新型腰果酚双子表面活性剂的合成及表面活性

以天然生物质腰果酚、1,3-二溴丙烷及氯磺酸为原料,通过醚化、磺化及中和三步反应合成了一类新型的腰果酚基磺酸盐双子(Gemini)表面活性剂.采用傅立叶转换红外光谱仪和核磁共振谱仪表征了产物的结构;采用滴体积法测定了腰果酚Gemini表面活性剂的表面张力,研究了水溶液的表面性质,并与相应的单基腰果酚基磺酸盐表面活性剂进行了对比.结果表明:腰果酚Gemini表面活性剂水溶液的临界胶束浓度(cmc)为6.20×10-2 mmol.L-1,远小于相应的单基腰果酚表面活性剂水溶液的cmc(8.40mmol.L-1);其临界表面张力γcmc为36.92mN.m-1,与单基腰果酚表面活性剂水溶液的相近(γcmc为38.41mN.m-1).与此同时,腰果酚Gemini表面活性剂水溶液的最小分子截面积Amin为0.27nm2,比相应的单基表面活性剂水溶液的小得多.     

磺化甜菜碱型双子表面活性剂的合成及性能

以N,N'-二甲基乙二胺为起始原料,合成了一类新型磺化甜菜碱型双子表面活性剂.通过红外光谱(IR)、核磁共振(~1H-NMR)对中间体及最终产物——磺化甜菜碱型两性离子双子表面活性剂的分子结构进行了表征.对合成产物的表面性能及相关物性参数作了初步的研究.实验表明:合成制得的磺化甜菜碱型双子表面活性剂具有优异的表面活性,最低的表面张力可降至27.81 mN/m,且有着良好的乳化性能.     

双酯基型Gemini表面活性剂的合成及其性能

以1,4-环己二醇、氯乙酰氯、长链叔胺(RN(CH_3)_2,R=10、12、14、16)为原料,合成了一系列不同长度烷基链的双酯基型Gemini表面活性剂(分别命名为C10-EG-10、C12-EG-C12、C14-EG-C14、C16-EG-C16),用FTIR、NMR(~1H、~(13)C)对中间体及产物进行了表征,并研究了表面活性剂的表面性能及抑菌能力。结果表明:在298.15K时,采用铂金环法测定了合成的4种不同长度烷基链Gemini表面活性剂的临界胶束浓度,C10-EG-C10、C12-EG-C12、C14-EG-C14、C16-EG-C16的CMC值分别为5.495、1.096、0.186、0.045 mmol·L~(-1),与传统单链季铵盐表面活性剂相比,合成的Gemini表面活性剂具有较低的CMC值。胶束化热力学参数结果表明在形成胶束过程中是自发放热的。对合成的4种表面活性剂进行了乳化性能、起泡性能和抑菌测试,C14-EG-C14表面活性剂具有很好的乳化能力;C16-EG-C16 Gemini表面活性剂具有良好的稳泡能力;C10-EG-C10表面活性剂具有良好的抑菌能力。     

萘(苯)双十四烷基双磺酸钠Gemini表面活性剂合成及性能研究

Gemini表面活性剂因其特殊的分子结构，使它在降低表面张力的效率与效能，以及起泡性、乳化力、润湿性等方面的性能大大优于传统表面活性剂。由此，Gemini表面活性剂成为近年日用化工及胶体与界面化学领域研究的热点课题之一。目前，Gemini表面活性剂优良的表化性能已被广泛认识，相应的理论研究趋于成熟，但Gemini表面活性剂在实际生产中的应用却不多见，究其原因主要是Gemini表面活性剂大都合成路线长，产品价格高，从而限制了它们的使用。本文拟以α-十四烯烃磺酸为原料，采用“一步法”合成萘（苯）双十四烷基双磺酸钠Gemini表面活性剂，其合成路线和反应条件均与现在生产α-烯烃磺酸钠相似，但成本却低于后者，有望实现高的性能价格比。     

含酰胺基Gemini阳离子表面活性剂的合成及性能

以棕榈酸、N,N-二甲基丙二胺、环氧氯丙烷和脂肪胺为原料合成了一系列Gemini阳离子表面活性剂.用红外光谱、质谱对产品进行了结构分析,并对产品性能进行了测定.结果表明:所合成的Gemini阳离子表面活性剂的临界胶束浓度低于传统阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)1-2个数量级;当浓度为1×10-3mol/...     

基于丙二酰胺的不对称双子表面活性剂的合成及其乳化性能

将二(3-二甲氨基丙基)丙二酰胺分别与溴代十六烷和溴代十四烷反应,生成的季铵盐化产物经丙酮-乙腈重结晶,得到含丙二酰胺基的不对称阳离子双子(Gemini)表面活性剂(命名为16-9-14),总收率为45.9%(以溴代十六烷计);利用红外光谱和核磁共振谱表征了合成产物的结构,采用电导法测定了其临界胶束浓度(CMC),采用滴体积法测定了其临界张力(γCMC),进而初步探讨了其发泡沫性能和乳化性能.结果表明,合成的Gemini表面活性剂的CMC为1.57×10-4 mol/L,γCMC为38.45mN/m;其发泡性能和乳化性能优于相应的单子表面活性剂.     

离子液体型表面活性剂C12mimBr与普通表面活性剂混合性质的研究

研究了离子液体型表面活性剂C12mimBr与阳离子表面活性剂Gemini 12-3-12, DTAB及阴离子表面活性剂SDS复配体系的性质, 并分别采用Rubingh-Margules模型和Rubingh-正规溶液模型计算了临界胶束浓度和混合胶团组成. 研究发现, 两表面活性剂分子结构的匹配性及带电头基之间的相互作用是影响混合溶液性质的主要因素. 对于分子结构差别较大的C12mimBr与Gemini 12-3-12的混合, 其行为远远偏离理想混合性质; 对疏水链长相同仅亲水头基不同的C12mimBr与DTAB则接近于理想混合; 而对C12mimBr＋SDS的复配体系, 正、负电荷间强烈的相互吸引使得混合体系大大偏离理想行为. 计算发现, 两种理论模型得到的混合胶团组成基本一致, 但Rubingh-Margules模型预测的临界胶束浓度比Rubingh-正规溶液模型要好     

酯基Gemini双季铵盐表面活性剂的研究进展

Gemini双季铵盐表面活性剂性能优异但生物和化学降解性差,在Gemini双季铵盐表面活性剂结构中引入酯基官能团可以提升产物性能。酯基Gemini双季铵盐表面活性剂含有酯基和双季铵盐基,具有高表面活性、吸附、絮凝、抗盐、湿润、乳化、杀菌防腐和易生物分解等优点,应用前景广阔。本文综述了酯基Gemini双季铵盐表面活性剂的合成路线、性能和石油化工的应用状况,结合发展需求对酯基Gemini双季铵盐表面活性剂的未来发展进行了分析和展望。     

Gemini型甜菜碱表面活性剂合成进展

Gemini型甜菜碱结合了甜菜碱和Gemini型表面活性剂的优点,可以在较低浓度下达到超低油水界面张力、配伍性好、耐温耐盐性好、Krafft点以及吸附量低,被广泛应用于日用化学、化学化工、纳米材料、生物技术和石油开采等领域。本文基于间隔基的类型介绍了近年来Gemini型甜菜碱表面活性剂方面的最新研究进展。重点阐述了对称胺型、三嗪环型、二卤代物型Gemini甜菜碱的合成方法,并从原料成本、产率、反应周期以及产物的性能等方面对合成方法进行了分析和比较。最后对Gemini型甜菜碱表面活性剂的发展进行了展望。     

Gemini表面活性剂合成进展*

系统总结了近百种Gemini表面活性剂的合成路线和方法,并且按照其结构特点分门别类地进行比较和归纳,对今后Gemini表面活性剂的合成发展方向提出了一些看法,这对促进此类新颖表面活性剂的工业化进程将具有指导意义。     

Application of new synthesized zwitterionic surfactants as hair shampoo components

Abstract

The purpose of the study was to applicate new synthesized zwitterionic surfactants as hair shampoo components. Hair shampoos formulated for the study contained newly synthesized sulfobetaines at a concentration of 2%. The above additives were evaluated to determine their effect on shampoo dynamic viscosity, texture, yield stress, foaming properties and surface tension of aqueous shampoo solutions. The viscosity of the sulfobetaine-enriched hair shampoos ranged between 6,000 and 21,000?mPa·s, which ensures the required application properties of the formulated products. The yield stress in three prototypical shampoos was equal to approximately 10?Pa, which represents the minimum value that should characterize cosmetics of this type. The sulfobetaines added to the formulations were not found to significantly affect the parameters of hardness and adhesive force. All the formulations under study, except for the shampoo containing N-dodecyl-N-piperidinium-1-propanesulfonate, exhibited good foaming properties. The incorporation of sulfobetaines into hair shampoos contributes to an effective decrease in the surface tension of their aqueous solutions, which may indicate beneficial washing properties. The use of the proposed sulfobetaines in hair shampoos favorably modifies their physicochemical and functional properties. The findings of the study can provide useful insights for the formulation of hair shampoos containing zwitterionic surfactants.     

Physicochemical properties of series of cardanol polyoxyethylene ether carboxylates with different ethoxylation unit at the interface

Series of cardanol polyoxyethylene ether carboxylates were synthesized with biomass cardanol as material to study their physicochemical properties at the interface. The surface tensions of the cardanol nonionic-anionic surfactants were measured at 25?°C and the thermodynamic parameters of adsorption were also calculated. The surface activity and thermodynamic properties of the cardanol nonionic-anionic surfactants were correlated to their chemical structures. With increasing of the number of the ethoxylation unit in the hydrophilic group, a decrease in adsorption efficiency and an increase in surface tension at critical micelle concentration and thermodynamic free energy of adsoption were observed and were attributed to a decrease in adsorption of the cardanol nonionic-anionic surfactants at the interface. Series of the cardanol nonionic-anionic surfactants have good wettability and foaming property. The foaming capacity and the foaming stability of the solution of the cardanol nonionic-anionic surfactants increase by decreasing in the ethoxylation unit and by increasing the double bond of the hydrophobic group. The physicochemical properties of the cardanol nonionic-anionic surfactants at the interface are correlated to the chemical structures of the investigated surfactants, and there is the synergy effect between the nonionic hydrophilic group and the anionic hydrophilic group at the interface.     

Synthesis and Surface Activity of Heterogemini Imidazolium Surfactants

A series of heterogemini imidazolium surfactants with two-methylene spacer groups ([C_m-2-C_nim]Br_{2, m, n}=8, 10, 12, 14, 16; m≠n) have been synthesized and characterized by 1H NMR and ESI-MS spectroscopy. The effects of various reaction parameters, including stoichiometry, reaction temperature and time, were investigated. In addition, the surface activity study about heterogemini imidazolium surfactants was carried out and the influences of dissymmetric degree on the surface properties were also discussed.     

杂双子表面活性剂的合成

α-溴代十四酸甲酯与对甲苯酚经W illiam son醚化、NBS溴化、季铵化、皂化得3个头基分别是羧酸盐和季铵盐的杂双子表面活性剂,其结构经1HNMR,IR和元素分析确认。     

新型孪尾Gemini两性离子表面活性剂应用性能

分别采用改进的Ross-Miles法及分水时间法,对3种新型孪尾Gemini两性离子表面活性剂(C8C8L3Sz、C8C8L4Sz和C10C8L3Sz)的泡沫性能及乳化性能进行了研究,并考察了表面活性剂浓度、分子结构和温度等对其的影响。 结果表明,该系列表面活性剂具有较好的泡沫性能,且随其浓度的增加,泡沫最大高度和半衰期均存在一个稳定值,疏水链越长,其起泡性能越差,泡沫稳定性越好;温度升高,起泡性能变好,泡沫稳定性变差;当表面活性剂浓度一定时,体系中加入低浓度的短链醇及无机盐均能提高泡沫的稳定性;C8C8L3Sz、C8C8L4Sz和C10C8L3Sz作乳化剂的最适宜的用量分别为6×10-4、6×10-4和4×10-4 mol/L,疏水基越长,乳化性能越好,而连接基对其影响较小;温度升高,乳化性能变差;当油相烷烃碳数相同时,环烷烃要比直连烷烃更易达到最佳乳化效果,但二者的乳状液稳定时间相当;对于油相烷烃碳数不同时,烷烃的碳链越长,乳状液的稳定性越差,乳化效果越不好。     

Molecular simulation study on the self-assembly behaviors of zwitterionic heterogemini surfactant in aqueous solution

The self-assembly behaviors of a series of zwitterionic heterogemini surfactants C_mH_2m+1-PO^4–(CH₂)₂-N⁺(CH₃)₂-C_nH_2n+1, abbreviated as C_m-P-N-C_n (m, n?=?9, 9; 9, 12; 9, 15; 9, 18; 12, 12; 12, 15; 12, 18; 15, 15; 15, 18; 18, 18), have been investigated in aqueous solution by the dissipative particle dynamics (DPD) method. Morphologies such as sphere (S), rod (R), planar grid (PG), lamella (L), honeycomb (H), one-, two-, and three-dimensional tunnels (1DT, 2DT, and 3DT) have been observed showing more diversities than those of the corresponding symmetric gemini surfactants C_m-N-N-C_m (m?=?9, 12, 15, 18). With the increase of surfactant concentration in the aqueous solution, a distinct transition path ‘‘S—R—PG—3DT—L—2DT—1DT’’ is proved to be common for all the C_m-P-N-C_n systems. Besides, the hydrophobic chain length has a significant influence on the self-assembly behaviors in the case of m?≠?n. Radial distribution function is an effective method to quantitatively evaluate the interaction and relationship between each functional group in the surfactant molecule and water. Results can provide a new insight into the self-assembly behaviors of zwitterionic heterogemini surfactants and the corresponding applications.     

正负离子表面活性剂与两性表面活性剂的相互作用

本文研究正负离子表面活性剂与两性表面活性剂混合水溶液的表面性质, 以及两性表面活性剂对正负离子裘面活性剂溶解度的影响。结果表明: (1) 两性表面活性剂的加溶作用,有助于正负离子表面活性剂的溶解; (2) 加入两性表面活性剂的量适当, 混合溶液基本保持原正负离子表面活性剂的表面活性; (3) 正负离子表面活性剂与两性表面活性剂在表面层和胶团中分子间的相互作用比正负离子表面活性剂与非离子表面活性剂分子间的相互作用稍强HC-FC正负; 离子表面活性剂与两性表面活性剂混合体系在表面层中有可能形成双分子或多分子层结构。     

Alpha-Lactalbumin is unfolded by all classes of surfactants but by different mechanisms

We show that all four classes of surfactants (anionic, cationic, non-ionic, and zwitterionic) denature alpha-lactalbumin (alphaLA), making alphaLA an excellent model system to compare their denaturation mechanisms. This involves at least two steps in all surfactants but is more complex in charged surfactants due to their strong binding properties. At very low concentrations, charged surfactants bind specifically as monomers, but the first denaturation process only sets in when 4-10 surfactant molecules are bound to form clusters on the protein surface and is followed by a second loss of structure as 20-25 surfactant molecules are bound. Sub-micellar interactions can be modeled as simple independent binding at multiple sites which does not achieve saturation before micelle formation sets in. In contrast, no specific sub-micellar surfactant binding is detected by calorimetry in the presence of zwitterionic and non-ionic surfactants, and denaturation only occurs around the cmc. Unfolding rates are very rapid in charged surfactants and reach a similar plateau level around the cmc, indicating that monomers and micelles operate on a mutually exclusive basis. In contrast, unfolding occurs slowly in zwitterionic and non-ionic surfactants and the rate increases with the cmc, suggesting that monomers cooperate with micelles in denaturation.     

芳基油酸酰胺羟丙基磺基甜菜碱的合成及性能

合成了3种具有不同疏水基团的新型磺基甜菜碱两性表面活性剂,通过红外光谱对它们的结构进行了表征。 用滴体积法测定表面活性剂水溶液在25 ℃下的表面张力,从而确定其临界胶束浓度(cmc)及临界胶束浓度下的表面张力(γcmc);采用罗氏泡沫仪考察了浓度、温度对其泡沫性能的影响;采用分水时间法考察了其乳化性能。 结果表明,随着芳环在烷基链中的体积增大,cmc以及γcmc增大,饱和吸附面积Amin增大,而饱和吸附量Γmax减小。 3种表面活性剂的起泡性随浓度增大而增加,到一定值后趋于稳定;泡沫稳定性随浓度增大逐渐增强;起泡性随着温度的升高而显著增加,泡沫稳定性随温度升高而显著降低。 3种表面活性剂的乳化能力随浓度增大而逐渐增强然后趋于稳定。