Synthesis of Poly(maleic anhydride-co-taurine) as a Biodegradable Detergent Builder

Biodegradable poly(maleic anhydride-co-taurine) was synthesized by anionic ring-opening copolymerization of maleic anhydride (MA) and taurine. The structures were characterized by elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance (¹H NMR) and mass spectroscopy. The weight-average molecular weight (M _w) of the copolymers was tested using multi-angle laser light scattering instrument. The biodegradability of the copolymers was judged by the shaking table test method. The possibility of the copolymers to be a detergent builder was assessed in terms of the calcium sequestration capacity which was evaluated in accordance with the China National Standard method (GB/T 21884-2008) and dispersive power test. The results showed that the copolymers were biodegradable, and possessed a high calcium sequestration capacity and a good dispersancy, which were environment-friendly detergent builders.     

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。     

The effect of builders on the sorption of sodium myristyl sulphate on cotton and on carbon

Summary In the case of sorption on cotton there was an approximately linear increase in sorption of the detergent with increasing builder concentration. The effectiveness of the builders in this respect increased with increasing anionic charge and decreasing pH of the builder. In the case of sorption on carbon the addition of builder again led to an increase in sorption, but in this case the sorption was an exponential function of the builder concentration. The differences in effectiveness of the various builders in increasing sorption was less clear-cut than in the case of sorption on cotton, and there did not appear to be any consistent correlation between the amount of detergent sorbed and either the pH or the anionic charge of the builder.     

The effect of some inorganic salts in dilute solution on the formation of calcium and magnesium soaps

1. The reactions in mixtures of dilute solutions of builders, pure soaps and hard water have been examined under conditions for optimum foam stability for the soap solution.
2. An attempt has been made to interpret these reactions on the basis of solubility products.
3. For dilute solutions of soaps of pure fatty acids a minimum mole ratio of builder to calcium or magnesium salts is required to prevent the formation of alkaline earth soaps. These mole ratios are different for each soap studied and vary with the particular calcium or magnesium salt and builder combinations.
4. The procedure used by previous investigators of this subject is discussed.

The authors wish to express their appreciation to C. W. Jakob for performing many of the determinations upon which this paper is based.     

Recent developments in the field of inorganic builders

Inorganic builders offer limited choice. Certain sodium aluminum silicates may be used as laundry detergents in combination with sodium triphosphate (STP). Sodium aluminum silicates are available on an industrial scale. They are toxicologically and ecologically safe, and because of their inorganic nature, they do not cause any problems concerning biological degra dability; also, they do not contribute to eutrophication. In our experience binary builder systems have proven useful. These consist of STP and the sodium aluminum silicate, in which there is a balance between the chelating ability of STP and the ion exchanging ability of the sodium aluminum silicate. The technical manufacture of laundry detergents on this basis does not present any fundamental problems and does not require technological change.     

二元Pluronic嵌段共聚物相互作用 I.PPO嵌段长度相近的P94/L92和F108/L92二元混合水溶液

以I2 作为探针 ,用可见光度方法测定不同浓度比例的P94/L92和F10 8/L92二元Pluronic嵌段共聚物水溶液的临界胶束浓度。实验结果表明 ,这些PPO嵌段长度相近的分子在全部浓度比例范围内都发生相互作用 ,生成了混合胶束。由于这些分子的PEO嵌段长度不等 ,随着具有较短PEO嵌段的L92分子加入 ,P94/L92和F10 8/L92混合胶束外壳的EO基团数减少 ,从而使混合胶束水化度降低     

表面活性剂对液体蛋白酶活性的影响

研究了常用表面活性剂LAS、AES、AOS、AEC、AEO9、MEE、TX 10、吐温80、APG等对液体蛋白酶活性的影响。结果表明:阴离子表面活性剂AEC的亲水基电荷强度较弱,与酶的作用最小,在考察条件下几乎不影响液体酶活性。非离子表面活性剂对液体蛋白酶酶活性影响不大;常用非离子表面活性剂AEO9与酶稳定剂共同作用,产生更强的稳定酶活性作用。LAS对酶活性的影响较大,但可以通过与AEO9等比例复配加以改善。     

Biodegradation of some tallow-based surface active agents in river water

Thirty-three anionic and six nonionic detergents have been screened for biodegradability using the river water “Die Away” test. Concentrations of nonionic detergents were best determined by the surface tension method. All fat-derived compounds without mid chain substitution were found to degrade in Schuylkill River water at 20C in less than a week. Presented at the AOCS Meeting in Minneapolis, 1963. E. Utiliz. Res. and Dev. Div., ARS, USDA.     

Solubilization Behavior of Phorbol Esters from Jatropha Oil in Surfactant Micellar Solutions

Phorbol esters (PEs) are important toxic compounds found in Jatropha curcas oil and pressed seeds. These compounds are tumor promoters; thus, their removal prior to further utilization of the pressed seed is important. This work aimed to investigate the solubilization behavior of PEs and Jatropha oil in nonionic [effect of the ethylene oxide number (EON), carbon‐chain length and temperature] and anionic (NaCl addition) surfactant systems. The results reveal that an increase in the EON of the nonionic surfactant molecules, rather than an increase in the carbon‐chain length, enhances PE solubilization. The hydrophile‐lipophile balance (HLB) value was correlated with PE solubilization for nonionic surfactant solutions. The solubilization of PEs decreased slightly with increasing temperature, in contrast to solubilization of the oil. Moreover, the mole fraction of PE solubilized in the micelle decreased with increasing electrolyte concentration in anionic surfactant solutions. The solubilization behavior of PEs in both nonionic and anionic solutions indicates that PE acts more like a polar compound than a nonpolar compound. In addition, the PEs in nonionic micelles are likely located in the palisade region (i.e., between the head group and the first few carbon atoms of the tail), whereas those in anionic micelles are likely near the outer core of the head group. This finding suggests that a nonionic surfactant with a higher EON has a greater potential to extract PE from Jatropha seeds. If an anionic surfactant is combined as co‐surfactant, a small amount of electrolyte should be added to increase PE solubilization.     

Permeation behavior of dextrans by charged ultrafiltration membranes of polyacrylonitrile photografted with ionic monomers

Charged copolymers, polyacrylonitrile, having grafts of quaternized poly(N,N-dimethylaminoethylmethacrylate) and poly(sodium p-styrenesulfonate), were synthesized by photograft-polymerization. The charged ultrafiltration membranes, which had heterogeneous porous structures, were prepared by casting graft polymer solution containing poly(vinyl alcohol) into water. The permeation of nonionic dextran and anionic dextransulfate through the charged membranes was studied by ultrafiltration in aqueous solution. The molecular weight cutoff characteristics of the charged membrances were obtained using dextrans of various molecular sizes. The permeation behavior was discussed in terms of the charge effect of the graft polymers and electrostatic interaction between the polymers and the solute molecules.     

洗涤剂配方中表面活性剂和助剂的研究进展

Surfactants and builders are the two most important ingredients in laundry, household and personal-care cleaning products. They play a key role in washing processes. The development of various surfactants （e.g., anionic, nonionic, cationic, zwitterionic, and silicone surfactants） and builders （inorganic, organic and polymeric builders）used in the detergent compositions are reviewed and their detergency performance and biodegradability are discussed. In the future, the development of the surfactants and builders used in detergent compositions should be based on economic and environmental considerations. The use of the eco-friendly surfactants and builders derived from inexpensive renewable resources （e.g., alkyl polyglucosides and bio-based polyesters） in detergent compositions is the developing trends in detergent industry.     

茶皂素与十二烷基硫酸钠复配体系浮选去除废水中金属离子的研究

研究了非离子生物表面活性剂茶皂素(TS)和阴离子表面活性剂十二烷基硫酸钠(SDS)复配体系的表面活性及无机盐的影响、浮选去除废水中铜离子的处理效果。结果表明,当TS与SDS的混合比例为0.2∶1~0.3∶1时,复配体系的表面张力和临界胶束浓度均降至最低,起泡性和稳泡性均比较稳定;无机盐主要对溶液中的SDS表面活性产生影响,茶皂素性质比较稳定,基本不受影响。采用TS∶SDS=0.25∶1的复配体系进行浮选,溶液中铜离子的去除效率可以达到92%。     

Protease stabilization by highly concentrated anionic surfactant mixtures

We have found that anionic surfactants such as linear alkylbenzene sulfonate (LAS) can solubilize proteases in a substantially nonaqueous environment without loss of proteolytic activity. Moreover, in mixtures of anionic and nonionic surfactants with a moderate amount of water (water less than 30 wt%), controlled levels of LAS and water solubilize proteases; yet, in these concentrated surfactant mixtures, enzymes maintain their activity for extended periods. Experimental design techniques have been used to delineate the relationship between protease stability and the water, pH and anionic surfactant levels in these surfactant concentrates. As the sum of water and LAS levels is increased, maximum enzyme stability is observed, after which stability falls off. At low water and LAS levels (sum of both <20%), protease solubility is low, while at high levels of water and LAS (sum of LAS and water >45%), denaturation predominates. Additionally, we have developed a new and simple method to predict protease stability by which a synthetic peptide is used to measure protease activity directly in the surfactant concentrate. From the application of this new technique to our system and to commercial liquid detergent formulations, it is apparent that water facilitates the loss of activity of proteases in surfactant concentrates by increasing the rate of autolysis.     

Monomer-micelle equilibrium in the diffusion of surfactants in binary systems through collagen films

Three different binary systems (two anionic/nonionic and one anionic/amphoteric) were selected to study the behavior of these mixtures in their diffusion through a collagen film and the formation of micelle aggregates in such systems. The inhibition observed in the surfactant diffusion of anionic/nonionic and anionic/amphoteric binary mixtures through a collagen film, in comparison with that of single surfactants, has been related to the behavior of these binary systems in the micellization process. The surfactant flux in these systems is mainly determined by the monomeric species. The modification of the equilibrium monomers-micelle aggregates shown by these surfactant binary systems could be also associated with the reduction of the irritancy power for such binary systems.     

Electrophoretic properties in aqueous detergent systems

Electrophoretic mobilities and zeta potentials were developed for triolein, Nujol, and glass particles in aqueous detergent solutions. Zeta potentials in deionized water were: -79, -69, and -62 mv, respectively, for triolein, Nujol, and glass. Electrolyte builders and anionic surfactants markedly increase triolein and Nujol particle mobilities and negative zeta potentials; this effect probably contributes to their detersive action. Nonionic surfactants lower mobility of triolein and glass, and thus show slight cationic character. Significant inflection points are found for nonionic detergents near cmc. A cationic detergent produced high positive charge and zeta potentials with triolein and glass. Data for surfactant-builder combinations show mobilities are primarily determined by the electrolyte. It was concluded that electrokinetic effects are important for dispersion and emulsification, but are not necessary and sufficient conditions for removing oily soil from glass.     

The shear degradation of high-molecular-weight flocculant solutions

Solutions of polyacrylamide and poly(acrylamide-co-sodium acrylate) flocculants with varying molecular weights were shear degraded under a range of mixing conditions. The viscosity and flocculant activity of the solutions generally decreased with time to limiting values dependent on the mixing intensity. The activity of 10 and 20% anionic flocculants displayed quite different trends from those for nonionic flocculants of equivalent molecular weight, with less apparent degradation due to mixing, particularly at low dosages. However, viscosity measurements on sheared solutions diluted with a salt buffer suggest that nonionic and anionic flocculants with similar initial molecular weights were degraded to the same degree. Multiangle laser light-scattering measurements were used to confirm that the shearing process resulted in a reduction in molecular weight which was independent of anionic character. The apparent shear resistance of anionic flocculation mechanisms for the nonionic and anionic flocculants. © 1996 John Wiley & Sons, Inc.     

Kinetic studies of the polymerization of nylon-6 block copolymers

The kinetics of the activated anionic polymerization of caprolactam to nylon-6 and its copolymers has been studied. Nylon-6 block copolymer and nylon-6 were prepared at various initial reaction temperatures (140°C to 165°C) by anionic polymerization in an adiabatic dewar flask. Different concentrations of poly(ethylene oxide) (PEO) in 4,4′-diphenyl methane diisocyanate (MDI)-capped PEO and 1 mole percent MDI, in a caprolactam solution, were used as the activators with the catalyst, the sodium salt of caprolactam. The kinetics of the reaction were analyzed from an adiabatic temperature rise. A new method was applied to determine the rate parameters. The activation energy, E_a, of nylon-6 and nylon-6 block copolymers were found to be 22 kcal/mole. The collision frequency factor, A_o, steadily decreased and the autocatalytic constant, B_o, decreased to a constant value of 16 with the introduction of PEO. However, it was found that the order of reaction, n, was almost a constant value at the second order for all experiments.     

Micelle formation in mixtures of nonionic and anionic detergents

This paper describes the effect of a homologous series of polyoxyethylene n-dodecanols on the critical micelle concentration (CMC) of sodium n-dodecyl alcohol sulfate as a function of composition of the mixtures and temperature. The CMC of the nonionic component of the mixed micelles is about one-hundredth of that of the anionic. Only a gradual increase in the CMC values of the mixed micelles above the values of the nonionic components was observed in the composition range of 0–90 mole % anionic detergent. This is followed by an abrupt transition to the high CMC values of the anionic component. The gradual increase of the CMC values in the range below 90 mole % anionic detergent of n-dodecanol+ 4 EO exceeds that of the higher homologs containing 7, 23 and 30 ethylene oxide units. It is postulated that the degree of ionic repulsion of the ionic component in mixed micelles is markedly decreased as the proportion of nonionic component reaches a threshold range of 10 mole %. This effect is more pronounced with large ethylene oxide coils operating at the periphery of the micelle core than with short ethylene oxide coils. Thermodynamic data have been included.     

代磷助剂的质量鉴别

概述了代磷助剂的作用机理，对市场上一些常见代磷助剂的质量鉴别问题进行了归类总结，大致分为沸石类代磷助剂和硅系代磷助剂。从晶体学的角度对市场上几个常见品种进行了质量分析。重点介绍了沸石类代磷助剂中4A沸石和硅系代磷助剂中层状结晶二硅酸钠的质量鉴别问题。在对代磷助剂物相鉴定、化学组成、作用机理、热失重、软化水能力、钙离子脱除速率、pH值和游离碱含量等8个方面的质量鉴别问题发表了看法。     

Purification and characterization of an extracellular lipase from Penicillium candidum

Penicillium candidum produces and secretes a single extracellular lipase with a monomer molecular weight of 29 kDa. However, this enzyme forms dimers and higher molecular weight aggregates under nondenaturing conditions. The lipase from P. candidum was purified 37-fold using Octyl-Sepharose CL-4B and DEAE-Sephadex columns. The optimal assay conditions for lipase activity were 35°C and pH 9. The lipase was stable in the pH range of 5–6 with a pl of 5.5, but rapid loss of the enzyme activity was observed above 25°C. Tributyrin was found to be the best substrate for the P. candidum lipase, among those tested. Metal ions such as Fe²⁺ and Cu²⁺ inhibited enzymatic activity and only Ca²⁺ was able to slightly enhance lipase activity. Ionic detergents inhibited the activity of the enzyme, whereas nonionic detergents stimulated lipase activity.