Synthesis and characterization of cleavable surfactants derived from poly(ethylene glycol) monomethyl ether

A series of noncyclic acetal-linked cleavable surfactants were simply prepared by condensation of aldehydes with poly(ethylene glycol) monomethyl ethers. All of the products were characterized by¹H nuclear magnetic resonance. Their hydrophile-lipophile balance, surface tension, cloud point, critical micelle concentration, and foam height were determined. Hydrolysis kinetic studies, followed by gas chromatography, showed that they had higher hydrolytic reactivity in acidic solution than cyclic acetal-linked cleavable surfactants.     

Nonionic cleavable ortho ester surfactants

A new class of cleavable surfactants based on the ortho ester link is described. Ortho ester surfactants were synthesized from a short-chain ortho ester, a fatty alcohol, and a poly(ethylene glycol) monomethyl ether. The triple functionality of the ortho ester link results in a mixture of surface-active and nonsurface-active species. Structures were confirmed by ¹H and ¹³C nuclear magnetic resonance. Hydrolysis characteristics at pH values ranging from 2 to 8 were determined. It was shown that, after a steep rise, hydrolysis curves flattened out before complete hydrolysis was reached. Ortho ester surfactants hydrolyze more rapidly than corresponding acetal surfactants. Hydrolysis rates are higher for purified samples and at higher temeprature, while plateau levels are higher for the purified surfactant mixtures and at lower pH. The origin of these results is discussed. Data also indicate that the hydrolysis mechanism changes with pH. A test of the loss of emulsification capacity for an ortho ester surfactant with time at pH values from 2 to 11.5 and at 22 or 50°C was carried out, showing rapid breaking of the emulsion at mild acid conditions and a requirement of pH≥10 for long-term stability. Surface tension and critical micelle concentration were determined for some of the surfactant mixtures. It was demonstrated that ortho ester surfactants possess excellent biodegradation properties. The new surfactants are promising candidates for use in industrial processes where temporary surfactant action is required.     

可分解香兰素基非离子表面活性剂的乳化性

针对已合成的含缩醛结构的环保型非离子表面活性剂香兰素辛二醇缩醛聚氧乙烯醚(VAEO),研究不同乙氧基链长的VAEO_n(n=6～24)的表面活性及乳化性,并与壬基酚聚氧乙烯醚(NPEO_(10))的表面活性及乳化性作比较。结果表明,随EO聚合度(n)增大,VAEO_n降低表面张力和油/水界面张力的能力下降,对石蜡乳化能力减弱。EO聚合度为6～10的VAEO_n与NPEO_(10)降低表面张力的能力相近,乳化性能也相当。VAEO_n降低油/水界面张力的能力较NPEO_(10)差。采用Material Studio软件模拟分析VAEO_n和NPEO_(10)乳化石蜡的能力,结果表明VAEO_n乙氧基链越长,乳化石蜡重新聚集的速度越快,即乳化性能越差,模拟结果与乳化石蜡分相法的实验结果相吻合。     

Ortho ester-based cleavable cationic surfactants

A new type of cleavable cationic surfactant, based on the ortho ester link, is described. Ortho ester amines with alkyl chain lengths from C₈ to C₁₆ were synthesized from a short-chain ortho ester, a fatty alcohol, and an amino acohol. The ortho ester amine was subsequently quaternized with methyl chloride, yielding a cationic surfactant. The structures were confirmed by ¹H and ¹³C nuclear magnetic resonance and the surface chemical properties were investigated by measuring both static and dynamic surface tensions. The results were compared to standard n-alkyl trimethyl ammonium bromides. The critical micelle concentrations were found to vary rather widely, whereas the surface tensions in some cases were comparatively low. The short alkyl chain ortho ester quaternaries were found to have low surface tensions at short surface ages and to induce rapid wetting of a hydrophobic surface in dynamic tests. Additionally, the new surfactants were found to hydrolyze rapidly under mild acidic conditions, as measured by both titation and monitoring of the dynamic surface tension. Further, they showed excellent long-term stability at pH 10 in dilute aqueous solutions. The effect of added electrolyte on rate of hydrolysis was also investigated. A marked enhancement in the hydrolysis rate was found when NaBr was added, whereas NaCl did not have the same effect. The new surfactants could potentially be used to provide temporary surfactant action in application areas such as disinfection, fabric care, personal care, chain lubrication, and mineral flotation as well as in textile processes such as dyeing or scouring.     

Synthesis and properties of bis(sodium sulfonated ester) types of cleavable surfactants derived from 1-O-alkylglycerols

Novel sulfonated ester types of cleavable surfactants were easily prepared by acid-catalyzed esterification of 1-O-alkylglycerols with bromocarboxylic acids, followed by the Strecker reaction. These surfactants have good solubility in water. Though this series of cleavable surfactants are divalent in type, they show good micelle formation and the ability to lower surface tension. The solubility of these surfactants in hard water was more than 10 times higher than sodium 1-dodecanesulfonate. They decompose quickly and completely in 0.5 M NaOD. Their biodegradabilities were higher or almost the same as that of sodium 1-dodecanesulfonate.     

Biodegradation of different carboxylate types of cleavable surfactants bearing a 1,3-dioxolane ring

The biodegradability of new carboxylate types of “acid-sensitive” cleavable surfactants bearing a 1,3-dioxolane ring was measured by the biochemical oxygen demand (BOD) method in the presence of activated sludge. The result for sodium dodecanoate, measured under the same conditions, was used as a standard for evaluating the biodegradability of these cleavable surfactants. For cleavable surfactants derived from epoxides and oxocarboxylates, the biodegradation was considerably influenced by the length of the lipophilic alkyl chain, the presence of the oxymethyl moiety in the lipophilic group, and the number of methylene units between the dioxolane ring and the carboxylate group. For another type of cleavable surfactant, 2-(long-chain alkyl)-1,3-dioxolane-4,5-dicarboxylate, the biodegradation rate for the compound, bearing a proton at position 2 in the dioxolane ring, is faster than that for the corresponding compound bearing a methyl group at position 2.     

Synthesis and surface-active properties of trimeric-type anionic surfactants derived from tris(2-aminoethyl)amine

Trimeric-type anionic surfactants (3C_ntaAm, where n is a hydrocarbon chain length of 8, 10, or 12) with three hydrocarbon chains and three carboxylate headgroups were synthesized from tris(2-aminoethyl)amine, and their properties were investigated by surface tension, electrical conductivity, dynamic and static light-scattering, fluorescence of pyrene, and emulsification power techniques. The critical micelle concentrations (CMC) of 3C_ntaAm were 0.00092–0.00834 mmol dm⁻³, and the surface tensions at the CMC were 33.3–39.9 mN m⁻¹. The areas per molecule occupied by 3C₁₀taAm and 3C₁₂taAm were extremely small, showing they were highly compact at the air/water interface. In addition, adsorption or micellization behavior of 3C_ntaAm was estimated by parameters such as pC ₂₀ (the efficiency of surface adsorption), CMC/C ₂₀ (the ease of adsorption relative to the ease of micellization), and ΔG _M ^o (Gibbs energy of micellization). Dynamic and static light-scattering mesurements of 3C_ntaAm showed a hydrodynamic radius of 45–61 nm above the CMC and aggregation numbers of 10–82 at the CMC, respectively. The fluorescence intensity ratio of the first to the third band in the emission spectra of pyrene started to lower from far above the CMC for 3C₈taAm and 3C₁₀taAm, and below the CMC for 3C₁₂taAm. This suggests that loose micelles or premicellar aggregates are formed in solutions. Mixtures of aqueous solutions of 3C_ntaAm and toluene formed oil-in-water-type emulsions, and the stabilizing abilities were in the order of 3C₈taAm>3C₁₀taAm>3C₁₂taAm. The degree of emulsification of 3C₈taAm remained at 69% after 24 h of standing. Thus, 3C_ntaAm exhibited unique properties superior to monomeric or dimeric surfactants that were significantly influenced by their hydrocarbon chain lengths.     

Synthesis and characterization of cleavable cationic surfactants with a 1,3-dioxane ring

A series of cationic cleavable surfactants was prepared by condensation of 2-alkyl-1,3-propanediols with 3-bromopropanal, followed by reaction with triethylamine. Each surfactant is a mixture of two diastereomers, and their precursors’ stereochemical assignments were based on¹H nuclear magnetic resonance spectra and melting points. The critical micelle concentrations, Krafft points and destructibility of these surfactants were determined.     

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。     

基于天然产物表面活性剂的研究进展

天然产物衍生的表面活性剂作为一种重要的化工原料,在洗涤、印染、造纸、纺织以及石油等行业被广泛研究和应用。就基于天然产物（糖类和疏水性化合物）的表面活性剂的合成方法进行介绍,对其溶解性、分散性、熔点、润湿性、乳化性和发泡性等物理化学特征进行详细讨论。基于天然产物的绿色表面活性剂由于具有良好的生物降解性以及温和性,成为精细化学品未来发展的主要方向之一。     

Novel hydrolyzable and biodegradable cationic gemini surfactants: 1,3-bis[(acyloxyalkyl)-dimethylammonio]-2-hydroxypropane dichloride

Novel cationic gemini surfactants, 1,3-bis[(acyloxyalkyl)dimethylammonio]-2-hydroxypropane dichloride, which possess hydrolyzable oxycarbonyl moieties in the lipophilic portions, were prepared. These surfactants showed much better micelle-forming ability, ability to lower surface tension, foaming ability, and foam stability than corresponding single-chain surfactants. Their surface properties were largely influenced by changing the position of the oxycarbonyl group in the lipophilic moiety. The critical micelle concentration decreased with a decreasing number of methylene units in the linking moiety between the ammonio and the oxycarbonyl groups within the comparison of lipophilic chains of the same length. These cationic gemini surfactants also showed good biodegradability.     

Preparation and properties of cleavable dianionic surfactants with a 1,3-dioxane ring

Some cleavable dianionic surfactants were prepared by the reaction of aldehydes with diethylbis(hydroxymethyl)-malonate, followed by saponification with sodium hydroxide. The critical micelle concentrations of the surfactants were determined.     

氟表面活性剂的工业应用

介绍了氟表面活性剂的分类、结构及性质;主要综述了由于氟表面活性剂具有"三高"、"两憎"的独特性能,广泛应用于消防、皮革、石油、造纸、纺织印染及金属材料加工等工业领域,起到普通碳氢表面活性剂所不能的作用;指出了根据应用领域的不同,应从分子结构设计入手,有针对性地、有目的地研发氟表面活性剂新品种新工艺,拓展应用领域,注重氟表面活性剂与普通表面活性剂的复配研究。     

壬基酚衍生的季铵盐阳离子表面活性剂的合成及性能

利用环氧氯丙烷和三乙胺分别与壬基酚、壬基酚聚氧乙烯醚 (n =4)反应 ,合成了 (2 -羟基 -3 -壬苯基 )丙基三乙基氯化铵 (1)和 (2 -羟基 -3 -壬苯基聚氧乙烯基 )丙基三乙基氯化铵 (2 )新型阳离子表面活性剂。化合物 (1)和 (2 )的γcmc 分别为 3 1 2 0mN/m、 3 3 47mN/m ,cmc分别为3 16× 10 -4mol/dm3 和 2 0 3× 10 -4mol/dm3 ,具有良好的絮凝能力。     

Preparation and properties of sulfonate salt-type cleavable surfactants with a 1,3-dioxane ring

A series of di-anionic cleavable surfactants were prepared by the condensation of aldehydes with 2,2-bis(hydroxymethyl)-1,3-propanediol, followed by reaction with 1,3-propanesultone in the presence of sodium hydride. Surfactant 5a had a different¹H nuclear magnetic resonance spectrum in D₂O than products 5b−d. This was rationalized by its different conformation, which originates from the self-coiling of its alkyl chain. The critical micelle concentrations, Krafft points and hydrolysis properties of these surfactants were determined.     

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.     

表面活性剂发展的新动向

近几年来，全球表面活性剂行业市场疲软，原料成本上涨和产品价格下跌导致利润率下降，表面活性剂行业不得不进行改组、合并。尽管如此，仍然有新的生产技术和新产品在开发，除了新阴离子表面活性剂外，非离子和两性离子表面活性剂增长也极迅速。除介绍全球表面活性剂市场的发展外，着重介绍新的生产技术和新产品。     

Gemini型表面活性剂的研究与应用进展

Gemini型表面活性剂是一种具有特殊结构的新型表面活性剂,由于其性能优良受到越来越多的关注.总结了近几年来国内外Gemini型表面活性剂的研究成果,对其特殊结构及性能(如界面性能、相行为和流体力学性质等)进行了较为全面的介绍,并对其在生产、生活和医药等领域的潜在应用进行了简要概括.     

异构醇型特种表面活性剂的合成及应用

介绍了异构醇型表面活性剂的种类、合成方法及物化性能,综述了异构醇聚氧乙烯聚氧丙烯醚、异构醇醚琥珀酸酯磺酸盐、异构醇聚醚羧酸盐在纺织、造纸、电镀和日化等行业的应用。     

New anionic alkylaryl surfactants based on olefin sulfonic acids

A new family of anionic surfactants has been produced by the simultaneous sulfonation and alkylation of aromatic compounds using olefin sulfonic acid(s). This new process does not require the conventional alkylation unit and the strong acid catalysts, such as AlCl₃ or HF, normally used for alkylation. The resulting alkylaryl sulfonic acids differ from existing prodeucts by having the sulfonate group attached to the alkyl chain rather than the aromatic ring. This allows for further derivatization of the aromatic compounds by leaving more positions open on the ring. Aromatic compounds that lend themselves to the new process include benzene, toluene, xylene, alkylbenzenes, phenol, alkylphenols, alkoxylated phenols, alkoxylated alkylphenols, alkoxylated alkylphenol/formaldehyde resins, naphthalene, and alkylnaphthalenes. Any type of olefin that can be sulfonated can be used as the starting material. These include internal and α-olefins, linear and branched olefins, polyolefins, and vinylidenes. Mono- and disulfonated compounds, as well as geminitype surfactants, are easily prepared.