Acyl Poly(Glycerol-Succinic Acid) Oligoesters: Synthesis,Physicochemical and Functional Properties,and Biodegradability

Biobased surfactants were synthesized using poly(glycerol-succinate) as the polar head group and variable acyl groups as hydrophobic tails. Acyl chain lengths ranged from 8 to 14 carbon atoms. The resulting oligomeric surfactants were characterized by quantitative ¹³C nuclear magnetic resonance (NMR), acid values and size exclusion chromatography. Investigation of the physicochemical properties of the acyl poly(glycerol-succinate) surfactants revealed their potential for use in a wide array of applications. The acyl poly(glycerol-succinate) functional properties appeared to be particularly concentration-dependent. This study highlights the relative impact of acyl chain length on the polymeric structure, physicochemical and functional behaviors, and biodegradability of the acyl poly(glycerol-succinate) surfactants.     

Succinylation of Non-ionic Surfactants: Physicochemical Characterization,Functional Properties,Biodegradability and Mathematical Modeling of the Polarity Tuning

Anionic surfactants comprising succinic acid end groups were synthesized by succinylation of non-ionic surfactants using succinic anhydride as a potentially bio-sourced building block. A solvent- and catalyst-free synthesis was designed for succinic anhydride mono esterification with octyl-, decyl and dodecylpolyxylosides, di- and tetraethylene glycol dodecylethers and glycerol monolaurate. The physicochemical and functional properties of anionic surfactants thus obtained were studied and compared with their non-succinylated counterparts. A correlation between these properties and the polarity changes induced by the addition of the hydrophilic succinic acid moiety was established. The biodegradability of the succinylated surfactants has also been investigated. Finally, through a desirability function approach, mathematic predictions were correlated to the properties in order to find an optimum and to discriminate surfactants with respect to targeted physicochemical properties and resulting applications.     

The Relationship Between the Structure and Properties of Amino Acid Surfactants Based on Glycine and Serine

Two series of surfactants based on glycine and serine were synthesized with aproic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid and hexadecanoic acid. All the surfactants were characterized by MS and ¹H NMR, the structures of the synthesized surfactants are correct and the signals in MS and ¹H NMR can be explained. The reaction conditions, surface properties and foam properties were studied. For the two series of surfactants, critical micelle concentration (CMC) and γ _CMC (surface tension at CMC) decrease and surface activity is enhanced as the length of carbon chain increases. The surfactants with tetradecanoyl and hexadecanoyl groups show a good foaming property and especially, the long-chain acyl-serine performs better. These are all related to the hydromethyl group in the serine.     

Influence of Cationic Surfactants on the Crystallization of Cis‐ and Trans‐Isomers

The crystals of cis‐ and trans‐isomers present in principle similar chemical groups on their respective crystal faces. Here, the crystallization of cis‐ and trans‐isomers (maleic acid and fumaric acid) in an aqueous solution containing cationic surfactants with different hydrophobic chains (the long hydrophobic chains of dodecyltrimethylammonium bromide < cetyltrimethylammonium bromide < trimethylstearylammonium bromide) was investigated. Results showed that the surfactants presented different effects on the crystallization of cis‐ and trans‐isomers. For trans‐isomers (fumaric acid), the surfactants with longer hydrophobic chains or higher solution concentrations will favor a wider metastable zone width (MZW) and a greater morphology change. By contrast, both the MZW and morphology development of cis‐isomers (maleic acid) were not affected by these surfactants. The chemical groups on crystal faces, surface grooves, and molecular polarity were compared to reveal the different influences of surfactants on the crystallization of cis‐ and trans‐isomers.     

两性表面活性剂的合成路线概述

重点介绍了国内新型两性表面活性剂的合成研究概况。咪唑啉型表面活性剂的合成主要是利用了咪唑啉中间体羟基的反应活性,通过酯化或磺化合成出了硼酸酯、硫酸酯和磺酸盐型咪唑啉两性表面活性剂;以二乙醇胺为原料合成两性表面活性剂时,先与脂肪酸或卤代烷反应合成出叔胺,叔胺再与各种季铵化剂反应制备各种两性表面活性剂;甜菜碱型两性表面活性剂的原料可以是脂肪酸、脂肪醇或脂肪伯胺。氨基酸型两性表面活性剂以伯胺为原料,合成出分子中引入了其他原子或基团。对这些两性表面活性剂的性能测定表明,它们的性能优良。     

Cholic Acid-Derived Facial Surfactants with Long Side-Chain Quaternary Ammonium: Synthesis and Antimicrobial Activity Study

Four cholic acid cationic surfactants containing a flexible long aliphatic chain were synthesized efficiently. A long aliphatic chain was introduced first on the side-chain carboxyl of cholic acid by one-pot condensation reaction of cholic acid and C12–C18 amines using DCC (Dicyclohexylcarbodiimide) and HOBt (N-hydroxybenzotrizole) as condensation agents for the formation of an amide framework. Then reduction of the amide and quaternization gave a cationic group for strengthening hydrophilicity. This strategy offered a very straightforward and efficient method for access to the designed surfactants in good overall yields. Preliminary results show that an increase both in the length of the hydrophobic tail and in the number of charged groups lowered the CMC of cholic acid-derived cationic surfactants. Cholic acid-based cationic surfactants containing a flexible longer aliphatic chain and a quaternary ammonium had the highest antimicrobial activity.     

皂氨型洁面的开发及性能研究

根据皂氨型洁面的开发需求,首先筛选合适的皂基型表面活性剂和氨基酸型表面活性剂;然后对皂基型表面活性剂和氨基酸型表面活性剂的配比进行优化,得出最优配比;最后将制得的复配皂氨型洁面与市售单一的皂基型洁面和单一的氨基酸型洁面的性能进行对比测试。结果表明,皂氨复配的皂氨型洁面对皮肤刺激性比单一皂基型洁面和单一氨基酸型洁面都小;皂氨复配的皂氨型洁面对油脂的清除率介于单一的皂基型和单一的氨基酸型洁面之间,为90.2%;皂氨型洁面在使用感方面整体上优于单一皂基型洁面和单一氨基酸型洁面。     

氨基酸型两性表面活性剂的合成进展

氨基酸型两性表面活性剂是一类以生物物质为基础的环保表面活性剂。主要综述了两种羧酸基氨基酸型两性表面活性剂（N-烷基-β-丙氨酸和N-酰基氨基酸）的合成方法和合成进展,简述了磺基、硫酸基、磷酸基及其它氨基酸型两性表面活性剂的合成路线。指出环境友好的酶法和化学一酶法合成氨基酸型两性表面活性剂具有广阔的应用前景。     

脂肪酸系列表面活性剂的研究进展

概括和综述了4大类10余个脂肪酸系列表面活性剂的合成、性能和应用现状，重点评述了烷醇酰胺及其衍生物、乙氧基化脂肪酸甲酯、脂肪酸甲酯磺酸盐、N-酰基ED3A、氨基酸、咪唑啉、甜菜碱、双子表面活性剂等脂肪酸系列表面活性剂的研究进展。此系列表面活性剂易生物降解、安全、多功能和高效能。     

脱氢枞酸的应用研究进展

综述了脱氢枞酸用于合成表面活性剂、具有生物活性的物质和手性催化剂,及其在抗老化、手性试剂拆分和在导电材料等方面的应用研究进展,并展望了其发展趋势。     

Cleaning Efficiency of Amino‐Acid Surfactants with Polyoxyethylene Ether and Isopropanol in Liquid Carbon Dioxide

Although anionic surfactants have a distinct positive influence on the removal of particulate soil, the removal of particulate soils is insufficient in CO₂ compared to perchloroethylene. A series of amino‐acid surfactants was selected as main surfactants to study the influence of polyoxyethylene ether and cosolvent on the cleaning effect. Glu‐C12 and C16(3) gave the best cleaning results, which increased from a detergency value of 4.6 when no surfactants were used to 8.32 when surfactants were used. In all experiments, charged anionic surfactant particles were formed, which are responsible for the removal of particulate soil from fabric by electrostatic repulsion. The use of a cosolvent (Isopropanol [IPA]) had a positive effect on the removal of particulate soil when using Glu‐C12 and TX‐45. However, for other compounding combinations, the addition of IPA had a negative effect on particulate soil removal. Of the cosolvents investigated, IPA was the most suitable. With the polarity of the system increasing after adding IPA, the ethylene oxide groups of TX‐45 were partially extended to CO₂. Through the steric effects of branched methyl groups, the cleaning effect was improved.     

两性表面活性剂（八）——两性表面活性剂的合成

较为详细地介绍了烷基甜菜碱、烷基酰胺基甜菜碱、磺基甜菜碱及其他若干种甜菜碱型表面活性剂的合成,并比较了其中一些合成路线,特别是磺基甜菜碱的几种合成方法。对咪唑啉中间体、两性咪唑啉合成中的主要副产物及两性咪唑啉的开环结构进行了报道。对氨基酸型两性表面活性剂的原料胺、长链烷基氨基酸及烷基低聚氨基酸的合成方法也进行了讨论。     

Green Synthesis,Characterization, and Properties of Acyl Lysine,Serine, Threonine,and Methionine Derived from Three Types of Natural Oils

The development of environmentally benign products has been the subject of growing interest in the field of surfactant chemistry. Acyl amino acid surfactants bearing lysine, serine, threonine, and methionine residues were synthesized using natural oils extracted from coconut, palm kernel, and soybean as acyl donors. The chemical structures were confirmed by high-performance liquid chromatography (HPLC/MS) and infrared (IR) spectra. Their surface activities, ion-specific effects, detergency, and foam properties were studied systematically. The critical micelle concentration (CMC) values depend significantly on amino acid and oil types and follow the orders: (i) Lys > Thr ≈ Ser > Met and (ii) Coconut ≈ Palm kernel > Soybean oil. Interestingly, the ion-specific effects showing that the γ_CMC value decreases with increasing counterion size and hydrophobicity were observed, and the results were consistent with the famous Hofmeister series. The detergency ability of acyl amino acid surfactants is better than multiple traditional surfactants in distilled water. Although the detergency ability of our products for oil-soiled swatches decreased significantly in hard water, this problem was solved by the C-Lys-Na/AES mixed system showing excellent synergistic effects. Excellent foamability and foam stability were achieved for acyl threonine and serine bearing hydroxyl groups on their headgroups, suggesting that the packing of these surfactants at the air–water interface was assisted by hydrogen bonding.     

Preparation and characterization of surface active erucic acid derivatives

Nonionic, cationic and anionic surfactants, derivatives ofcis-13-docosenoic acid (erucic acid), have been prepared and characterized, and their performance has been evaluated and compared with the corresponding derivatives of fatty acids with shorter alkyl chain length. Nonionic erucic acid ethoxylates give a solution behavior anticipated from the hydrophilic-lipophilic balance of the molecule; however, the increased molecular size as compared to ordinary surfactants results, e.g., in higher temperature stability of the surfactant aggregates. Anomalous solution behavior was found and investigated for anionic surfactants, triethanolammonium salts of erucic acid, and some shorter homologues. The effects are discussed in terms of the acid-base equilibria of the alkanolammonium counterion and the acid, together with effects due to the molecular size of the counterion.     

弱相互作用调控表面活性剂自组装(Ⅲ)——响应性表面活性剂

天然的或合成的两亲分子(表面活性剂)可以自组装形成多尺度的聚集体结构,比如胶束、囊泡、液晶和纤维等。在表面活性剂中引入功能性基团,借助外界环境(比如光、温度、pH、CO2、磁等)的改变可以实现对表面活性剂的聚集方式的调控。本文主要介绍响应性表面活性剂的种类、结构以及环境刺激与响应性能之间的关系。     

聚乙二醇型含硼表面活性剂的合成

含硼特种表面活性剂具有碳氢表面活性剂无法替代的长处,具有广阔的应用前景。因此,合成含硼表面活性剂意义重大。本论文采用聚乙二醇、三乙醇胺、硼酸为原料,应用潜溶剂法（以甲苯为溶剂,通过回流带出酯化反应所生成的水）制备了含硼表面活性剂。设计正交实验确定最佳的酯化条件。实验结果表明,最佳的酯化条件为：温度（90±2）℃,硼酸、三乙醇胺、PEG（400）的摩尔比为2：1：2。最佳酯化条件下合成的聚乙二醇型三乙醇酰胺硼酸酯表面活性剂的电导率为0．36mS·cm^-1,表面张力为67．00mN·m^-1,pH值为8～9,水溶液为均一透明溶液。所合成的硼酸酯表面活性剂可以很好地应用于金属切削加工液中。     

Synthesis and characterization of surfactants <Emphasis Type="Italic">via</Emphasis> epoxidation of tall oil fatty acid

The synthesis and characterization of novel surfactants derived from tall oil fatty acid methyl esters are presented. The tall oil fatty acid methyl esters, which mainly contain methyl oleate, were converted to 9,10-epoxy derivatives and further transformed to the 9 (or 10) polyethylene glycol (PEG) ethers. Compounds with three different monomethylated PEG chain lengths with molecular weights of 350, 550, and 750, corresponding roughly to 7, 11, and 16 ethylene oxide units, were prepared. Surfactants were formed at an 89% overall yield from tall oil fatty acid. Cloud points were 46, 63, and 84°C, respectively, and surface tensions at the CMC (2.0, 1.0, and 0.4 mM, respectively) varied from 33 to 38 mN/m. Equilibrium surface tension and reflectometry measurements were made and results were similar to those of conventional long alkyl chain PEG surfactants. Results of the tensiometry and reflectometry measurements showed that the surfactants aligned better at the air-water interface than conventional surfactants. The adsorption properties for the three surfactants were similar to those of polyoxyethylene glycol alkyl ethers.     

Back to the future: Fatty acids,the green genie to design smart soft materials

Fatty acids are widely used in industries for various applications as soaps or in their crystalline form. Fatty acid soaps are used as surface-active agent to stabilize foams and emulsions, for detergency, and surface wetting. Fatty acid molecules in organic solvents are used as low-molecular-mass organic gelators. Currently, there is a renewed interest in using fatty acids in industrial applications instead of petrochemical surfactants since fatty acid soaps are green surfactants. Fatty acids exhibit also many advantages, including the design of responsive soft-materials. Fatty acid soaps are natural pH and thermoresponsive surfactants, which can lead to responsive foams and emulsions. In their crystalline form, fatty acid crystals in both aqueous and non-aqueous solvents stabilize liquid foams. These crystals are also efficient in the production of liquid marbles. Fatty acids are solvosurfactants with the ability to form microemulsions and capillary suspensions. In this review, we illustrate how fatty acid molecules can be used in the manufacture of multiresponsive soft-materials ranging from aqueous and non-aqueous foams, emulsions, nanoemulsions, microemulsions, liquid marbles and capillary suspensions.     

有机硼表面活性剂的合成及其应用研究

以硼酸和甘油为起始原料 ,合成了几种以硼酸双甘油酯为中间体及环氧乙烷修饰的有机硼表面活性剂。通过红外光谱确定了产物的结构 ,并对有机硼表面活性剂的酸值、表面张力以及临界胶束浓度等性能进行了研究。最后重点探讨了有机硼表面活性剂在塑料抗静电领域的应用性能。     

磷酸蒸发浓缩助剂的实验研究

实验研究各种表面活性剂作为磷酸浓缩蒸发的助剂,用以提高水的蒸发强度,加入量只需磷酸质量的200×10-6,以TWEEN+NNO和TWEEN+GC效果较好。同时实验研究了各种阻垢剂,其中以SO-3和十二烷基苯磺酸钠最佳,对氟硅酸钾(钠)的阻垢率可达60%以上。湿法磷酸浓缩过程中同时加入上述表面活性剂,可提高蒸发强度,减少蒸汽用量,提高浓缩酸浓度,并有一定的阻垢作用。