Soap-based detergent formulations: XIII. Formulations with alpha-olefin sulfonates as lime soap dispersants

Heavy duty household type detergents were formulated from tallow soap-AOS(α-olefin sulfonate)-builder combinations. Various commercial AOS samples were evaluated. These were derived either from closely fractionated α-olefins such as C₁₄, C₁₆, and C₁₈ or from samples representing broader mol wt ranges such as C₁₄−C₁₆ and C₁₆−C₁₈. The builders incorporated into these combinations were a sodium silicate (Na₂O∶SiO₂=1∶1.6), sodium tripolyphosphate, sodium citrate, sodium carbonate, and trisodium nitrilotriacetate. Detergency evaluations of 0.2% solutions in 300 ppm hard water (as CaCO₃) were determined with three commercial soiled cloths and by a multiwash test in which clean cloth was repeatedly soiled and washed. The relative proportions of soap, AOS, and builder were varied to obtain maximum detergency, and comparisons were made to other soap-LSDA (lime soap dispersing agents)-builder combinations as well as to a commercial high phosphate detergent used as a control. Detergency performance of soap-AOS combinations ranked just below that of the commercial high phosphate detergent control and below that of soap formulations containing sodium methyl α-sulfotallowate. Presented at the AOCS meeting, Philadelphia, September 1974.     

无机盐对表面活性剂去污力影响的研究

用去污实验机测定了直链烷基苯磺酸钠(LAS)、脂肪醇聚氧乙烯醚硫酸钠、α-烯基磺酸钠、脂肪酸甲酯磺酸钠等阴离子表面活性剂的去污力,考察了无机盐对去污力的影响。结果表明,三聚磷酸钠使这几种表面活性剂的去污值增加了29.11%~121.26%,磷酸三钠使LAS的去污值增加了128.25%;三聚磷酸钠、δ-层状结晶二硅酸钠、4A沸石等软水剂增强去污力的效果最好,碳酸钠和硅酸钠等碱性助剂次之;硫酸钠、氯化钠、磷酸二氢钠和十水四硼酸二钠不适合用作洗涤剂的助洗剂。     

Novel Route of Producing Zeolite A Resin for Quality‐Improved Detergents

Most of the commercial manufacturers of soap and detergents are still using sodium tripolyphosphate and trisodium phosphate as the builder material which results into eutrophication through laundry. Phosphate mainly originates from detergents and affects the aquatic ecosystem severely. This may increase decomposer organisms that require oxygen, which can deplete the amount of oxygen dissolved in the water. To remedy this, many leading detergent manufacturers currently use zeolite A as the builder material which has proven to be a better substitute for phosphatic additives. Zeolite A is a three‐dimensional crystalline aluminosilicate resin having a high exchange capacity towards ions that cause water hardness. In spite of this tremendous potential, the high cost of zeolite A has limited its effective use in detergents. The specific objectives of this study were to synthesize zeolite A resin in a more economically viable fashion using waste material, a composite ash, which is the post‐combustion residue of rice husk blended with coal, and to formulate an eco‐friendly phosphate‐free detergent powder using the same. The studies also focused on evaluating its detergency action by analyzing moisture content, foam height, surface tension, tea/coffee stain test along, and alcohol solubility. The results show that the synthesized detergent has comparable detergency to two known commercial brands of detergent. This economical synthesis combined with the exceptional parameters of zeolite A resin, such as fine particle size, high exchange capacity, inert nature, and anti‐redeposition properties, makes this detergent an elite and cost‐effective product.     

Algerian montmorillonite as a builder in a detergent powder

Algerian montmorillonite treated with sodium chloride was used as a substitute for the builders sodium tripolyphosphate (STPP) and sodium sulfate in a detergent powder. The following performance parameters of the substituted composition powder were examined: pH, foaming, cleaning, sequestering, and ion exchange capacities. The latter factors remained the most important ones for effective detergency. Despite anticipated improvement in hard water ion removal, constant detergency results were observed with the treated montmorillonite-containing powder. This level of efficacy does not meet the cost-effectiveness of a standard detergent powder containing STPP.     

丙烯酸-马来酸酐共聚物在碱性无磷洗涤剂中的应用研究

去掉磷酸钠后 ,洗涤剂的去污力有所降低 ,而其他碱性助剂如硅酸钠、碳酸钠、 4A沸石等的大量加入又会使洗涤剂pH值升高 ,灰分沉积严重。研究了丙烯酸 马来酸酐共聚物 (AA -MA)在碱性无磷洗涤剂中的应用 ,证明丙烯酸 马来酸酐共聚物具有很好的螯合性能和分散性能 ,应用在洗涤剂中能缓冲pH值 ,有效防止灰分沉积     

Soap-based detergent formulations: VI. Alkylaryl sulfonamide derivatives as lime soap dispersing agents

Alkylbenzenes, such as industrial detergent alkylates, as well as pure 1-phenylalkanes whose side chain lengths varied C₈−C₁₂, were converted into the corresponding alkylbenzenensulfonyl chlorides with chlorosulfonic acid. Surface active sulfonamides were obtained from the reaction of the sulfonyl chlorides with various low mol wt aminosulfonic acids, such as N-methyltaurine, or with aminoalkyl esters of sulfuric acid, such as 2-aminoethyl hydrogen sulfate. The hydrolytic stability of the resulting surface active sulfonamide derivatives was investigated. As expected, the sulfonates were quite resistant to acid or alkaline hydrolysis, while the sulfates were more susceptible to hydrolysis. Hydrolytic stability of the sulfonamides was compared with that of the analogous fatty acid amide sulfactants. All of the compounds were excellent lime soap dispersing agents giving Borhetty-Bergman values of 4–10. The compounds were evaluated for detergency either alone or formulated either with tallow soap or with tallow soap and sodium silicate (Na₂O/SiO₂ ratio of 1∶1.6) The derivatives of the pure hydrocarbons which gave the best overall detergency were those of 1-phenyldecane and 1-phenyldodecane, whereas those of 1-phenyloctane exhibited poor detergency. This ranking was observed when the compounds were tested alone as well as when formulated. The sulfonamide derivatives of the detergent alkylate type of alkylbenzenes exhibited excellent detergency characteristics and showed substantial potentiation of detergency when mixed with soap or with a soap-sodium silicate blend. The detergency performance of some of these formulated detergents was equal to that of a commercial household detergent used as a control.     

利用橘皮精油制备“绿色”洗涤膏

橘皮精油的主要成分D-柠檬烯具有较强的去污能力、天然的芳香味及抑菌功效。本论文以去污力为考察指标,通过单因素实验研究了橘皮精油,十二烷基磺酸钠及三乙醇胺的配比,制备出一种去污力较强的“绿色”环保型洗涤膏。其最佳配比为：D-柠檬烯：5．0％,十二烷基磺酸钠：13．6％,乙醇：4．4％,三乙醇胺：29．0％,氯化钠：2．2％,蒸馏水：45．8％。并对含橘皮精油的洗涤膏、市售洗涤剂的洗涤去污效粜进行了比较研究。测试结果表明,所制备的含橘皮精油洗涤膏与市售洗涤剂沈涤效果相当（去污比值约为1）,且在洗涤树脂类污垢优于市售洗涤剂（去污比值为1．2）。     

马来酐—丙烯酸共聚物钠盐的合成及助洗剂性能研究

以水为溶剂合成了马来酐－丙烯酸共聚物钠盐（简称内共聚物钠盐）对其螯合性能、分散性能及复配成洗衣粉的去污效果进行了研究。结果表明：马丙共聚物钠盐具有良好的螯合能力和分散能力,与４Ａ沸石复配后得到的洗衣粉去污指数高于以ＳＴＰＰ为助剂的标准粉。     

钴掺杂NaP分子筛合成及其吸附Pb(II)性能

以硅酸钠和偏铝酸钠为原料,通过水热合成法制备钴掺杂NaP分子筛,通过X射线衍射光谱(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附等表征手段对样品的晶相、形貌和孔结构进行表征分析,并对其Pb(II)吸附性能进行评价。结果表明:与未掺杂钴的NaP分子筛相比,掺杂量为n(Al₂O₃)∶n(Co(NO₃)₂)=8∶1的Co-NaP分子筛的比表面积增大了约5倍(从26.767 m²/g增大到162.490 m²/g);其孔容约增大了约2.5倍(从0.029 cm³/g增大到0.104 cm³/g)。吸附时间为120 min,吸附温度为25 ℃,Pb(II)初始浓度为100 mg/L时,Co-NaP分子筛对Pb(II)的去除率可达98.8%,以乙二胺四乙酸二钠为再生助剂,在30 ℃下再生30 min,可使吸附后时Co-NaP分子筛完全再生,再生后的吸附剂经过3次吸附-再生循环后,Pb(II)去除率仍可达97%。     

Water hardness control by detergent builders

Commercial detergent additives to control water hardness are of three main types, sequestrant, precipitant or ion-exchange builders. These builders lower the free hardness ion (Ca⁺², Mg⁺²) concentration in a wash system by different mechanisms. An electrometric experimental method was used to evaluate the relative water hardness control performances of different builder-types under conditions closely simulating those of detergent’s end-use. Experimental data for the following builders are presented: EDTA, NTA, STPP, PAA, CMOS, Na-Citrate, Na₂CO₃ and type A zeolite. It is shown that the relative rankings of the various builders in water hardness control differ significantly with differences in use level concentration of the builder (0.005–0.100 gm per 100 ml). The application of the method to the selection of optimum molecular weight range of the newly emerging class of organic polymeric detergent builders like sodium polyacrylates (Na-PAA) (M_w=2000−220,000) also is discussed.     

Modification of Sodium Lignosulfonate and Evaluation of its Potential Use as Detergent Builders

Sodium lignosulfonate (LS) was modified by polypropylene glycol diglycidyl ether (PPGDE) for the preparation of a surfactant (GLS), and firstly used for detergent builder. The effects of PPGDE content on the reaction and the properties of GLS were investigated. The structure of GLS was studied by Fourier transform infrared spectra (FTIR), ultraviolet spectrophotometer (UV), and gel permeation chromatography (GPC). The surface tension, critical micelle concentration (CMC), emulsifying ability, lime soap dispersing power (LSDP), and detergency were characterized. The results showed that GLS had higher surface activity and better emulsifying ability, LSDP, and detergency than that of LS. After decolorized by H₂O₂, the whiteness retention value of decolorized LS on white cloth reached 91.9%, while that of decolorized GLS increased up to 99.4%. These results suggested that the decolorized GLS may provide a new perspective for detergent builders.     

4A沸石在洗涤剂中的应用及前景

4 A沸石作为优良的替代STPP(三聚磷酸钠)的洗涤助剂得到广泛应用,其一般颗粒大小为1~4μm,占90%左右,密度为2.07g.cm-3。4A沸石对水中Ca2+、Mg2+等离子的交换,可去除98%钙离子、至少50%的镁离子,使水得到软化;对非离子表面活性剂的吸附,沸石是NTA(次氨基三乙酸盐)和碳酸钠的3倍,是STPP和硫酸钠的5倍;与其他电解质一样与表面活性剂有协同效应;4A沸石与STPP混合使用,其去污力至少可达到单一用STPP效果;并兼有防止不溶性污垢再沉积,安全、无污染等性能。并阐述了4A沸石在洗涤剂中的应用前景。     

Clinoptilolites of western anatolia as detergent builders

The use of clinoptilolites of Western Anatolia in detergents as phosphate substitutes was investigated. The cations present in the clinoptilolite samples were first exchanged with sodium ions. The washing characteristics of detergent mixtures containing surfactants, clinoptilolite, sodium carbonate and sodium sulphate were analysed. The stains of coffee, tea and tomato paste were tested. The washing tests were repeated for different surfactants, i.e. linear alkyl benzene sulphonate, sodium alkyl sulphate and alcohol ethoxylate and for different co-builders, i.e. sodium carbonate and EDTA. In addition, the effects of detergent dose and detergent formulation on washing were investigated. Other factors affecting the degree of soil removal such as shaking time, temperature and water hardness were also studied. The contribution of clinoptilolite to the washability was compared with zeolite A, zeolite X and sodium tripolyphosphate. Increasing the shaking time and temperature improves the degree of cleaning. LAS was the most effective surfactant for use with clinoptilolite. The washing performance of the detergent mixtures used in the present work was found to be comparable with that of commercial detergents at low washing temperatures.     

洗涤剂助剂的发展

介绍了三聚磷酸钠在洗涤剂中的应用和富营养化,洗涤剂助剂从三聚磷酸钠到4A沸石以及最新的层状硅酸钠的发展过程,讨论了洗涤剂配方的发展趋势和对环境的影响。     

洗涤剂助剂的演变——从磷酸盐到沸石到硅酸盐

在洗涤剂组分中，三聚磷酸钠、A型沸石和层状结晶二硅酸盐SKS－6已是被广泛接受的助剂。新型洗涤剂的开发促进了新型洗涤助剂的应用。针对这些助剂进行了产品的市场趋势、生态效应和产品应用等方面的比较。     

Methyl Ester Sulfonate: A High-Performance Surfactant Capable of Reducing Builders Dosage in Detergents

The detergency performance of α-sulfo fatty-methyl ester sulfonate (α-MES) under different water hardness conditions was compared against the dominant workhorse in Home Care products, linear alkylbenzene sulfonate (LAS). Results demonstrate that α-MES has a higher soil removal index and its detergency performance is not drastically affected by water hardness, compared to that of LAS. The addition of α-MES to LAS also shows an improved cleaning performance and better water hardness resistance, due to the structural characteristics of α-MES, which allow the molecules to be relatively insensitive toward polyvalent ions such as Ca²⁺ and Mg²⁺. The washing performance of α-MES, α-MES/LAS, and LAS with different builders at various dosages was studied, and the results indicated that the dosage of builders in the detergent product could be reduced up to 33% with the application of α-MES, while the detergency is not sacrificed.     

粉状洗涤剂组分对霉脂肪酶活性的影响

研究了粉状洗涤剂用活性物如LAS、AES、AOS、MES、肥皂、AEO9、TX10,特种阳离子表面活性剂,常规洗涤助剂以及特种助剂如过碳酸盐、偏硅酸钠、聚合物、酶制剂等组分对所开发的青霉脂肪酶活性的影响。结果表明,阴离子表面活性剂对酶的活性有较大影响,影响程度为：LAS＞AOS＞肥皂＞AES＞AES;AEO9和TX10对酶活的影响较小,将基与LAS复配可显著降低LAS对酶活性的影响：阳离子表面活性剂在低浓度时对酶有激活作用,浓度增加影响增大;绝大多数洗涤助剂在配方用量范围内对酶活影响不大,只有碱性蛋白酶在用量多时有较大影响。     

利用橘皮精油制备“绿色”洗涤剂及其性能测试

橘皮精油中的主要成分D-柠檬烯具有较强的去污能力、抑菌功效以及天然芳香味。本研究以橘皮精油为有效成分,研制了一种绿色环保型洗衣液。通过单因素试验研究了洗衣液配方中AES、AEO-7的初步配比及质量分数,并采用正交试验优化了洗衣液中各组分的配比:D-柠檬烯15%,AEO-7 14%,AES 8%,乙醇8%,柠檬酸钠2%,KCl 0.25%,余量为蒸馏水。将含D-柠檬烯的洗衣液与市售LB洗衣液进行了去污效果、发泡力、pH值对比测试。结果表明,所制备的洗衣液洗涤效果优于市售LB洗衣液(去污比值大于1)。     

Effect of water hardness ions on the solution properties of an anionic surfactant

The solution characteristics of the system linear alkylbenzene sulfonate (LAS)/Ca⁺⁺/builder were studied using a dynamic surface tension technique. The results showed that the rate of CA⁺⁺/LAS interaction is slower than the CA⁺⁺ binding rate of zeolite A. Consequently, zeolite A is effective in preventing precipitation of LAS by calcium ions. The data obtained from the study of Ca⁺⁺ binding detergent builders on solubilization of Ca(LAS)₂ showed that zeolite A was effective but the rate of solubilization was much slower than that for STPP. Incorporation of a small amount of phosphate with zeolite A in a detergent significantly increases the rate of solubilizing of Ca(LAS)₂.     

基于碱融活化的高岭土水热法制备干燥剂NaP分子筛

研究了含有石英成分的高岭土的活化方法,并采用水热法制备了干燥剂NaP分子筛.研究了碳酸钠对高岭土的活化效果、不同水热反应条件对NaP分子筛吸水率的影响,得到该高岭土的活化条件为:m(高岭土):m(碳酸钠)=1:1、在750℃下煅烧2 h;制备NaP分子筛的优化条件为:n(SiO2)/n(Al2O3)=4.0、n(Na2 O)/n(SiO2)=1.4、n(H2O)/n(Na2 O)=40、93℃下晶化8 h.