Antistatic and wetting properties of chemodegradable cationic surfactants containing 1,3-dioxolane moiety

In this paper we report some performance properties of [(2-alkyl-1,3-dioxolane-4-yl)methyl]trimethylammonium bromides (C _n -D-TAB, where C _n =n-C₉H₁₉, n-C₁₁H₂₃, n-C₁₃H₂₇), [(2,2-dialkyl-1,3-dioxolane-4-yl)methyl] dimethylammonium bromides (C _n C _m -D-TAB, where C _n =n-C₈H₁₇, n-C₁₀H₂₁ and C _m =CH₃ or C _n =C _m =n-C₆H₁₃), in relation to classical alkyltrimethylammonium bromides (C _n -TAB, where C _n =n-C₁₂H₂₅, n-C₁₄H₂₉ or C₁₆H₃₃) and dialkyldimethylammonium bromides (C _n C _m -DAB, where C _n =C _m =n-C₁₀H₂₁ and C₁₂H₂₅). Antistatic properties were measured by means of surface resistance (R _s), half charge decay time τ_1/2, and maximal voltage induced (U _ind) on polyethylene (PE) film and polypropylene (PP) nonwoven fabric. Wetting ability is reported as the concentration of surfactant necessary for immersion of a cottonfabric ring in 100 s, according to the Polish Standard PN-74/C-04800. All acetal-type surfactants showed the antistatic effect. The best results were given by C₉-D-TAB [R _s=8.5·10⁷ (PE), 1.1·10⁸ Ω (PP); τ_1/2=0.25 (PE), 0.30 s (PP); U _ind=205 (PE), 220 V (PP)] and C₁₁-D-TAB [R _s=8.7·10⁷ (PE), 1.3·10⁸ Ω (PP); τ_1/2=0.25 (PE), 0.30 s (PP); U _ind=190 (PE), 340 V (PP)] in relation to pure PE foils and PP fabric: R _s=3.0·10¹⁴ (PE), 9.8·10¹⁴ Ω (PP); τ_1/2=>600 (PE), >600 s (PP); U _ind=985 (PE), 940 V (PP). Both C₉-D-TAB and C₁₁-D-TAB indicate similar degrees of antistatic ability compared to C₁₀C₁₀-DAB. All C _n -TAB compounds do not show any antistatic effects. It was concluded that addition of the 1,3-dioxolane moiety to the hydrophobic tail of quaternary ammonium salts promotes both antistatic and wetting properties. Additionally, methyl or n-hexyl group incorporation at the C-2 carbon atom in the 1,3-dioxolane ring significantly decreases the surface conductivity.     

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.     

HPLC analysis of quaternary ammonium surfactants with the evaporative light scattering detector

A normal-phase high-pressure liquid chromatography technique has been elaborated for the separation of quaternary ammonium surfactants. The separation was achieved on a bonded polyphenol silica gel column with gradient elution and evaporative light-scattering (ELS) detection. The proposed method has been applied to the quantitative determination of low levels of monoalkyltrimethylammonium and trialkylmethylammonium chlorides in dialkyldimethylammonium chloride.     

Kinetics of precipitation of surfactants. I. Anionic surfactants with calcium and with cationic surfactants

Isoperibol calorimetry was used to measure the rates of precipitation for aqueous solutions of several anionic surfactants with calcium and of anionic and cationic surfactants. A monomer concentration-dependent supersaturation ratio was used to describe the relative rates of precipitation for the surfactant systems studied. This supersaturation ratio allows for the relative rates of precipitation of any surfactant solution to be compared whether micelles are present in solution or not. In general, as the supersaturation ratio increases, the rate of precipitation decreases and the induction time decreases, bot above and below the critical micelle concentration (CMC). The rate of precipitation of sodium dodecyl sulfate (SDS) with dodecyl pyridinium chloride is much slower than the rate of precipitation of the anionic surfactants with calcium for similar supersaturation ratios. The rate of precipitation of SDS with calcium is slightly faster than the rate of precipitation of sodium octyl benzene sulfonate for similar supersaturation ratios. Studies of precipitate crystals, conducted using image analysis, showed that size and shape dependent on the initial supersaturation, the precipitating surfactant molecule, and the extent of aging (until an equilibrium size and shape was reached). Also, differences in the appearance of crystals formed from solutions above and below the CMC were observed. These were most likely due to the difference in supersaturation of these solutions. The crystals formed due to precipitation of SDS with calcium at a concentration above the CMC formed flat trapezoidal, rhombic and hexagonal shapes. These aged into clusters by 1 wk. For a solution that was precipitated at concentrations beginning below the CMC, the crystals began as elongated and rhombic flat plates and aged into trapezoidal, rhombic, and needle-like structures.     

含酯基双子表面活性剂的合成

以长碳链烷基酸与2-二甲氨基乙醇、盐酸、环氧氯丙烷为原料,通过3步反应合成了3种季铵盐阳离子双子表面活性剂。正交试验确定合成目标产物的最佳反应条件为:中间体N-(3-氯-2-羟丙基)-N,N-二甲基月桂酸乙基氯化铵与二甲基脂肪酸乙基叔胺的物质的量比为1∶1.1,100℃下反应12h。3种目标产物结构均通过IR、1HNMR得到证实。     

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.     

十八烷基甲基二羟乙基溴化铵的应用性能研究

研究了合成的阳离子季铵盐表面活性剂十八烷基甲基二羟乙基溴化铵的乳化性能、泡沫性能、增溶性能、再润湿力、柔软性及白度、杀菌性及抗静电性等应用性能,其CMC值为3.18×10-5mol/L,表面张力为22.7 mN/m,Krafft点小于0℃。其增溶性能、杀菌性、再润湿性能优越,同时有较好的乳化性能、发泡力和柔软性能,对织物白度的影响较小。该阳离子表面活性剂可用于配置性能优良的洗涤剂、纺织助剂、杀菌剂。     

Primary aerobic biodegradation of cationic and amphoteric surfactants

The primary aerobic biodegradation of several cationic and amphoteric surfactants has been studied by using the shaking-flask degradation test and orange II spectrophotometric analysis. The results show that cationic and amphoteric surfactants can be readily biodegraded, with their degradation exceeding 94%. The degradation kinetics can be accurately described by the Boltzmann model. The relationship between structure and biodegradability is discussed. The presence of hydrophobic groups has a strong effect on the biodegradability of these surfactants. Biodegradability decreases with increasing chain length. The presence of hydrophilic groups mainly affects the degradation rate of these surfactants, but not their ultimate biodegradeability. Bio-degradability is deterred and degradation is slowed as steric hindrance increases. Degradation rates increase markedly when hydrophilic groups containing an amide bond are pres-ent.     

含酯基双子季铵盐阳离子表面活性剂的合成及性能

分别以氯乙酸辛酯 ,氯乙酸十二醇酯、氯乙酸十四醇酯和四甲基乙二胺反应合成了相应的含酯基双子季铵盐阳离子表面活性剂化合物 (Ⅰ～Ⅲ )。滴体积法测定化合物Ⅰ～Ⅲ的表面张力和cmc。γcmc分别为2 7 3 1、 3 3 73和 3 4 0 1(mN/m) ,cmc分别为 5 0 1× 10 -3 、 3 98× 10 -3 和 3 16× 10 -3 (mol/dm3 )。     

Characterization,surface properties and biological activity of new prepared cationic surfactants

Three cationic surfactants were prepared. A condensation reaction between dimethylaminopropylamine (DMAPA) and benzaldehyde was performed. The produced Schiff base was quaternization with three fatty alkyl bromide with different carbon chain length separately to form the desired cationic surfactants. The chemical structure of synthesized cationic surfactants was confirmed by FTIR, ¹H NMR and mass spectroscopy. It was found that the chemical structure of prepared compounds has an effect on surface properties, where increasing the hydrophobic chain length decrease the values of CMC, Г_max while A_min value was increased. The thermodynamic parameters showed that adsorption and micellization processes are spontaneous. It is clear that the prepared cationic surfactants at first tend to adsorb at surface, then it aggregate to form micelle. The prepared surfactants showed good biological activity against gram positive and negative bacteria and fungi in the following order of II (C12) > I (C10) > III (C16). The serial dilution method was used to evaluate the inhibiting effect of these compounds on the sulfate reducing bacteria growth.     

阳离子淀粉的干法合成研究

使用溶剂循环方法,研究了季铵型阳离子淀粉的干法合成及性能。将原淀粉加入到乙醇氢氧化钠溶液中,加入醚化剂。控制氢氧化钠与醚化剂的摩尔比为2.8∶1,反应温度为60℃,pH值为11～12,在不断搅拌下反应约5h,用硫酸调节pH值为5～6。冷却、过滤,在60℃下干燥,得季铵型阳离子淀粉。该方法生产过程简便,降低了生产成本,减少了对环境的污染,产品性能稳定,质量进一步提高。     

生物可降解型阳离子酯类表面活性剂的研究

以自制的失水甘油基三甲基氯化铵(GTMAC)和硬脂酸为原料,经一步反应合成阳离子单酯表面活性剂(CMESA)。研究了反应介质、反应温度和反应时间对生成物CMESA收率的影响,通过元素分析、官能团分析和红外光谱确证其化学结构,较佳反应条件为:n(GTMAC)∶n(硬脂酸)=1∶1,异丙醇为溶剂,85℃,反应16h,CMESA收率86 8%。接着采用电导法测临界胶团浓度(cmc),拉环法测表面张力(γ),得到20℃下CMESAcmc为0 035mmol/L,在cmc时的γ=44 95mN·m-1。最后研究了在静态时厌氧污泥对CMESA的作用,结果表明:厌氧污泥对CMESA适应性强,其产甲烷气的量不受影响,IC50可能超过1 0g/L。     

季铵型高取代度阳离子淀粉的合成

采用3-氯-2-羟丙基三甲基氯化铵(CTA)为醚化剂,通过干法对淀粉进行改性,合成季铵型高取代度阳离子淀粉。研究了体系中水的质量分数、CTA用量、CTA与NaOH的摩尔比、反应时间、反应温度对产品的取代度和黏度的影响。最佳合成条件为:淀粉100 g,体系中水的质量分数25%,n(CTA)∶n(NaOH)=1∶1.2,反应时间4 h,反应温度70℃。在此条件下制得的阳离子淀粉取代度高达0.598,质量分数0.5%糊液的黏度为0.079Pa.s。干法具有合成工艺简单、反应效率高、环境污染小、成本低等优点。对其市场前景进行了展望。     

黄腐酸阳离子表面活性剂的合成及性能研究

以风化煤中提取的黄腐酸为原料,进行季铵化反应制备阳离子表面活性剂。研究了投料比、反应温度、反应时间等对产品性能的影响。结果表明:黄腐酸阳离子表面活性剂合成的最佳工艺条件为黄腐酸、环氧丙基三甲基氯化铵质量比为2∶1,温度为60℃,反应时间3 h;在此条件下,黄腐酸季铵盐1%水溶液的表面张力为45.129mN/m,溶解百分比为99.3%,发泡性能具有明显改善。     

含杂环的阳离子双子表面活性剂合成研究进展

综述了合成含杂环的阳离子双子表面活性剂的研究工作,着重介绍了含咪唑、吡啶、三嗪、四氢吡咯、六氢哌啶和三唑等杂环的阳离子双子表面活性剂的制备方法。同时简单阐述了其临界胶束浓度、表面张力、胶束聚集数等性能,并展望了含杂环的阳离子双子表面活性剂的发展方向。     

Synthesis and characterization of new cationic surfactants derived from lactic acid

A series of new cationic surfactants was prepared by condensation of lactic acid with N,N-dimethyl propylamine, followed successively by acetylation with acid chloride or ester and by quaternization with dimethylsulfate. Each surfactant and its precursors' structural assignments were based on infrared spectra and ¹H and ¹³C nuclear magnetic resonance spectra. Critical micelle concentrations, contact angles, kinetics of drop spreading, and foam capacities were determined.     

Synthesis and some studies on fluorinated cationic surfactants: surface and biocidal activities

Three fluorinated cationic surfactants were prepared by condensing N-(2-bromoethyl)perfluoroalkylamides with stoichiometric amounts of pyridine, triethanolamine, and triethylamine to produce three quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated to find the relation between the structure of the hydrophilic portion of the compounds and their efficiency as biocides. The properties studied included critical micelle concentration (CMC), effectiveness (II_CMC), surface excess concentration (T_max), and area occupied by a molecule (A_min). Free energies of micellization (ΔG _mic ^o) and adsorption (ΔG _ads ^o) of the surfactants in aqueous solution were calculated. The minimal inhibitory concentrations of the prepared compounds were tested against five strains as representative group of microorganisms.     

季铵型阳离子淀粉絮凝剂的制备及其应用

以玉米淀粉为原料,3-氯-2-羟丙基三甲基氯化铵为阳离子醚化剂,采用预干燥干法制备高取代度季铵型阳离子淀粉絮凝剂.考察了醚化剂用量、氢氧化钠与醚化剂摩尔比、反应温度及反应时间对取代度和反应效率的影响,优化出制备高取代度阳离子淀粉的最佳工艺条件为:醚化剂的加入量为绝干淀粉量的55%,氢氧化钠与醚化剂摩尔比为1.2,反应温度85℃,反应时间4h.将阳离子淀粉对工业中较难处理的高色值糖蜜酒精废液进行絮凝脱色性能测定,结果表明当阳离子淀粉质量浓度为500mg/L、取代度为0.39、废液初始pH值为9.0时,脱色率达53.6%.     

测定环境水中阳离子表面活性剂方法的改进

对酸性蓝分光光度法测定阳离子表面活性剂,如十二烷基二甲基苄基氯化铵进行了改进研究,探讨了分析过程中的影响因素和优化条件,应用统计学原理确定了该方法在实验室内的误差结构、精密度、准确度和线性范围。结果表明:改进后的方法简化了操作步骤,最大吸收波长628 nm,表观摩尔吸光系数为1.56×105L.mol-1.cm-1,标准曲线的相关系数达到0.999,线性范围为0.06 mg.L-1~3.33 mg.L-1,具有良好的精密度和准确度,可用于模拟环境水样中阳离子表面活性剂测定。     

Synthesis and properties of new cationic surfactants: 1-Alkylthiomethyl-3-carbamoylpyridinium chlorides

1-Alkylthiomethyl-3-carbamoylpyridinium and 1-alkylthiomethyl-4-carbamoylpyridinium chlorides were prepared by the reaction of nicotinamide or isonicotinamide with chloromethyl alkyl sulfides. The obtained chlorides were examined for their antimicrobial activities. 4-Carbamoyl-1-dodecylthiomethylpyridinium chloride exhibited strong antimicrobial activity, similar to the activity of benzalkonium chloride. All synthesized chlorides underwent hydrolysis in aqueous solutions at temperatures higher than 70–75°C. In aqueous solution 1-alkylthiomethyl-3-carbamoylpyridinium chlorides reacted with ozone. A new generation of cationic surfactants that were hydrolyzed and ozone-reactive in an aqueous solution was synthesized during this study.