硫酸酯型氟表面活性剂的合成与表面活性

以4-全氟壬烯氧基苯磺酰氯和2-甲氨基乙醇为主要原料,经酰胺化、酯化和中和反应制备了硫酸2-（N-甲基-4-全氟壬烯氧基苯磺酰胺基）乙酯钠（I）,用红外光谱和19F NMR,1H NMR对中间体和产物分子结构进行了表征,借助正交试验法优化了反应条件。酰胺化反应较佳工艺条件：n（4-全氟壬烯氧基苯磺酰氯）: n（2-甲氨基乙醇）＝1.0 : 2.0,以三乙胺为缚酸剂,在THF溶剂中,室温下搅拌反应3.0 h,收率93.4 ％;酯化反应较佳工艺条件：n（ N-羟乙基-N-甲基-4-全氟壬烯氧基苯磺酰胺）: n（氯磺酸）＝1.0 : 2.0,在THF溶剂中,室温下反应0.5 h,收率97.1 ％。硫酸2-（N-甲基-4-全氟壬烯氧基苯磺酰胺基）乙酯钠表面活性剂的临界胶束浓度 8.0×10-4mol/L,γcmc 23.1 mN/m (25℃)。     

聚氧乙烯醚型表面活性剂的合成及表面性质

合成了一系列不同聚合度的聚壬基酚聚氧乙烯醚型非离子表面活性剂, 通过红外光谱和核磁共振等手段对其结构进行表征, 用表面张力法对合成产物的表面性能进行研究. 结果表明, 随着表面活性剂分子中亲水基团环氧乙烷(EO)片段的增加, 单体、 二聚体和三聚体的临界胶束浓度(cmc)值都逐渐增大, 当EO数目相同时, 单体、 二聚体和三聚体的cmc值依次明显降低. 二聚体与三聚体都显示出很好的表面性质, 其中三聚体的表面性质比二聚体表面性能更优. 在空气/水表面二聚体和三聚体比单体的排列更加紧密, 表现出更好的吸附和分散性能.     

新型含氟系列阳离子表面活性剂的合成

以六氟丙烯二聚体和N,N-二甲基丙二胺为原料,合成N,N-二甲基-N’-(2-三氟甲基-1-五氟乙基)全氟丙烯基丙二胺（I）,通过正交实验确定了I的最佳工艺条件为：反应温度为35℃,反应时间为为8h,六氟丙烯二聚体与N,N-二甲基丙二胺的摩尔比为1:1.0,并通过IR、NMR光谱分析方法对I的结构进行确定;然后利用I分别与溴乙烷、溴代正丙烷、溴代正丁烷、溴代正己烷、溴代正辛烷和溴代正十二烷等烷基化试剂反应合成了一系列季铵盐阳离子表面活性剂,并对其结构进行了表征;结果表明,所得阳离子型含氟表面活性剂具有极低的表面张力：17.8、22.9、23.8、21.5、25.和28.1mN/m;临界胶束浓度：2.03、1.98、1.93、1.83、1.74和1.58mmol/L;且其Kraff点均低于0℃,显示了优良的水溶稳定性能。     

一种季铵盐双子表面活性剂的微波合成及性能研究

以四甲基丙二胺和溴代十二烷为原料,以异丙醇为溶剂,用微波辐射的方法反应合成一种季铵盐双子表面活性剂:二溴化-N,N′-二(二甲基十二烷基)丙二铵.研究了合成反应的最佳工艺条件:四甲基丙二胺与溴代十二烷的摩尔比为1.0∶ 2.2,反应时间为15分钟,反应温度为85℃,微波功率300W时,产率为70.55%.测定了不同浓度表面活性剂水溶液的表面张力,对产品的杀菌性能进行评价.结果表明:合成产品的临界胶束浓度为1.00mmol/L,杀菌率达100%时的药剂用量为40mg/L.     

系列阳离子双子表面活性剂的合成及其表面活性的研究

合成了一系列新型的阳离子双子表面活性剂二溴化-N,N'-二(二甲基烷基)乙二铵(12-2-m', m'＝4, 8, 12, 16), 初步研究了其水溶液的表面活性和电导率性质. 结果表明, 此类表面活性剂的表面活性与所含疏水尾基的碳数密切相关.     

琥珀酸酯磺酸盐Gemini表面活性剂的合成及表面活性

以1-十二醇、1-十四醇、1-十六醇、1-十八醇、马来酸酐和乙二醇为主要原料,合成4种琥珀酸酯磺酸盐Gemini表面活性剂;借助红外光谱和核磁共振氢谱对所合成的化合物结构进行了表征。 4种表面活性剂均具有较低的临界胶束浓度,较强的乳化性能以及较好的泡沫性能。 进一步讨论了4种表面活性剂结构与性能的关系。     

新型Gemini咪唑表面活性剂的合成及表面性能

以2,2-双(溴甲基)-1,3-丙二醇为连接基合成了新型的连接基为枝状的Gemini咪唑表面活性剂2,4-二(溴化-3-烷基咪唑)-1,3-丙二醇([Cn-P-Cnim]Br2,n=10,12,14).产物经核磁共振氢谱(1H NMR)、红外(IR)光谱和元素分析等进行了分析,证明所得产物即为目标产物.通过表面张力法和电导法测量其表面活性并计算胶束形成热力学参数(ΔG m—0,ΔH m—0,ΔS m—0).结果表明,25℃时3种表面活性剂均具有很高的表面活性,胶束的形成是自发的熵驱动过程.     

Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺的合成及性质研究

以L-苯丙氨酸为亲水部分和1,8-辛二胺为疏水部分,通过酯化生成酰胺和HCl脱去BOC保护基两步反应,合成一种新型Bola型表面活性剂N,N′-二苯丙氨酸酰基-1,8-辛二胺(DAOPh),采用IR、质谱和~1H NMR对其结构进行了表征.应用酸碱滴定法测得其pKa,采用电导率法、表面张力和芘荧光探针法测定了DAOPh水溶液的临界胶束浓度(CMC),进而预测其在水溶液中的聚集行为,探讨其作为药物载体的潜在优势.     

壬基酚聚氧乙烯醚型Gemini季铵盐表面活性剂的合成 及其表面性质的研究

合成了系列壬基酚聚氧乙烯醚型Gemini季铵盐表面活性剂(GNPQA), 用核磁、红外和元素分析对它们的结构进行了表征, 考察了反应条件对转化率的影响, 并用表面张力法和稳态荧光探针法对GNPQA的表面性能及胶束聚集数(N)进行了研究. 结果表明, 较优的反应条件: 反应时间为12 h, 反应温度为70 ℃, 反应原料摩尔比为n(双聚壬基酚聚氧乙烯醚)∶n(三乙胺)∶n(环氧氯丙烷)＝1∶1∶1; GNPQA的临界胶束浓度(CMC)值较相应的单体壬基酚聚氧乙烯醚型季铵盐表面活性剂(NPQA)降低了1～2个数量级, 显示了较高的表面活性; 当GNPQA溶液浓度为5～9倍CMC时, N值随浓度增大而线性增大; 随着氧乙烯(EO)单元数的增长, GNPQA的CMC和N值均逐渐减小; 结合GNPQA的表面性能参数和N值的变化规律, 探讨了这类表面活性剂表面及胶束聚集体的结构形态.     

四硅氧烷Gemini咪唑表面活性剂的合成及表面性能

以三甲基氯硅烷、 γ-氯丙基三氯硅烷、 1,4-二氯丁烷和咪唑等为原料合成了一种新型的四硅氧烷Gemini咪唑表面活性剂([Si₄-4-Si₄im]Cl₂), 通过质谱(MS)和核磁共振氢谱(¹H NMR)证明所得产物为目标产物. 通过Wilhelmy板法测得其在25 ℃下的临界胶束浓度(cmc)为0.54 mmol/L, 水溶液的表面张力(γ_cmc)降至18.6 mN/m. 通过电导率法研究了其胶束形成热力学参数(Δ\begin{array}{c}{G}_m^{0—}\end{array},Δ\begin{array}{c}{H}_m^{0—}\end{array}和Δ\begin{array}{c}{S}_m^{0—}\end{array}), 表明在15~35 ℃下其胶束化过程是自发进行的, 且为熵驱动过程.     

Design and synthesis of the novel branched fluorinated surfactant intermediates with CF3CF2CF2C(CF3)2 group

Here we reported a novel and efficient method for the synthesis of the critical intermediates of branched fluorinated surfactants with CF₃CF₂CF₂C (CF₃)₂- group using HFPD as starting material. The reaction conditions were mild and easy to handle, which was promisingly applied to the industrial production.     

Synthesis of Highly Fluorinated Aryl N-Acylsulfamates and Evaluation of Their Surfactant Properties

Abstract

Reaction of highly fluorinated carboxylic acids with aroxysulfonylisocyanates in the presence of triethylamine allowed the preparation of the corresponding highly fluorinated aroxy-N-sulfonylsulfamates. The reaction proceeds with good yield in toluene at room temperature or more rapidly in the same solvent at 60 °C. Surface tension measurement at the air/water interface showed that these compounds constitute new excellent nonionic surfactants exhibiting high surface activity in the range of the best nonionic fluoro surfactants, already described in the literature. The critical micelle concentration (CMC) has been calculated from the surface tension measurements on surface aqueous solutions.     

Synthesis and Surface Properties Activity of Novel Monoester Triethanolamine-Based Cationic Gemini Surfactants

The synthesis of surfactants derivatives of new two series of cationic gemini surfactants containing ethane or benzene as a spacer are described. The prepared compounds were analyzed using standard tools of analysis, elemental analysis, FTIR measurements, and H¹ NMR spectra. The influence of dimerization and of the spacer group were examined in order to establish structure-property relationships. The critical micelle concentration (CMC) of each series has been determined using equilibrium surface tension measurements. Furthermore, air/water interface parameter including effectiveness (Π_cmc), efficiency (P20), maximum surface excess (τ_max), and minimum surface area (A_min) have been also derived using Gibbs adsorption equation at 25°C. Standard free energies of micelleization were calculated and biological activities were examined. The results revealed that the dimeric surfactants have a good effect on the biological activities.     

Surface Properties and Etherification in Microemulsion Systems of Novel Brönsted Acid Surfactants

Novel Brönsted acid-surfactants with different alkyl chains were synthesized via a two-step process, and their surface properties were studied. The critical micelle concentration(cmc), surface tension at the cmc(γ_cmc), and ability of these compounds to lower the surface tension by 0.02 N/m(C₂₀ and pC₂₀) were investigated at 25 and 40℃. The molecular architecture of the compounds strongly influenced these physicochemical parameters. The ability of these compounds to lower surface tension was found to be good. Etherification in microemulsions formed by these surfactants as well as dodecylbenzenesulfonic acid(DBSA) was performed; surfactants 3a and 3b were found to be much more efficient than dodecylbenzenesulfonic acid(DBSA).     

Synthesis and Surface Activity of Anionic Gemini Surfactants with Alkyl Spacers

A series of anionic Gemini surfactants called alkanediyl-α,ω-bis(m-octylphenoxy sulfonate) with different length of (CH₂)_x spacer, C₈C_xC₈ (x = 2, 4, 6, 8), have been synthesized from 4-n-octylphenol and their basic physicochemical properties are investigated. The results indicate that they are different from cationic Gemini surfactants called alkanediyl-α,ω-bis(dimethyldodecylammonium bromide), 12-(CH₂)_s-12, in the literature. It is found that as the carbon atom number of the spacer increases, the cmc (critical micelle concentration) decreases gradually, and the surface area per molecule (A_min) decreases initially and then increases. The breakpoints appear at number 4 of carbon atom in the spacer. Though the length of the spacer is different for the Gemini surfactants from C₈C₂C₈ to C₈C₆C₈, there is no obvious change on the micropolarity.     

稳态荧光探针法研究对-烷基-苄基聚氧乙烯醚羧酸甜菜碱的聚集行为

利用荧光探针法和表面张力法测定了一类疏水基中含有苯基的新型甜菜碱两性离子表面活性剂对-烷基-苄基聚氧乙烯醚羧酸甜菜碱(ABECB)的临界胶团浓度(cmc)、胶团微极性和表面张力(γ_cmc).研究结果表明,荧光探针(芘)法可用来测定这类表面活性剂的临界胶团浓度(cmc),且测定结果与表面张力法(吊片法)接近;ABECB具有较低的cmc和γ_cmc值,表明此类表面活性剂具有优良的表面活性; 胶团的微极性随着疏水链长的增大而略微减小,氧乙烯(EO)单元数的增大对ABECB胶团核内的微极性影响不明显.     

一种新型羟基铅配合物的合成及其荧光性质

以3,5-吡唑二甲酸(H₃pdc)为配体,Pb(NO₃)₂为金属盐,在水热反应条件下通过调节pH,合成了一种新的二维羟基Pb配合物--［Pb₂OH(pdc)(H₂O)·H₂O］_n(1),其结构经IR,元素分析和X-射线衍射表征。1(CCDC: 1 469 184)属单斜晶系,P2₁/n空间群,晶胞参数a=10.502(2) , b=9.176 5(2) , c=10.602(2) , β=97.417(7)°, V=1 013.2(3) ³, Z=4, R₁=0.022 4, wR₂=0.045 8, S=1.02。每个不对称结构单元中具有两种不同配位环境的Pb,在同一结构单元中,2个Pb通过羟基O相连,相邻不对称结构单元通过配体连接Pb(Ⅱ)形成二维网络结构。荧光发射光谱研究结果表明：在最大激发波长(264 nm)激发下,1在380 nm, 419 nm和440 nm附近显示出较强的荧光性能。