二醇的最佳反应温度为80℃。核磁共振氢谱和傅立叶变换红外光谱证实了它们及其中间产品的结构。部分产品最小表面张力低于30 mN/m,临界胶束浓度低于0.1 mmol/L,具有良好的表面活性。实验表明,随着碳链的增长和间隔基长度的增加,其CMC降低,间隔基长度的增加使am in变大,但其γCMC变化不大。     

烷基碳链对N-烷基二甲基甜菜碱性能的影响

甜菜碱表面活性剂的烷基碳链的长度对其表面活性及其它性质有不同程度的影响。通过实验测定碳链长度对泡沫力、洗涤力等的影响情况,为不同使用目的选择合适长度碳链的烷基甜菜碱提供依据。结果表明:十四烷基甜菜碱的起泡力较强,十二烷基的次之;十四、十六烷基甜菜碱的洗涤力较强,十四烷基的洗涤力更强;相对碳链长的甜菜碱活性剂具有较好的加溶作用和钙皂分散力。     

碳链长度对阴阳离子表面活性剂体系性质的影响

研究了N－烷基－N,N,N－三羟乙基氯化铵CnNE(其中n为10,12,16）与十二烷基聚氧乙烯（3）硫酸钠AES混合体系的临界胶束学,混合胶束和混合单分子层的组成及相互作用参数（βs和βm)和沉淀浓度等性能,结果表明,对于阴阳离子表面活性剂体系,对于任何混合比,单一组分产生的偏表面压高者优先吸附,文章还总结和发现了碳链长度,相互作用参数,混合cmc和沉淀浓度等之间的相关性。     

一种非离子氟碳表面活性剂的合成及表征

以聚乙二醇、全氟丁酸为主要原料,采用直接酯化的方法,合成了一系列聚乙二醇系非离子型氟碳表面活性剂——聚乙二醇全氟丁酸酯(以单酯为主,且含有少量双酯),且对其红外光谱、表面张力、临界胶束浓度、浊点进行了测试。结果表明,该类氟碳表面活性剂具有很高的表面活性,同时,随PEG链段长度的变化,其表面张力、CMC值、浊点都发生规律性的变化。     

广州市立尔科贸有限公司

广州市立尔科贸有限公司是一家集研发、生产、贸易为一体的综合性高新技术企业,主要从事电子化学品、表面活性剂和造纸助剂等的生产和经营。现已形成：（1）氟表面活性剂、（2）电子化学品、（3）涂料助剂、（4）造纸助剂、（5）化学复合镀、电镀等五个系列,几十种型号的产品。公司主要产品有：氟碳表面活性剂、全氟表面活性剂、含氟表面活性剂、氟化表面活性剂、全氟烷基磺酰化合物、全氟烷基季铵碘化物、全氟辛基磺酰季铵碘化物、全氟辛基磺酸钾、全氟辛基磺酰胺、全氟辛基磺酰氟、全氟辛基甜菜碱、全氟烷基磺酰胺、全氟烷基类化全物、全氟丁基磺酸钾、     

1，1，2，2-四氢全氟烷基碘合成工艺研究

含氟表面活性剂具有高表面活性、高耐热稳定性及高化学稳定性以及既憎水又憎油的独特性能，目前已广泛应用于化工、机械、纺织、造纸、涂料、玻璃、陶瓷等许多行业。全氟烷基碘化物（CnF2n＋1I，n=1～12）易与乙烯发生加成反应，生成全氟烷基碘乙烯加成物——1，1，2，2-四氢全氟烷基碘．该加成物中碘原子不再与全氟烷基相连，受到全氟烷基的诱导作用减弱，因此1．1，2，2-四氢全氟烷基碘上的碘易发生取代反应，可以转变成相应的醇、硫醇和磺酰氯等各种含氟中间体，故1，1，2，2-四氢全氟烷基碘是制备含氟表面活性剂的重要中间体。在此基础上，可开展大量含氟表面活性剂的研制。其合成路线主要有：（1）在水或水与另一极性溶剂为共溶剂的体系中，以能产生二氧化硫阴离子基的物质为引发剂，以金属的碱或盐为吸酸剂。经全氟碘代烷对乙烯的自由基加成反应而制得。该法反应时间较短．但对设备要求高．反应过程较为复杂。（2）使用金属铜催化剂，在50-200℃．0．01-3MPa下得到目标产物。该法对设备要求高，还需进行催化剂的制备。（3）利用钌／活性炭、铂／活性炭、银／氧化铝等贵金属作为催化剂的方法。该法贵金属价格高，制造成本高。（4）利用偶氮二异丁腈、过氧化苯甲酰等过氧化物作为催化剂的方法。该法工艺简单，引发剂用量少，反应液无需处理可直接进行下一步反应。 本工艺采用了第四条路线．以全氟烷基碘、乙烯为原料，过氧化物为引发剂。经过加成反应一步制得1，1，2，2-四氢全氟烷基碘。     

新型阴离子孪连表面活性剂的合成

系列长链环氧烷与不同短链二醇在75~80℃、NaH作用下合成了系列中间体孪连长链二醇,此中间体再与1,3-丙烷磺酸内酯在THF、NaH中反应得到了疏水链长度和连接基长度不同的7种磺酸盐孪连表面活性剂。核磁共振氢谱及红外光谱的结构分析证实了它们的结构。它们的表面张力为26.5~34 mN/m,临界胶束浓度为0.001~0.01 mmol/L,结果表明,它们的表面活性比相应碳链的常规表面活性剂强很多。疏水链长度和连接基长度的增长,有助于表面活性的提高。     

磺酸盐Gemini表面活性剂的合成与表面活性

以单链表面活性剂SCT及1,3-丙二胺为原料,通过一步取代反应,合成了4种含三嗪环的磺酸盐Gemini型表面活性剂Cn-3-Cn(n=6,8,12,14),测定了25℃时4种表面活性剂的临界胶束浓度CMC。结果表明,Cn-3-Cn的临界胶束浓度CMC均随着疏水烷基链长度的增加而减小,C12-3-C12(实际疏水基碳原子数为14)达到最小值7.23×10-5mol/L,当实际疏水基中碳原子数增加到16时,CMC有所增加。同传统单烷基离子型表面活性剂十二烷基硫酸钠(SDS)相比,该类表面活性剂的CMC值低1～2个数量级,显示出很高的表面活性。此外,表面张力随着疏水烷基链长度的增加呈现先减小后增大的趋势,最低γcmc为35.48 mN/m。     

双尾及多尾氟表面活性剂在有机溶剂中的表面活性研究

拟通过增加油溶性氟表面活性剂分子中碳氟链的数目,从而增大有机溶剂表面吸附层的碳氟链密度,以提高其降低有机溶剂表面张力的能力。合成了2个系列的氟表面活性剂:将全氟辛基磺酰氟与二胺(NH_2(CH_2)nNH_2,n=2,3,6,10)反应,合成以磺酰胺键为连接基、分子中含有2个碳氟链的油溶性氟表面活性剂;通过全氟辛酸与多元醇(乙二醇、1,2-丙二醇、丙三醇和季戊四醇)反应,合成以酯键为连接基、分子中分别含有2,3和4个碳氟链的油溶性氟表面活性剂。研究了这2个系列氟表面活性剂在乙醇、乙酸乙酯、丁酮以及乙醇-乙酸乙酯-丁酮三元混合溶剂中的表面活性,考察了氟表面活性剂分子结构、溶剂种类对表面活性的影响。结果显示,单纯增加碳氟链数目与降低表面张力之间不具有必然的依赖关系,分子整体构型也很重要,同时有机溶剂的种类对氟表面活性剂溶液的表面张力有显著影响。     

The Impact of In‐situ Fabric Surface Energy on Dehydration of Fabrics

Reducing liquid surface tension is widely used to increase the efficiency of the centrifugal dehydration in textile wet processing. However, increasing the dehydration efficiency by decreasing fabric surface energy is seldom studied. In this work, the impact of in situ fabric surface energy on residual moisture content (RMC) of fabrics in the dehydration processes was investigated. Different types of fluorocarbon surfactants including cationic, anionic, nonionic and amphoteric were adopted as additives in this study. The liquid surface tension and RMC were efficiently decreased when fluorocarbon surfactants were used. Notably, a cationic fluorocarbon surfactant displays similar surface tension but distinct dehydration efficiency. The in situ fabric surface energy was evaluated by measuring the n‐octane contact angle on the cotton fabric surface under the surfactant solution using the captive bubble method. It was found that the cationic fluorocarbon surfactant system gave the lowest fabric surface energy, which was probably because cationic fluorocarbon surfactants are easier to adsorb onto the surface of cotton fabric to form a fluorocarbon layer. The chemical composition (¹⁹F, ¹²C and ¹⁶O) analysis of the cotton fabric surface by X‐ray photoelectron spectroscopy confirms the hypothesis.     

一种全氟辛基两性磷酸酯氟碳表面活性剂的复配研究

对一种全氟辛基两性磷酸酯氟碳表面活性剂协同作用进行了研究,考察了该表面活性剂与无机盐、阴离子碳氢表面活性剂、阴离子氟碳表面活性剂和非离子氟碳表面活性剂的复配性能,并对结果进行了讨论。研究表明:该两性磷酸酯氟碳表面活性剂自身表面张力为24.0 mN/m;电解质氯化钠对该两性磷酸酯氟碳表面活性剂影响显著,可使表面张力下降到22.4 mN/m;阴离子碳氢表面活性剂十二烷基硫酸钠(SDS)可使表面张力降至21.4 mN/m;阴离子氟碳表面活性剂全氟丁基磺酸钾和四乙基全氟辛基磺酸铵分别使表面张力降至20.9 mN/m和20.2 mN/m;而非离子氟碳表面活性剂N-乙基-N-聚氧乙烯(9)醚-全氟辛基磺酰胺能使表面张力降至20.9 mN/m。     

季铵盐有机硅双子表面活性剂的合成及性能研究

以丙酮和正己烷为溶剂,聚乙二醇二缩水甘油醚和羟基封端聚二甲基硅氧烷为主要原料在四丁基溴化铵(TBAB)和氢氧化钠(Na OH)的催化下合成环氧基聚醚改性硅氧烷(EPEPS),再与N,N-二甲基长链烷基胺〔C_mH_(2m+1)NH(CH_3)_2〕在无水乙醇溶剂中、盐酸催化下进行季铵化反应,制备季铵盐有机硅双子表面活性剂(mpsi-m),通过FTIR和1HNMR对目标产物进行结构表征,研究m-psi-m中疏水链长度对其表面活性、临界胶束浓度、润湿性能以及乳化稳定性的影响。结果表明,随着疏水链长度的增加,m-psi-m的表面活性和润湿性能下降,临界胶束浓度增大,乳化稳定性增强。     

Role of fluorocarbon surfactant in the preparation of polytetrafluoroethylene‐modified polyacrylate emulsion

Role of fluorocarbon surfactant in the preparation of polytetrafluoroethylene‐modified polyacrylate emulsion is investigated. The fluorocarbon surfactant has an efficient preemulsification to polytetrafluoroethylene (PTFE) powder. It enables PTFE powder to be introduced into the copolymer of n‐butyl acrylate, n‐methyl methacrylate, n‐styrene, and α‐methacrylic acid. Thereby, stable PTFE‐modified polyacrylate emulsion can be formed. The effects of fluorocarbon surfactant on the surface tension, particle size and particle size distribution of the emulsion, as well as the relation between fluorocarbon surfactant and the amount of PTFE powder are fully investigated. The particle size and the surface tension of emulsion strongly depend on the fluorocarbon surfactant concentration in the reaction system. The particle size distribution becomes narrower and the stability of the emulsion is improved with the increasing of the fluorocarbon surfactant concentration. According to the experiments, a possible mechanism of fluorocarbon surfactant in polymerization is proposed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface characteristics of water‐soluble cationic fluoro copolymers containing perfluoroalkyl,quaternized amino,and hydroxyl groups

Various water‐soluble cationic fluoro copolymers in quaternized form with perfluoroalkyl, amino, and hydroxyl groups were prepared by varying the contents of perfluoroalkyl ethyl acrylate (FA), 2‐(dimethylamino) ethyl methacrylate (DAMA), and 2‐hydroxyethyl methacrylate (HEMA). The solvent polymerization was carried out in acetone, with the subsequent addition of acetic acid to form a quaternized polymer. Polyurethanes films were prepared by curing aqueous solutions containing water‐soluble cationic fluoro copolymers and a blocked isocyanate at 190°C. The surface characteristics of the water‐soluble cationic fluoro copolymers and the polyurethanes were investigated on the basis of FA and DAMA contents. The contact angles for both water and methylene iodide (MI) on the cationic fluoro copolymer and the polyurethane increase steadily as FA content increases, and decrease gradually with increasing DAMA content. The contact angles on the polyurethane are slightly higher than those on the cationic fluoro copolymer. The cationic fluoro copolymer and the polyurethane with FA content of 40 wt % and DAMA content of <30 wt % show extremely low surface free energies of 13–15 dynes/cm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3702–3707, 2002     

Intechem-1氟碳表面活性剂溶液性能研究

以六氟丙烯环氧化合物齐聚体为原料,合成一种新型非离子氟碳表面活性剂。测试其表面张力、临界胶束浓度以及发泡性能等物化性质,与Du Pont1157相比,其水溶液表现出更加优异的表面活性,同时在环己烷、汽油和丙酮表面具有良好的铺展性能。     

Study on aqueous film-forming foam extinguishing agent based on fluorocarbon cationic–hydrocarbon anionic surfactants mixture system

Fluorocarbon surfactants were the main components of aqueous film-forming foam extinguishing agents (AFFF). Unfortunately, the widely used fluorocarbon surfactant perfluorooctane sulfonate (PFOS) was limited due to its toxicity, bioaccumulation and biodegradability. In this paper, an environmentally friendly quaternary ammonium cationic fluorocarbon surfactant with high surface activity and simple synthesis route was reported. The surface performance and aggregation behavior of the mixed solution of this fluorocarbon surfactant and sodium n-octyl sulfate were studied by means of surface tension meter and transmission electron microscope (TEM). The results showed that the synergistic effect of sodium n-octyl sulfate and this fluorocarbon surfactant was significant, and many vesicles could be observed in the mixed solution with the concentration of 0.1 mol/L under TEM. Subsequently, three environmental friendly AFFF formulations (F-1, F-2, F-3) were designed with the mixture of the fluorocarbon surfactant, sodium n-octyl sulfate and lauryl betaine BS-12 as foaming agent. Through its foam performance test, it could be seen that F-3 showed relatively excellent foam performance. The initial foam height h₀ was 70 mm, the 25% drainage time was 315 s, the extinguishing time was 28 s, and the burn-back time was 720 s. This kind of fire extinguishing agent had the potential of fire protection application.     

非离子型氟碳表面活性剂的合成与表面性能

以六氟环氧丙烷和壬基酚聚氧乙烯醚40为原料,使用齐聚法合成一种新型非离子型氟碳表面活性剂C9H19C6H4O(CH2CH2O)40C9F17O3,运用傅里叶变换红外光谱仪(FT-IR)和核磁共振波谱仪(NMR)对其结构进行表征,并对其表面性能进行测试和计算。结果表明,该表面活性剂能将水的表面张力最低降至21.2 mN/m,其临界胶束浓度cm c为8.32×10-6mol/L,γcm c为26.5 mN/m。