N-月桂酰基乙二胺三乙酸的合成及性能研究

采用无水乙二胺、月桂酸和氯乙酸为原料合成N-月桂酰基乙二胺三乙酸,通过正交实验确定了最佳实验条件,同时对产物的润湿力、乳化力和螯合能力等性能进行了研究。性能研究表明:产品泡沫稳定性能很好,29.2℃时,cmc=3.48 mmol/L,γ(cmc)=23.7 mN/m。     

Characterization and emulsification properties of rhamnolipid and sophorolipid biosurfactants and their applications

Due to their non-toxic nature, biodegradability and production from renewable resources, research has shown an increasing interest in the use of biosurfactants in a wide variety of applications. This paper reviews the characterization of rhamnolipid and sophorolipid biosurfactants based on their hydrophilicity/hydrophobicity and their ability to form microemulsions with a range of oils without additives. The use of the biosurfactants in applications such as detergency and vegetable oil extraction for biodiesel application is also discussed. Rhamnolipid was found to be a hydrophilic surfactant while sophorolipid was found to be very hydrophobic. Therefore, rhamnolipid and sophorolipid biosurfactants in mixtures showed robust performance in these applications.     

一株脂肽类生物表面活性剂产生菌的性能及其影响因素研究

通过对实验筛选出一株产脂肽类生物表面活性剂的菌株BW-23,进行性能及其影响因素研究.结果表明:脂肽表面活性剂的CMC浓度为70 mg/L时,表面张力为31.0 mN/m;发酵液稀释10倍后,乳化指数仍为24.72％;在10～60℃间菌株BW-23所产的生物表面活性剂的耐热性较好;菌株BW-23在pH值为5.0～8.0时表面活性最好;当NaCl浓度小于15％时,菌株BW-23水溶液的表面张力变化幅度最小;当Ca2+浓度达到5000 mg/L时,菌株BW-23水溶液的表面张力为30.5 mN/m.     

Enzymatic preparation of polyethylene glycol esters of castor oil fatty acids and their surface-active properties

This study concerns the preparation and evaluation of nonionic surfactants prepared from polyethylene glycol (PEG) esters of castor oil fatty acid, a source of hydroxy fatty acid. A lipase-catalyzed esterification reaction has been employed to prepare PEG esters of hydroxy acid to overcome problems associated with chemical processes. Castor oil fatty acid (85% ricinoleic acid) was mixed with PEG of different molecular weight. Rhizomucor miehei lipase was added as catalyst (10% level) and the reaction was continued at 60°C under 2 mm Hg pressure for 360 min. Conversion of PEG to esters was in the range of 86–94%, depending on the molecular size of PEG. The products were isolated and examined for surface activity by surface tension measurement. Surface tension values measured at 25°C were about 36–37 dynes/cm.     

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.     

Preparation and surface-active properties of telomer-type anionic surfactants from maleic anhydride

Maleic acid alkyl ester and N-alkyl maleamic acid monomers (R_nMa and R_nMaAm; n is alkyl chain length; n=6, 8, 10, 12, 14) were synthesized by the reaction of maleic anhydride with alkyl alcohol or alkylamine. The telomerization of R_nMa or R_nMaAm in the presence of alkanethiol as a chain transfer agent gave telomer-type anionic surfactants (xR_nMa, xR_nMaAm; x is total average number of alkyl chains; x=2.8–3.3) having multialkyl chains and multicarboxylate groups. Their surface-active properties were investigated by several techniques such as surface tension, foaming property, and emulsification power measurements. Critical micelle concentrations (CMC) of xR_nMa were 1/110–1/14 of those of R_nMa with the same alkyl chain length. xR_nMa and xR_nMaAm gave higher efficiencies in lowering the surface tension than R_nMa and R_nMaAm in aqueous solutions. In particular, the surface tension of 3.2R₁₂MaAm was 24.4 mN m⁻¹ at the CMC. Foaming abilities and foam stabilities of xR_nMa and xR_nMaAm were higher than those of R_nMa and R_nMaAm. The addition of 300 ppm of Ca²⁺ to the aqueous solutions rendered the telomers less surface active. Shaking the aqueous solutions of telomers with toluene emulsified them. The highly stable oil-in-water type emulsion was formed by using 3.0R₁₀MaAm and 3.2R₁₂MaAm, and the degree of emulsification was kept at a level of about 80% after 60 min of standing. Thus, telomer-type surfactants showed excellent surface activities that were superior to the corresponding monomers as well as to conventional surfactants. The relationship between alkyl chain length of the telomers and the properties of surface tension, foaming, and emulsification was unclear.     

脂肪酸烷醇酰胺磷酸酯表面活性剂的合成及性能研究

以C14~18的脂肪酸与二乙醇胺反应合成了系列脂肪酸烷醇酰胺,再经磷酸化反应及中和反应制备了6种脂肪酸烷醇酰胺磷酸酯盐表面活性剂。分别测定了各产物的组成及表面活性,考察了无机盐对表面张力(γ)及临界胶束浓度(cmc)的影响,测试了不同碱中和产物水溶液与系列烷烃间的界面张力。结果表明,脂肪酸碳数为14,16和18的烷醇酰胺磷酸酯盐表面活性剂的cmc分别为50,50和30 mg/L,γcmc为26~31 mN.m-1;无机盐对产物的cmc影响不大;在质量分数为0.3%时,6种表面活性剂水溶液与正构烷烃形成最低界面张力的最小烷烃碳数为10~16,其中用NaOH中和得到的C14N与十二烷、十四烷以及C16N与十六烷均可达到超低界面张力,分别为0.007 8,0.008 3和0.001 6 mN.m-1,用二乙醇胺中和得到的C14D也可与癸烷达到超低界面张力。     

新杂环不对称双偶氮变色酸类试剂的合成及其性能研究

设计并合成了5种新新的未见文献报道的苯并噻唑不对称双偶氮变色酸类试剂,研究了试剂的性质及其与金属离子的反应行为。     

Synthesis and surface activity of sodium salts of branched perfluorocarboxylic acids and their analogs containing one chlorine atom

Individual sodium salts of branched perfluorocarboxylic acids, (CF₃)₂CF(CF₂CF₂)_nCOONa, and their analogs containing one chlorine atom, CF₃CF(CF₂CI)(CF₂CF₂)_nCOONa, were synthesized by telomerization of 2-iodoheptafluoropropane and l-chloro-2-iodohexafluoropropane with tetrafluoroethene, the addition of ethylene to both types of iodides considered, HI elimination and the oxidation of perfluoroalkylethylenes with potassium bichromate. The surface tension measurements demonstrated the high surface activity of sodium salts containing 9 and 11 carbon atoms in the hydrophobe. Perfluorocompounds were more surface active than their analogs having one chlorine atom but the differences were not great.     

Synthesis and physical properties of isostearic acids and their esters

Saturated branched‐chain fatty acids (sbc‐FAs) are found as minor constituents in several natural fats and oils. Sbc‐FAs are of interest since they have lower melting points than their linear counterparts and exhibit good oxidative stability; properties that make them ideally suited in a number of applications. We (and others) have previously synthesized sbc‐FAs by clay‐ or zeolite‐catalyzed isomerization of unsaturated linear‐chain fatty acids (ulc‐FAs) to unsaturated branched‐chain fatty acids (ubc‐FAs) that were subsequently hydrogenated to the desired sbc‐FAs. These acid‐catalyzed isomerization reactions, however, proceed in moderate conversion and selectivity. Recently, our group found that H‐Ferrierite zeolite catalyst isomerized ulc‐FAs to their branched‐chain counterparts in high conversion (>95%) and selectivity (85%). This paper reports the use of this type of catalyst for the preparation of a series of sbc‐FAs and their ester derivatives. Selected physical properties of these branched acids and esters such as cloud point (CP) and pour point (PP), cold filter plugging point (CFPP), viscosity index (VI), thermo‐oxidation stability, iodine value, and lubricity are also reported.     

Evaluation of production of lipopeptide biosurfactants and surfactin micelles by native Bacillus of Iran,for a broader application range

Surfactin is one of the most important lipopeptide biosurfactants obtained by biocatalysts of Bacillus subtilis. The aim of this study was to isolate surfactin-producing bacilli from native soils of the country (Iran), investigate their properties, convert surfactin to surfactin micelles, determine the properties of surfactin micelles and investigate the effect of starch-coated Fe⁰ and Fe³⁺ nanoparticles on the production of surfactin from B. subtilis. To do so, 20 bacilli were isolated from the native soil sample by heat shock method and genome sequenced by SrRNA16 method. The samples with strong β-hemolysis activity were screened as surfactant-producing strains. Two species of 61 and 63 (B. subtilis subspecies. Inaquosorum) were selected and examined by quantitative and qualitative screening tests such as hemolysis activity, surfactin production, droplet aggregation, emulsifying activity, and surface tension reduction in MSM medium containing Fe⁰ and Fe³⁺ nanoparticles. Surfactin was converted to surfactin micelles by sonication and confirmed by SEM. The antimicrobial and emulsifying activity and surface tension reduction of surfactin micelles were investigated. According to the results, the surface tension reduction of surfactin micelles was greater than that of surfactin. The strain 61 (99.7%) culture in 5 L bioreactors containing Fe³⁺ nanoparticles produced more surfactin than culture of the same strain without nanoparticles. This study presents an efficient method to increase the biosynthesis of microbial metabolites.     

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。     

系列室温离子液体1-烷基-3-甲基咪唑六氟磷酸盐的合成及性质研究

合成了系列1-烷基-3-甲基咪唑六氟磷酸盐([C4～7mim]PF6)室温离子液体,并通过核磁氢谱、红外光谱、质谱等手段对其进行了结构表征。采用Wilhelmy白金板法在室温25℃测定了离子液体的表面张力,随着1位氮上取代基碳链的增长,表面张力从[C4mim]PF6的48.0 mJ/m2逐渐下降到[C7mim]PF6的35.7 mJ/m2,呈现出较宽的变化范围。离子液体的吸水性较差,1位氮上取代基碳链的长短影响不大,其饱和含水量均低于0.9%。     

单乙醇脂肪酰胺的合合成及性能

以辛酸，癸酸，月桂酸，肉豆蔻酸，棕榈酸，硬胆酸和油酸为原料分别与单乙醇胺反应，合成了一系列单乙醇脂肪酰胺，上述产品经重结晶提纯后，测定了系列单乙醇脂肪酰胺对w(AES)=10%和w(Ninol)=3%等表面活性剂水溶液体系的增稠，泡沫性能和珠光效果，研究表明，各种意志乙醇脂肪酰胺可以分别用异丙醇，水，丙酮和石油醚重结晶，单乙醇脂肪酰胺为白色片状晶体，C12－C18的单乙醇脂肪酰胺有较好的增稠性能，其中单乙醇油酰胺最好，单乙醇月桂酰胺对体系发泡与稳泡有明显的促进作用，单乙醇硬脂酰胺在体系中有很好的珠光效果。     

O-三苯基锡不饱和烃基膦酸的合成与性质

通过三苯基锡不饱和烃基膦酸反应,合成了8种新的O－三苯基锡不饱和烃基膦酸Ph3SnOP(O)(OH)R.。利用元素分析、IR、^1HNMR和MS确定了这些化合物的结构。     

Predicting the surface tension of biodiesel fuels from their fatty acid composition

The emergence of biodiesel fuels as diesel fuel substitutes has led to several studies on their properties. Surface tension, which plays a role in atomization, has lacked attention compared to other properties. This paper presents a method to predict the surface tension of biodiesel fuels based on the fatty acid composition. Several binary, ternary, and quaternary mixtures of fatty acid ethyl ester gas chromatographic (GC) standards were prepared, and we found that a mass-average equation predicted the surface tension of these mixtures within ±3.5% of their measured values. Six complex mixtures of fatty acid methyl ester GC standards that simulated typical oils used as biodiesel fuels were also prepared. For these complex mixtures the predicted surface tensions of the mixtures, calculated from a mass-average equation, were 2–6% higher than the measured values. A mass-average equation was developed in which we used a weighted surface tension for the individual components, and we found that this method predicted the surface tension of the simulated oils within ±4.5% of their measured values. Five natural vegetable oils were used to produce biodiesel fuels by the transesterification process. The predicted surface tensions of these fuels were all within ±3.5% of their measured values. The surface tensions of 15 biodiesel types were then predicted, based on their fatty acid composition as published in the literature. These results show that the differences in surface tension between biodiesel types are not the main cause of the reported differences in engine tests.     

十六醇聚氧乙烯醚(3)羧酸盐的合成及其耐盐性和界面性能研究

以十六醇聚氧乙烯(3)醚为原料,经羧甲基化合成了十六醇聚氧乙烯醚羧酸钠,产率最高达到83.8%。产品经红外光谱和质谱表征为十六醇聚氧乙烯醚(n)羧酸盐(C16AEC,n=1～3)。研究表明,C16AEC具有优良的抗Na+能力,45℃下对NaCl的容忍度达到135 g.L-1,与典型的耐盐型表面活性剂十二醇聚氧乙烯醚(3)硫酸盐(AES)相当;但C16AEC抗二价离子(Ca2+和Mg2+)的能力一般,45℃下对CaCl2和MgSO4的容忍度仅为0.5和1.8 g.L-1,远不如AES;C16AEC微乳体系的最佳盐度(NaCl)和中相盐宽亦与AES微乳体系接近;C16AEC具有优良的表面活性,25和45℃下临界胶束浓度(cmc)都在10-5mol.L-1数量级,γcmc小于30 mN.m-1;C16AEC具有较好的亲油性,通过与两性表面活性剂复配,45℃下可在0.1%～0.3%的总质量浓度范围内使大庆原油/地层水界面张力降到10-3mN.m-1数量级,无需添加任何碱或中性电解质。     

脂肪酸双酯双磺酸盐型双子表面活性剂的合成及性能

以脂肪酸、二甘醇、氯磺酸为原料,经酯化、磺化反应制备了4种二甘醇双(α-磺酸钠)烷基羧酸酯表面活性剂。用红外光谱、元素分析对产物进行了表征,并对其表面活性和聚集行为进行了研究。结果表明,该类脂肪酸双酯双磺酸盐型双子表面活性剂比十二烷基硫酸钠的临界胶束浓度低1～2个数量级和更强的降低表面张力的能力。稳态荧光猝灭实验表明,表面活性剂胶束聚集数随着烷烃链碳原子数的增加而逐渐减小。     

N-十六烷基乙二胺三乙酸钠的合成及性能

用无水乙二胺、1-溴-十六烷和氯乙酸为原料,合成N-十六烷基乙二胺三乙酸钠,以提高阴离子表面活性剂在硬水中的稳定性。性能研究表明:它在硬水中的稳定性达到4级,cmc为2 13mmol·dm-3,γcmc=34.7mN·m-1。对产物的润湿力、分散力、乳化力等其他性能也进行了研究。