Synthesis of new extended surfactants containing a xylitol polar group

A new class of extended surfactants was prepared in which the spacer arm between the polar portion and the hydrophobic alkyl chain was a polymer of propylene glycol with an average length of six propylene oxide units. The polar head was a single or double xylitol moiety or a xylitol molecule with carboxylic acid functionality. Surfactants containing double xylitol polar head groups showed a much higher critical micelle concentration value than surfactants with a single polar head.     

羧酸盐型双子表面活性剂合成研究进展

羧酸盐双子表面活性剂因其具有独特的物理化学性能及易生物降解等特性而广受国内外学者关注。本文主要对羧酸盐双子表面活性剂分子的疏水链、亲水基及联接基团的键合方式进行了概述。     

双尾烷基硫酸盐的合成与表面性质

以2-丁基辛醇、2-己基癸醇和2-辛基十二醇以及氯磺酸为主要原料,通过磺化、中和法合成了碳数分别为12、16和20双尾烷基硫酸盐表面活性剂(GC12S、GC16S和GC20S),并用IR1、HNMR对其结构进行了表征;测定了表面活性剂水溶液性质。实验结果表明:双尾烷基硫酸盐的临界胶束浓度(cmc)比同碳数的直链烷基硫酸盐的高,降低表面张力的能力比直链的更显著;碳链越长,表面活性剂的cmc越小,γcmc下降得更快。GC12S、GC16S和GC20S的γcmc分别为28.50 mN.m-1、27.56 mN.m-1和24.91 mN.m-1。     

磺酸盐/硫酸酯盐Gemini表面活性剂的合成及应用进展

Gemini表面活性剂因其特殊的结构及优良的性能倍受关注,20年来已合成出众多的品种,但至今仍很少有工业应用。总结了磺酸盐/硫酸酯盐双子的合成思路,提出用定量构性（SPR-Quantitative Structure-Property Relationship）方法从分子角度设计有工业化应用前景的双子表面活性剂,用23个磺酸盐/硫酸酯盐双子表面活性剂分子建立结构性质模型,并用2个外部数据进行了验证,最大误差为7.96%。     

羧酸盐型Gemini表面活性性剂的合成及表征

以脂肪胺、三聚氯氰、二乙醇胺、丁二酸酐为原料,三步法合成了,2种表面活性剂,用。HNMR、ESI—MS、IR对产物进行了表征,并用吊片法考察了目标产物水溶液的表面活性。实验结果表明,目标产物具有较好的表面活性,25℃时DXCeA和DXC。A的最低表面张力（7cmc）分别为31．85mN／m和28．76mN／m,临界胶束浓度（CMC）分别为2．32×10-4mol／L和1．41×10-5mol／L,表面活性优于传统表面活性剂十二烷基硫酸钠（SDS）。     

磷酸酯型extended表面活性剂的合成和性能

十二醇经丙氧基化、磷酸酯化及中和反应合成了环氧丙烷(PO)平均加成数(p)为3、6、9的extended表面活性剂单十二烷基聚氧丙烯醚磷酸酯钠(C_(12)P_pP)。采用FTIR、ESI-MS表征了其结构。测试了其Krafft点(TK)、耐电解质性、表面张力、发泡力、乳化力、润湿力和去污力,并与单十二烷基磷酸酯钾(MAPK)对比。结果表明,C_(12)P_pP的发泡力、乳化力、润湿力和去污性能均优于MAPK;其TK 0℃,具有优秀的低温水溶性,克服了MAPK的钠盐形式不能低温水溶的缺点。同时,合成的C_(12)P_pP的钙离子抗性高于MAPK5～8倍,其耐电解质性明显改善。另外,其对蛋白和皮脂的去污力与MAPK大致相同,推测与MAPK具有相近的低刺激性,可以替代MAPK用于个人清洁和护理用品中。     

新型带有磺酸基团的高分子表面活性剂的制备

采用COBF[his（aqua）bis（dinuomboryl）dimethyl yoximato）cobalt（II）]为催化剂,AIBN为引发剂,以甲基丙烯酸丁酯、2-丙烯酰胺基-2-甲基-丙磺酸,甲基丙烯酸-β-2-羟乙酯等合成了带有磺酸基团和羟基的高分子表面活性剂。运用红外光谱IR和-HNMR对合成的产物进行了结构表征,测定了聚合物的表面张力、临界胶束浓度,结果表明,合成的聚合物具有良好的表面活性。把得到的聚合物用于乳液聚合,通过动态光散射和原子力显微镜测定乳液的粒径、观察形貌,乳胶粒粒径分布均匀。     

羧酸盐表面活性剂与两亲聚合物相互作用研究

根据黏度和表面张力的测定数据研究了羧酸盐表面活性剂(HF-E)与两亲聚合物的相互作用,结果表明,HF-E/两亲聚合物混合溶液的表观黏度随HF-E质量浓度的增加先升高后下降;两亲聚合物的质量浓度越大,HF-E/两亲聚合物混合溶液表面张力越高;随着水的矿化度的升高,HF-E/两亲聚合物混合溶液的表观黏度先略有增加,到一定值后反而降低,而表面张力则随矿化度的增加而降低;温度升高,HF-E/两亲聚合物混合溶液的表观黏度随之降低而其与大庆模拟油间的界面张力则升高。优化后的高黏度低界面张力二元体系配方为HF-E和两亲聚合物的质量浓度分别为3和1.5 g·L-1;此外,还加入质量浓度为1 g·L-1的烷基醇酰胺(NS)。     

含酰胺基双子阳离子表面活性剂的合成与性能研究

以N,N-二甲基丙二胺分别与十二酸、十四酸、十六酸和十八酸反应得到酰胺基叔胺,再制成其盐酸盐,盐酸盐与环氧氯丙烷在水溶剂中合成了相应的含酰胺基双子(gemini)阳离子表面活性剂,采用红外光谱、质谱、元素分析、核磁共振波谱进行了结构表征,并测定了阳离子表面活性剂表面化学性能.结果表明,真空干燥后含酰胺基gemini阳离子表面活性剂的质量分数大于98%,该含酰胺基gemini阳离子表面活性剂具有很强的表面吸附和胶束生成能力,随着脂肪碳链长度由12增加到18,cmc由9.12×10-5mol·L-1减少至3.31×10-5mol·L-1,ccmc/c20由3.02增加到3.98,Krafft点也有升高的趋势.     

新型双子两性表面活性剂的合成及性能

以十二烷基叔胺、环氧氯丙烷和氧氯化磷为原料合成了一种新型双子两性磷酸酯表面活性剂。在三亚甲基中引入PO43-作为柔性基团来提高联接基团的亲水性。通过红外光谱对合成的表面活性剂进行了结构表征。测试了该表面活性剂的水溶液最低表面张力为31.9 mN/m、临界胶束浓度为1.4×10-4mol/L、等电点为pH 8.5~10.5,c20=1.41×10-5mol/L。考察了其发泡性、乳化性等,通过摄像显微镜对乳化效果进行了观察。     

Effect of hydrophilic group on thin film formation using redox-active surfactants with an azobenzene group

Thin films of organic pigments were prepared at higher than pH 1 by the contact plating method using an anionic surfactant (AZNa, first figure of this article (part c) (n = 4)) containing an azobenzene moiety. The effects of hydrophilic group of the surfactants on the rate of following reaction of the reduction product were studied by cyclic voltammetry. The positive shift of the reduction peak potential of AZNa compared to those of cationic and non-ionic surfactants was ascribed to higher rate of following reaction of reduction product due to the presence of the anionic hydrophilic group of the surfactant. The present investigation revealed that the anionic hydrophilic group accelerates the cleavage of the NN bond of the azobenzene group. This phenomenon enabled us to prepare the organic thin film at higher pH condition.     

Formulation of ultralow interfacial tension systems using extended surfactants

Inspired by the concept of lipophilic and hydrophilic linkers, extended surfactants have been proposed as highly desirable candidates for the formulation of microemulsions with high solubilization capacity and ultralow interfacial tension (IFT), especially for triglyceride oils. The defining characteristic of an extended surfactant is the presence of one or more intermediate-polarity groups between the hydrophilic head and the hydrophobic tail. Currently only limited information exists on extended surfactants; such knowledge is especially relevant for cleaning and separation applications where the cost of the surfactant and environmental regulations prohibit the use of concentrated surfactant solutions. In this work, we examine surfactant formulations for a wide range of oils using dilute solutions of the extended surfactant classes sodium alkyl polypropyleneoxide sulfate (R-(PO) _x −SO₄Na), and sodium alkyl polypropyleneoxide-polyethyleneoxide sulfate (R-(PO) _y -(EO) _z −SO₄Na). The IFT of these systems was measured as a function of electrolyte and surfactant concentration for polar and nonpolar oils. The results show that these extended surfactant systems have low critical micelle concentrations (CMC) and critical microemulsion concentrations (CμC) compared with other surfactants. We also found that the unique structure of these extended surfactants allows them to achieve ultralow IFT with a wide range of oils, including highly hydrophobic oils (e.g., hexadecane), triolein, and vegetable oils, using only ppm levels of these extended surfactants. It was also found that the introduction of additional PO and EO groups in the extended surfactant yielded lower IFT and lower optimum salinity, both of which are desirable in most formulations. Based on the optimum formulation conditions, it was found that the triolein sample used in these experiments behaved as a very polar oil, and all other vegetable oils displayed very hydrophobic behavior. This unexpected triolein behavior is suspected to be due to uncharacterized impurities in the triolein sample, and will be further evaluated in future research.     

催化氧化制备醇醚羧酸盐及其复配性能研究

以脂肪醇聚氧乙烯醚(AEO9)、氧气和氢氧化钠为原料,在自制的Pd/C催化剂作用下催化氧化制备醇醚羧酸盐(AE9C)阴离子表面活性剂.考察了反应条件对产品收率的影响,并研究了AE9C与双癸基二甲基氯化铵(DDMAC10)复配体系的润湿、乳化和泡沫性能.结果表明较佳的反应条件为:温度70℃、压力0.08 Mpa、反应时间4 h,产品的收率可达85%.AE9C与DDMAC10复配具有较好的协同效应.     

香料羧酸糠醇酯合成的新方法

用糠醇、乙酸酐和丙酸酐为原料,Fe2(SO4)3.xH2O为催化剂,NaHCO3为缚酸剂,合成了乙酸糠醇酯和丙酸糠醇酯。考察了反应物料比、反应时间、催化剂和缚酸剂用量对收率的影响。合成乙酸糠醇酯的最佳条件为:物料配比n糠醇∶n乙酸酐∶nFe2(SO4)3.xH2O∶nNaHCO3=2∶2∶0.03∶2(摩尔比),室温下反应4 h;合成丙酸糠醇酯的最佳反应条件为:物料配比n糠醇∶n丙酸酐∶nFe2(SO4)3.xH2O∶nNaHCO3=2∶2∶0.04∶2(摩尔比),室温下反应4 h。乙酸糠醇酯和丙酸糠醇酯的收率分别为88.8%和90.2%。该反应条件温和、产率高,可用于工业化大规模生产。目标产物结构经IR、1H NMR表征得以证实。     

Synthesis and properties of novel alkyl sulfate gemini surfactants

Four anionic gemini surfactants of the sulfate type C₁₂C_nC₁₂, where n is the spacer chain length (n = 3, 4, 6, and 10) were synthesized. The structures of these surfactants were confirmed by FT‐IR, ¹H NMR, ESI mass spectra (ESI‐MS), and elemental analysis. The surface‐active properties of these compounds were investigated by means of surface tension, electrical conductivity, and fluorescence measurements. Premicellar aggregations were found for the four gemini surfactants, as revealed by the conductivity measurement. The formation of premicellar aggregates may account for the discrepancy between the critical micelle concentration (cmc) obtained by the surface tension and conductivity measurement. The cmc values of these gemini surfactants were much lower than that of sodium dodecylsulfate (SDS) and decreased monotonously with the increase of spacer chain length from 3 to 10. The effect of spacer chain length on the performance properties like foaming, emulsion stability, and lime soap dispersing ability were also studied and discussed. Practical applications : Alkyl sulfate surfactants are one of the most widely used surfactants. The new alkyl sulfate gemini surfactants synthesized in our study are more surface‐active than sodium dodecylsulfate. These gemini surfactants possess low critical micelle concentrations, high emulsion stability, and excellent lime soap dispersing ability. They have potential applications in the fields of cosmetics, detergents, etc.     

Synthesis and properties of cationic surfactants containing a disulfide bond

Two new cationic surfactants containing a disulfide bond were synthesized, and the physical chemical characteristics and the fundamental surface-active properties were determined. These new surfactants have potential applications in the textile and cosmetic field. These compounds have been prepared by condensation of a commercial N^α,N^α-dimethyl amino betaine with cystine dimethyl ester or cystamine by means of the mixed anhydride method. The study of their properties revealed that these molecules are soluble in water (stable at pH⩽8) and show surface activity with similar low critical micelle concentration values. Microscopic examination of water/surfactant systems containing these compounds shows that they form liquid crystals with patterns corresponding to typical hexagonal and lamellar structures.     

Synthesis and physico‐chemical properties of novel dialkyl diphosphate gemini surfactants based on octadecanol

A series of dialkyl diphosphate gemini surfactants has been synthesized using C₁₈ as hydrophobic chains and phosphate as head groups. Three flexible spacers have been used. In the present study, an attempt has also been made to synthesize mono octadecyl phosphate (MOP) at 35°C, which was used as an intermediate in the synthesis of geminis. This long chain of MOP has been effectively converted to gemini surfactants and subsequently converted to their disodium salts. The effect of reaction variables like temperature, duration, molar ratios of reactants, catalyst and spacer on the yield of dialkyl diphosphate gemini surfactant has also been reported. The MOP, gemini surfactants and disodium salt of gemini surfactants were characterized using FT‐IR and ¹H‐NMR. Surface active and physico‐chemical properties of synthesized gemini surfactants and their monomer were also determined. The results revealed that the yield of dialkyl diphosphate gemini surfactants ranged from 80 to 90%. Among all synthesized dialkyl diphosphate gemini surfactants D, S‐1,6‐GSOD had maximum anionic content, i.e. 80.7%, showed highest foaming ability and superior dispersing ability, whereas D, S‐1,8‐GSOD showed low cmc values, i.e. 0.00012 mM/L; minimum surface tension and interfacial tension, i.e. 39.1 and 36.3 mN/m, respectively.     

含哌啶环的阳离子双子表面活性剂的合成及性能研究

以苯胺、环氧氯丙烷、哌啶和1-溴癸烷为原料经过三步反应合成了含有哌啶环的阳离子双子表面活性剂C_(10)-CGP。采用FT-IR、MS和~1H NMR对产物进行了结构表征。研究了其Krafft点、乳化性能和乳化沥青时的相关性能,并测定了25~40℃的临界胶束浓度(cmc)、平衡表面张力(γ_(cmc))及相应的热力学函数。结果表明,C_(10)-CGP的Krafft点低于0℃,乳化分水时间为532s。25℃时,cmc为0.976×10~(-3)mol/L,γ_(cmc)为28.93 mN/m。随着温度的升高,cmc增大、γ_(cmc)减小、饱和吸附量(Γ_(max))减小、极限占有面积(A_(min))增大。乳化沥青测试表明,C_(10)-CGP是慢裂型沥青乳化剂,贮存稳定性好且乳化沥青粒径分布较窄。     

Surface and aqueous properties of anionic gemini surfactants having dialkyl amide,carboxyl, and carboxylate groups

A systematic study of the equilibrium surface properties (in water and in the presence of 10⁻² M NaCl) of a novel series of anionic gemini surfactants, (CH₂)₂[N(COC_nH_2n+1)CH(COOH)CH₂COOH]·2NaOH (GA), where (n+1)=8, 10, 12, 14, and 16, was investigated. The responses of humans to closed patch tests with (CH₂)₂[N(COC₁₁H₂₃)CH(COOH)−CH₂COOH]₂·2NaOH (GA-12) were also investigated. Premicellar self-aggregation (both in water and 10⁻² M NaCl) occurred when the N-acyl group contained more than 14 carbon atoms, since the critical micelle concentration (CMC) values decreased and the pC₂₀ values increased as (n+1) increased for (n+1) ≤14; the CMC values increased and the pC ₂₀ values decreased as (n+1) increased for (n+1)>14, both in water and in 10⁻² M NaCl. The absence of a break in the specific conductance-surfactant molar concentration plots for the GA homologs indicates protonation of the carboxylate group and strong Na⁺ release during micellization. This is a structural characteristic of the anionic geminis having N-dialkylamide and carboxylate groups in a molecule. The skin irritation potential of GA-12 is lower than that of the corresponding “monomer”, C₁₁H₂₃CON(CH₃)CH(COOH)CH₂(COOH)·NaOH, and the analog, C₁₁H₂₃CON(CH₃)CH₂COONa·H₂O.     

琥珀酸酯磺酸盐表面活性剂的合成和性能研究

从顺丁烯二酸酐衍生物表面活性剂出发,合成了琥珀酸酯磺酸盐这一类型具有多个亲水、亲油基团的新型表面活性剂;分别对合成的几个系列的多种醇类对应酯的琥珀酸酯磺酸盐表面活性剂在起泡、表面张力等方面的性能进行了测试和分析。