CN1814722A - Liquid detergent viscosity-increasing agent - Google Patents

Liquid detergent viscosity-increasing agent Download PDF

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CN1814722A
CN1814722A CN 200610032978 CN200610032978A CN1814722A CN 1814722 A CN1814722 A CN 1814722A CN 200610032978 CN200610032978 CN 200610032978 CN 200610032978 A CN200610032978 A CN 200610032978A CN 1814722 A CN1814722 A CN 1814722A
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acid
thickener
component
polyoxyethylene
added
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CN 200610032978
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CN100451094C (en )
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张宏格
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张宏格
周据江
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Abstract

This invention relates to a bodying agent used in lotion and its preparation method and application, which is mixed by polyether and crylic acid in the mol ratio: 1:0.5-1:6 to be added with inhibitor and acid catalyst under 90-180deg.C and mixed for 0.5-6h to be esterified, then the temperature is reduced to 20-100deg.C and added with an initiator and mixed for 0.5-5h under 50-150deg.C to carry out polymerization of free radical and add additives to mix them evenly, which has fine bodying ability and increases the viscosity of a product when using it in a lotion of low density to reduce cost of products.

Description

一种液体洗涤剂粘度增高剂 A liquid detergent viscosity increases agent

技术领域 FIELD

本发明涉及一种增稠剂及其制备方法,更具体地讲,本发明涉及一种用于增加液体洗涤剂粘度的增稠剂及其制备方法。 The present invention relates to a method of preparing a thickening agent and, more particularly, the present invention relates to a method for preparing thickeners and increase the viscosity of the liquid detergent.

背景技术 Background technique

液体洗涤剂的外观是质量控制的一个非常重要的因素,为了让消费者使用方便,还要满足外观要求,液体洗涤剂应有一定的粘稠度。 The appearance of liquid detergent is a very important factor in quality control, in order to allow consumers easy to use, but also to meet appearance requirements, liquid detergent should be a certain consistency. 液体洗涤剂活性物较高时,比较容易调制出理想的粘度,活性物低时调制出理想的粘度则比较困难,一般低活性物液洗剂可采用硬脂酸聚乙二醇酯638,配合较大量的食盐NaCl作增稠剂,但因NaCl用量大,其粘度不稳定,易使溶液体系泛白,其去污效果不佳,638用量大时,则会产生啫哩状凝胶,不适用于配制流动性好的液洗剂。 At higher liquid detergent actives, relatively easy to prepare a desired to prepare a low viscosity, the viscosity of the active substance over the more difficult, generally less active lotion polyethylene glycol 638 stearate can be employed, with larger amount of table salt NaCl as thickener, but the large amount of NaCl, the viscosity unstable, the solution was whitened system, decontamination effect thereof is poor, the amount of 638 large, it will produce gel like gel not good flowability suitable lotion formulation. 另外,从配制液洗剂的角度来看,希望增稠剂除了能提供良好的增稠力外,还能提供出色的洗涤能力及耐硬水能力,具有良好的协同能力,并减少洗涤剂的滑腻感。 Further, from the viewpoint of lotion formulation, in addition to providing desirable thickening good thickening power, but also can provide excellent washing power and resistance to hard water, it has good synergy, and reduce creamy detergents sense.

中国专利申请CN97180436.2公开了一种特别适合于清洁硬表面如玻璃的、用洗涤剂浸渍的物品,其中,洗涤剂包括固体研磨颗粒、保护层形成组分、有机溶剂、干燥加速剂、增粘多糖和表面活性剂。 Chinese patent application CN97180436.2 discloses a particularly suitable for cleaning hard surfaces such as glass, impregnated with detergent article, wherein the detergent comprises solid abrasive particles, the protective layer-forming component, an organic solvent, drying accelerating agents, glycosaminoglycan and a surfactant. 该专利申请中采用的增稠剂为多糖类物质。 Thickeners used in this patent application for the polysaccharide.

中国专利CN99127711.2公开了一种洗涤剂组合物,其包括:a)一种疏水改性的丙烯酸共聚物增稠剂;b)一种多元醇烷氧基酯增稠剂;和c)至少一种表面活性剂,该表面活性剂选自阴离子表面活性剂、非离子表面活性剂、两性表面活性剂、甜菜碱表面活性剂和其混合物;而且,以组合物的总重量计,该洗涤剂组合物中含有大于约1%的多元醇烷氧基酯增稠剂。 Chinese Patent CN99127711.2 discloses a detergent composition comprising: a) one hydrophobically modified acrylic copolymer thickener; b) a polyol alkoxy ester thickener; and c) at least a surfactant, the surfactant is selected from anionic surfactants, nonionic surfactants, amphoteric surfactants, betaine surfactants and mixtures thereof; and, to the total weight of the composition, the detergent compositions contain greater than about 1% of the polyol alkoxy ester thickener. 该专利的洗涤剂组合物中采用丙烯酸共聚物和多元醇烷氧基酯两种增稠剂。 The patent detergent compositions employed in the acrylic copolymer and a polyol alkoxy ester thickener two kinds.

中国专利CN96192210.9公开了一种浓缩液体凝胶器皿洗涤剂组合物,其包括:(a)约5%至约30wt%碱金属洗涤剂助洗剂盐;(b)约8至约50wt%碱源;(c)约0至约5wt%水分性或水溶性有机表面活性剂;(d)约0.1至约2wt%的分子量约1,000,000至约4,000,000的已中和的交联亲水性聚羧酸酯增稠剂;(e)约0.1至约2wt%所述中和的交联的聚羧酸酯增稠剂的氢键键合剂;(f)约0至约15wt%的分子量约1,000至约100,000的未交联聚丙烯酸酯;(g)余量的水,其中组合物的基本上所有固体组分都溶于水相中,并且组合物中所有水基本上都与所述已中和的交联聚羧酸酯增稠剂结合。 Chinese Patent CN96192210.9 discloses a liquid gel detergent composition concentrate vessel, comprising: (a) from about 5% to about 30wt% of alkali metal detergent builder salt; (b) from about 8 to about 50wt% alkali source; (c) from about 0 to about 5wt% of water or a water-soluble organic surfactant; (d) from about 0.1 to about 2wt% of the molecular weight and cross-neutralized from about 1,000,000 to about 4,000,000 linked hydrophilic polycarboxylates ester thickener; (e) from about 0.1 to about polycarboxylate thickeners 2wt% of the neutralized hydrogen bonding crosslinking agent; (f) from about 0 to about 15wt% of a molecular weight of from about 1,000 to about 100,000 non-crosslinked polyacrylates; substantially all solid components are dissolved in the aqueous phase (g) balance water, wherein the composition, and substantially all of the water in the composition are neutralized and the crosslinked polycarboxylate thickener binding. 该专利的洗涤剂组合物中采用交联聚羧酸酯作为增稠剂。 The patent detergent compositions employed as cross-linked polycarboxylate thickener.

中国专利CN91111575.7公开了一种协合型丙烯酸系增稠剂及其制备方法,其包括甲基丙烯酸、衣康酸、丙烯酸低烷基酯、丙烯酸高级烷基酯、烯酸胺和反应型表面活性剂。 Chinese Patent CN91111575.7 discloses a synergistic type acrylic thickening agent and a preparation method thereof include methacrylic acid, itaconic acid, acrylic acid lower alkyl esters, higher alkyl esters of acrylic acid, and an amine reactive acid Surfactant. 该专利的增稠剂为水性体系增稠剂,可用于乳胶漆、瓷砖胶、浮雕漆、压敏胶、织物涂层、地毯背胶、洗涤剂、化妆品以及油井钻探中。 Thickeners for aqueous systems of this patent thickeners, can be used for paint, tile adhesive, relief paint, adhesive, textile coatings, carpet backing, detergents, cosmetics and oil drilling.

中国专利CN94100176.8公开了一种增稠的液体漂白剂组合物,该组合物采用交联聚丙烯酸酯类聚合物作为增稠组分,其用量约为组合物重量的0.2-2.0%,其可使组合物在25℃时的粘度至少达到约20厘泊。 Chinese Patent CN94100176.8 discloses a liquid bleach composition thickened composition using a crosslinked polyacrylate polymer as a thickening component in an amount from about 0.2 to 2.0% by weight of the composition, which composition viscosity can be reached at 25 ℃ at least about 20 centipoise. 这类增稠组分的另一作用在于当组合物被喷射到待清洁表面时可有效地减小漂白剂味,以及保持组合物的稳定性。 Another function of such thickening components is that when the composition is sprayed onto a surface to be cleaned can be effectively reduced bleach odor, and to maintain stability of the composition. 但这类增稠组分本身也需要稳定剂,以便在次氯酸盐的存在下有效地稳定交联的聚丙烯酸酯。 However, such a thickening stabilizer components itself also needs to effectively stabilize crosslinked polyacrylate in the presence of hypochlorite.

中国专利申请CN02149677.3公开了一种丙烯酸酯类增稠剂的制备方法,采用单体在引发剂、乳化剂下合成,合成过程在超临界二氧化碳中进行,反应温度31.2~150℃,反应压力7.5~150MPa。 Chinese patent application CN02149677.3 discloses a method for preparing an acrylic-based thickener, the use of monomers, synthetic processes conducted in supercritical carbon dioxide under the emulsifier initiator, the reaction temperature is 31.2 ~ 150 ℃, reaction pressure 7.5 ~ 150MPa. 该申请的制备方法不需要溶剂回收设备,最终产物为固体粉末,易分离纯化,但设备复杂,需在高压下进行反应。 The method of preparation of this application does not require solvent recovery equipment, the final product as a solid powder, easily isolated and purified, but the complexity of the device, the need for a reaction under high pressure.

目前业界尚无一种不使用溶剂的、易于操作的制备增稠剂的简便方法。 At present there is no industry without using any solvent, a simple method of preparing thickener easy to operate.

发明内容 SUMMARY

本发明的目的在于提供一种新型的用于增加液体洗涤剂粘度的增稠剂及其制备方法。 Object of the present invention to provide a method for preparing thickeners and increase the viscosity of liquid detergent for a new type.

一方面,本发明提供了一种包含亲水性聚丙烯酸酯活性成分的增稠剂,该聚丙烯酸酯活性成分为丙烯酸和/或甲基丙烯酸与一种或一种以上的亲水性聚醚发生酯化反应所得到的酯化产物的聚合物,其中,聚醚可选自于壬基酚聚氧乙烯醚、聚乙二醇、蓖麻油聚氧乙烯醚、辛基酚聚氧乙烯醚、苯乙烯基苯基聚氧乙烯醚、苯乙烯苯基聚氧乙烯醚、聚氧丙烯基醚、脂肪醇聚氧乙烯醚如平平加O、吐温类非离子表面活性剂、环氧乙烷共聚物和环氧丙烷共聚物。 In one aspect, the present invention provides a thickener comprising a hydrophilic polyacrylate active ingredient, the active ingredient is a polyacrylate acrylic acid and / or methacrylic acid with one or more hydrophilic polyether polymeric esterification product is an esterification reaction of the resultant, wherein the polyether may be selected from polyoxyethylene nonyl phenyl ether, polyethylene glycol, polyoxyethylene castor oil, polyoxyethylene octylphenol ethers, polyoxyethylene styryl phenyl ether, polyoxyethylene styrenic phenyl ether, polyoxypropylene ether, polyoxyethylene fatty alcohol ethers such as peregal O, Tween nonionic surfactant, ethylene oxide copolymer and propylene oxide copolymers thereof. 优选的聚醚为壬基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚。 The preferred polyether is a polyoxyethylene nonylphenol ether, polyoxyethylene fatty alcohol ether. 更优选为脂肪醇聚氧乙烯醚,最优选为平平加O等脂肪醇聚氧乙烯醚,因为平平加O等脂肪醇聚氧乙烯醚对环境友好。 More preferably polyoxyethylene fatty alcohol ethers, most preferably O, Peregal fatty alcohol polyoxyethylene ethers, alcohols and the like as Peregal O polyoxyethylene environmentally friendly.

本发明中,上述的增稠剂还可以包含一种或一种以上的添加组分,该添加组分可选自于其它增稠组分、粘度调节组分和/或洗涤剂组分,而且该添加组分占上述聚丙烯酸酯活性成分总重的5-150%,优选占上述聚丙烯酸酯活性成分总重的30-120%,更优选占上述聚丙烯酸酯活性成分总重的50-90%。 The present invention, the thickener may also comprise one or more additional components, the additive component may be selected from other thickening component, viscosity adjusting component and / or detergent components, and the above-described additive component accounted polyacrylate 5-150% of the total weight of the active ingredient, preferably from 30-120% above the total weight of polyacrylate active ingredient, more preferably from polyacrylates weight of the total active ingredient 50-90 %.

其中,上述的添加组分可以为一种或一种以上的其它增稠组分,该其它增稠组分可以选自于椰油酸二乙醇酰胺、椰油酸单乙醇酰胺、十二烷基二甲基甜菜碱和十四烷基二甲基甜菜碱;上述的添加组分也可以为一种或一种以上的粘度调节组分,该粘度调节组分可选自于水、乙醇、甘油和季戊四醇;上述的添加组分还可以为一种或一种以上的洗涤剂组分,该洗涤剂组分可以为十二烷基苯磺酸和/或脂肪醇聚氧乙烯醚。 Wherein the additional component may be one or more than one additional thickening component, the additional thickening component may be selected from coconut diethanolamide, coconut acid monoethanolamide, lauryl dimethyl betaine and myristyl dimethyl betaine; and the additive components may be adjusted as a component of one or more viscosity or the viscosity-adjusting component selected from water, ethanol, glycerol and pentaerythritol; additional components described above may also be one or more than one detergent ingredients, the detergent component may be dodecylbenzenesulfonic acid and / or fatty alcohol polyoxyethylene ether. 当然,本发明的增稠剂可以同时含有以上各种添加组分。 Of course, the present invention may contain a thickening agent simultaneously added over a variety of components. 其中,优选的添加组分为椰油酸二乙醇酰胺、十二烷基二甲基甜菜碱、水,因为椰油酸二乙醇酰胺、十二烷基二甲基甜菜碱对液体洗涤剂同样具有增稠作用,并且价格便宜易得,水可以调节产物自身状态,又可以降低成本。 Among them, preferred additional component is coconut diethanolamide, lauryl dimethyl betaine, water, as coconut diethanolamide, lauryl dimethyl betaine having the same liquid detergent thickening action, readily available and inexpensive, water may adjust its state product, but also reduce costs.

本发明的增稠剂中,聚丙烯酸酯活性成分是通过丙烯酸和/或甲基丙烯酸与亲水性聚醚在酸催化剂的作用下,按1∶0.5~1∶6的摩尔比反应制得的,而且本发明的增稠剂可以不必分离出未反应的反应物。 Thickeners of the present invention, the active ingredient is a polyacrylate acrylic acid under the action of an acid catalyst, the reaction molar ratio of 0.5 to 1/6 and hydrophilic polyether obtained by acrylic acid and / or methyl and the thickener of the present invention may be not necessary to isolate the unreacted reactants.

优选的聚醚与丙烯酸和/或甲基丙烯酸的摩尔比为1∶1~1∶2,这是因为当丙烯酸和/或甲基丙烯酸用量少则增稠效果不显著,而丙烯酸和/或甲基丙烯酸用量大虽则增稠效果好,但产物的自身粘度很大,搅拌较困难。 Preferred polyether with acrylic acid and / or methacrylic acid molar ratio of 1/1 to 1:2, this is because when the acrylic and / or methacrylic acid used in an amount at least no significant thickening effect, and acrylic acid and / or though a large amount of methacrylic acid is good thickening effect, but their great viscosity of the product, stirring difficult.

制备本发明增稠剂的聚醚的分子量可以控制在100-1500之间,若聚醚的分子量小于100,则增稠能力太小;若聚醚的分子量大于1500,则粘度太大,产物易固化;优选的聚醚的分子量在200-1000之间,更优选的聚醚的分子量在300-800之间,最优选的聚醚的分子量在600左右。 The molecular weight of the polyether thickeners of the present invention may be prepared between 100-1500 controlled, if the molecular weight of the polyether is less than 100, the thickening capacity is too small; if polyether molecular weight greater than 1500, the viscosity is too large, the product is easy to curing; preferred polyether molecular weight between 200-1000, more preferably between 300-800 molecular weight polyethers, polyethers most preferably about 600 molecular weight.

另一方面,本发明还提供了一种制备上述增稠剂的方法,该方法包括如下的步骤:(a)将一种或一种以上的聚醚与丙烯酸和/或甲基丙烯酸按1∶0.5~1∶6的摩尔比进行混合;(b)在上述混合物中加入阻聚剂和酸催化剂,并将其温度保持在80~180℃下,搅拌0.5~6h,进行酯化反应;(c)将上述酯化反应后所得到的混合物降温至20~100℃,然后加入引发剂溶液,并在50~150℃下搅拌0.5~5h,进行自由基聚合反应。 Another aspect, the present invention also provides a process for preparing the above-described thickener, the method comprising the steps of: (a) one or more than one polyether with acrylic and / or methacrylic acid by 1: 0.5 to 1/6 molar ratio were mixed in; (b) addition of a polymerization inhibitor and an acid catalyst in the mixture, and keeping the temperature at 80 ~ 180 ℃, stirred for 0.5 ~ 6H, esterification reaction; (c ) the above-described esterification reaction mixture obtained was cooled to 20 ~ 100 ℃, initiator solution was then added, and stirred at 50 ~ 150 ℃ 0.5 ~ 5h, radical polymerization reaction.

上述的方法还可以包括加入其它添加组分的步骤,例如可以添加一种或一种以上的其它增稠组分、粘度调节组分和/或洗涤剂组分。 The above method may further comprise the step of adding other ingredients added, for example, addition of one or more other thickening component, viscosity adjusting component and / or detergent components.

本发明方法所采用的酸催化剂可以为选自于如下一组物质中的一种或一种以上的酸:硫酸、硝酸、氨基磺酸、磷酸、马来酸、烷基苯磺酸、氯磺酸、对甲苯磺酸、衣康酸、葡萄酸、草酸和柠檬酸。 The method of the present invention, an acid catalyst may be employed as one selected from the group consisting of one or more acids: sulfuric, nitric, sulfamic, phosphoric, maleic acid, sulfonic acid, chlorosulfonic acid, p-toluenesulfonic acid, itaconic acid, gluconic acid, oxalic acid and citric acid. 所用酸催化剂的量可以占聚醚和丙烯酸总重的0.2-3.0%。 The amount of the acid catalyst may comprise 0.2 to 3.0% of the total weight of polyether and acrylic. 优选的酸催化剂为对甲苯磺酸,因为对甲苯磺酸对产物色泽影响较小。 The preferred acid catalyst is p-toluenesulfonic acid, p-toluenesulfonic acid as little effect on product color.

本发明方法所采用的阻聚剂可以为对苯二酚和/或对羟基苯甲醚,所用阻聚剂的量可以占聚醚和丙烯酸总重的0.0-1.0%;优选的阻聚剂为对羟基苯甲醚,因为对羟基苯甲醚对产物色泽影响较小。 The method of the present invention, the polymerization inhibitor may be employed hydroquinone and / or p-hydroxyanisole, with the amount of the polymerization inhibitor may constitute 0.0-1.0% of the total weight of polyether and acrylic acid; preferred polymerization inhibitor is hydroxy anisole, p-hydroxyanisole as little influence on the product color.

本发明方法所采用的引发剂可以为如下一组物质中一种或一种以上物质的水溶液:过硫酸钾、过硫酸钠和过硫酸铵。 The method of the present invention, the initiator may be employed as an aqueous solution of a group consisting of one or more of: potassium persulfate, sodium persulfate and ammonium persulfate.

本发明增稠剂的优点和效果可通过下述方法检测验证:因反应过程存在酯化反应,故其酸值会逐渐降低,而且亦存在聚合反应,故产物的自身粘度会不断增大,故可通过测定产物的酸值及自身粘度来判断反应程度。 Thickeners advantages and effects of the present invention may be detected by the following authentication methods: by the presence of the esterification reaction process, so its acid value will gradually decrease, but also the presence of the polymerization reaction, so the viscosity of the product itself will continue to increase, so the extent of reaction can be determined by measuring the acid value of the product itself and viscosity. 其最终增稠性能可通过配制液体洗洁精来测定。 Its ultimate thickening properties can be determined by formulating liquid detergent. 一般可选用如下配方测试:直链烷基苯磺酸:4%,本发明产物:2%,6501(1∶1型):2%,NaCl:0.3%,使用NaOH调PH=7~8,加水至100%。 Tests generally use the following formulation: linear alkyl benzene sulphonic acid: 4%, the product of the present invention: 2%, 6501 (1:1 type): 2%, NaCl: 0.3%, adjusted with NaOH PH = 7 ~ 8, water to 100%. 测试条件:25℃,使用NDJ-1型旋转粘度计的3#转子,转速12r/min。 Test Conditions: 25 ℃, using spindle # 3 NDJ-1 type viscometer, rotational speed 12r / min. 该测试结果一般为1500~3000mPa.s。 The test result is generally 1500 ~ 3000mPa.s. 经测试,本发明增稠剂具有优良的增稠能力,用于配制低浓度液体洗涤剂可显著增大产品的粘稠度,有效降低产品成本,同时具有良好的螯合力,能够络合水中的钙、镁、铜、铁等金属离子,增进洗涤效果,并且具有良好的洗涤、去油污协同能力,提高其他表面活性剂洗涤作用,并可减少液体洗涤剂的滑腻感。 After testing, the thickener of the present invention has excellent thickening ability for the preparation of low concentration in the liquid detergent may increase significantly the viscosity of the product, reduce product cost, while having good chelating power, capable of complexing the water calcium, magnesium, copper, iron and other metal ions, enhance the washing effect, and having a good washing, degreasing interoperability, other detersive surfactants to improve the effect, reduced greasy feel and liquid detergents. 另外,本发明还提供了一种简便、易于操作的增稠剂制备方法,不使用溶剂,使得反应易于控制,并且不会因溶剂而污染环境。 Further, the present invention provides a simple, easy to operate thickener preparation, no solvent is used, such a reaction is easy to control, and does not pollute the environment due to the solvent.

本发明增稠剂既具有良好的增稠能力,又可减少液体洗涤剂的滑腻感的增稠剂。 The thickeners useful herein both good thickening power, and reduces the greasy feel liquid detergent thickeners.

具体实施方式 Detailed ways

实施例1先把壬基酚聚氧乙烯醚Tx-10(其分子量约为660)300g加入1000ml的四口玻璃烧瓶中,接上回流冷凝管,聚四氟搅拌棒,然后加入丙烯酸60g、稀硫酸3g、对羟基苯甲醚0.1g,搅拌均匀,使用导热油浴加热,加热至瓶内温度110℃~120℃,保温1~2h,降温至50~80℃,加入过硫酸钠水溶液:5g,调整温度为80~100℃,聚合反应开始后保持温度90~110℃反应2~3h,冷却至80~90℃,再加入130g十二烷基二甲基甜菜碱,搅拌均匀得目的产物,为淡黄色透明粘稠状液体。 Example 1 first nonylphenol ether Tx-10 (molecular weight of about 660) 300g 1000ml four-necked glass flask, a reflux condenser connected, PTFE stir bar, then add acrylic 60g, dilute 3g sulfuric acid, p-hydroxyanisole 0.1g, stir, using heat transfer oil heating bath, heated to an inner temperature of 110 ℃ ~ 120 ℃, heat 1 ~ 2h, cooled to 50 ~ 80 ℃, was added aqueous sodium persulfate solution: 5g the temperature was adjusted to 80 ~ 100 ℃, after the initiation of the polymerization reaction to maintain a reaction temperature of 90 ~ 110 ℃ 2 ~ 3h, cooled to 80 ~ 90 ℃, was added 130g dodecyl dimethyl betaine, stir to give the desired product, as a pale yellow transparent viscous liquid.

实施例2先把脂肪醇聚氧乙烯醚AEO-7(其分子量约为494):310g加入1000ml的四口玻璃烧瓶中,接上回流冷凝管,聚四氟搅拌棒,然后加入丙烯酸80g、对苯二酚0.2g、对甲苯磺酸2g,搅拌均匀,使用导热油浴加热,加热至瓶内温度120℃~130℃,保温1~2h,降温至60~70℃,加入过硫酸铵水溶液3g,调整温度为80~100℃,聚合反应开始后保持温度90~110℃反应2~3h,冷却至80~90℃,再加入100g椰油酸二乙醇酰胺6501和50g水,搅拌均匀得目的产物,为淡黄色微浑粘稠状液体。 Example 2 polyoxyethylene fatty first AEO-7 (molecular weight of about 494): 310g 1000ml four in a glass flask, connected to a reflux condenser, PTFE stir bar, then add acrylic 80g, for hydroquinone 0.2g, p-toluenesulfonic acid 2g, stir, using heat transfer oil heating bath, heated to an inner temperature of 120 ℃ ~ 130 ℃, heat 1 ~ 2h, cooled to 60 ~ 70 ℃, aqueous ammonium persulfate solution was added 3g the temperature was adjusted to 80 ~ 100 ℃, after the initiation of the polymerization reaction to maintain a reaction temperature of 90 ~ 110 ℃ 2 ~ 3h, cooled to 80 ~ 90 ℃, was added 100g coconut diethanolamide 6501 and 50g of water, stir to give the desired product as a pale yellow viscous liquid slightly muddy.

实施例3在实施例2中,AEO-7换成AEO-9(其分子量约为582),其余条件不变,得到淡黄色浑浊粘稠状液体。 Example 3 In Example 2, AEO-7 replaced AEO-9 (molecular weight of about 582), with other conditions unchanged, to give a pale yellow turbid viscous liquid.

实施例4将发明的增稠剂在液体洗洁精中应用,使用实施例3的所制得的增稠剂用于配制液体洗洁精,其配方为:实施例3产物0.8%、十二烷基苯磺酸LAS 1.0%、脂肪醇聚氧乙烯醚磺酸钠AES 1.0%、椰油酸二乙醇酰胺6501 1.5%、NaCl 0.5%、NaOH适量(调PH值为7~8)、水加至100%。 Thickener Example 4 The application of the invention in a liquid detergent, a thickening agent prepared in Example 3 for liquid detergent formulations, the formula is: 0.8% Example 3 The product, twelve alkylbenzene sulfonate LAS 1.0%, polyoxyethylene fatty alcohol ether sulfonates AES 1.0%, coconut acid diethanolamide 6501 1.5%, NaCl 0.5%, NaOH amount (adjust PH value of 7 to 8), plus water to 100%. 所得的复配物为微黄色透明液体,使用NDJ-1型旋转粘度计温度为25℃,3#转子,转速为12转/秒测试,其粘度为1400mPa.s。 The compound was obtained as a yellowish transparent liquid, NDJ-1 using the temperature of the rotary type viscometer was 25 ℃, 3 # rotor speed of 12 revolutions / second test, having a viscosity of 1400mPa.s. 使用常用的增稠剂638代替上述实施例3产物,则粘度测试数据为:100mPa.s。 Using common thickeners 638 in place of the product from Example 3, the viscosity of test data: 100mPa.s.

实施例5其它条件同实施例2,只是用甲基丙烯酸代替丙烯酸。 Other conditions of Example 5 with Example 2, except that instead of acrylic acid with methacrylic acid.

Claims (10)

  1. 1.一种用于液体洗涤剂的增稠剂,其特征在于,所述的增稠剂包含一种亲水性的聚丙烯酸酯活性成分,该聚丙烯酸酯活性成分为丙烯酸和/或甲基丙烯酸与一种或一种以上的亲水性聚醚发生酯化反应所得酯化产物的聚合物,其中,所述的一种或一种以上的聚醚选自于壬基酚聚氧乙烯醚、聚乙二醇、蓖麻油聚氧乙烯醚、辛基酚聚氧乙烯醚、苯乙烯基苯基聚氧乙烯醚、苯乙烯苯基聚氧乙烯醚、聚氧丙烯基醚、脂肪醇聚氧乙烯醚、吐温类非离子表面活性剂、环氧乙烷共聚物和环氧丙烷共聚物。 A thickener for liquid detergent, characterized in that the thickener comprises one hydrophilic polyacrylates active ingredient, the active ingredient is a polyacrylate acrylic acid and / or methacrylic the resulting esterification reaction product of a polymer of acrylic acid esterification occurs with one or more hydrophilic polyether, wherein the one or more polyethers selected from nonylphenol ether , polyethylene glycol, polyoxyethylene castor oil, polyoxyethylene octylphenol ether, polyoxyethylene styryl phenyl ether, polyoxyethylene styrenic phenyl ether, polyoxypropylene ether, polyoxyethylene fatty alcohol vinyl ethers, non-ionic Tween-based surfactant, a copolymer of ethylene oxide and propylene oxide copolymer.
  2. 2.如权利要求1所述的增稠剂,其特征在于,所述的增稠剂还包含一种或一种以上的添加组分,该添加组分为其它增稠组分、粘度调节组分和/或洗涤剂组分,而且该添加组分占聚丙烯酸酯活性成分总重的5-150%。 2. A thickener according to claim 1, wherein said thickener further comprises one or more than one additional component, the additional component added thickening component, a viscosity modifier group points and / or detergent components, and the addition polyacrylate component comprises 5-150% of the total weight of the active ingredient.
  3. 3.如权利要求2所述的增稠剂,其特征在于,所述的添加组分为一种或一种以上的其它增稠组分,该其它增稠组分选自于椰油酸二乙醇酰胺、椰油酸单乙醇酰胺、十二烷基二甲基甜菜碱和十四烷基二甲基甜菜碱。 3. A thickener according to claim 2, wherein said additive component is one or more additional thickening component, the additional thickening component is selected from the coconut acid diethanolamide, coconut acid monoethanolamide, lauryl dimethyl betaine and myristyl dimethyl betaine.
  4. 4.如权利要求2所述的增稠剂,其特征在于,所述的添加组分为一种或一种以上的粘度调节组分,该粘度调节组分选自于水、乙醇、甘油和季戊四醇。 4. The thickener according to claim 2, wherein the group is added into the one or more viscosity adjusting component, the viscosity adjusting component selected from water, ethanol, glycerol, and pentaerythritol.
  5. 5.如权利要求2所述的增稠剂,其特征在于,所述的添加组分为一种或一种以上的洗涤剂组分,所述的洗涤剂组分选自于十二烷基苯磺酸和脂肪醇聚氧乙烯醚。 5. The thickener according to claim 2, wherein said additive component of one or more detergent ingredients, the detergent component is selected from dodecyl benzenesulfonic acid and fatty alcohol polyoxyethylene ether.
  6. 6.如权利要求1-5之一所述的增稠剂,其特征在于,所述的聚丙烯酸酯活性成分为所述的丙烯酸和/或甲基丙烯酸与所述的聚醚在酸催化剂的作用下,按1∶0.5~1∶6的摩尔比反应制得的,而且所述的增稠剂中包含未反应的反应物。 6. The thickener according to any one of claims 1-5, wherein said active ingredient is a polyacrylate acrylic acid and / or methacrylic acid with the acid catalyst in the polyether under the action, 0.5 to 1/6 by mole ratio prepared by the reaction, and the thickener contains the unreacted reactants.
  7. 7.如权利要求6所述的增稠剂,其特征在于,所述的聚醚的分子量在100-1500之间,优选在200-1000之间,更优选在300-800之间。 7. The thickener according to claim 6, wherein the molecular weight of the polyether is between 100-1500, preferably between 200-1000, more preferably between 300-800.
  8. 8.一种制备如权利要求1-7之一所述的增稠剂的方法,该方法包括如下的步骤:(a)将一种或一种以上的聚醚与丙烯酸和/或甲基丙烯酸按1∶0.5~1∶6的摩尔比进行混合;(b)在上述混合物中加入阻聚剂和酸催化剂,并将其温度保持在80~180℃下,搅拌0.5~6h,进行酯化反应;(c)将上述酯化反应后所得到的混合物降温至20~100℃,然后加入引发剂溶液,并在50~150℃下搅拌0.5~5h,进行自由基聚合反应。 A method of preparing thickener as claimed in any one of the claims 1-7, the method comprising the steps of: (a) one or more than one polyether with acrylic and / or methacrylic acid 0.5 to 1/6 molar ratio were mixed in; (b) addition of a polymerization inhibitor and an acid catalyst in the mixture, and keeping the temperature at 80 ~ 180 ℃, stirred for 0.5 ~ 6h, an esterification reaction ; (c) esterification of the mixture obtained above was cooled to 20 ~ 100 ℃, initiator solution was then added, and stirred at 50 ~ 150 ℃ 0.5 ~ 5h, radical polymerization reaction.
  9. 9.如权利要求8所述的方法,其特征在于,该方法还包括加入其它添加组分的步骤,而且所述的酸催化剂为选自于如下一组物质中的一种或一种以上:硫酸、硝酸、氨基磺酸、磷酸、马来酸、烷基苯磺酸、氯磺酸、对甲苯磺酸、衣康酸、葡萄酸、草酸和柠檬酸。 9. The method according to claim 8, characterized in that the method further comprises the step of adding an acid catalyst is added to the other components, and according to one of the following selected from a group consisting of one or more: sulfuric, nitric, sulfamic, phosphoric, maleic acid, benzene sulfonic acid, chlorosulfonic acid, p-toluenesulfonic acid, itaconic acid, gluconic acid, oxalic acid and citric acid.
  10. 10.如权利要求8或9所述的方法,其特征在于,所述的阻聚剂为对苯二酚和/或对羟基苯甲醚;所述的引发剂为如下一组物质中一种或一种以上物质的水溶液:过硫酸钾、过硫酸钠和过硫酸铵。 10. The method of claim 8 or claim 9, wherein said polymerization inhibitor is hydroquinone and / or p-hydroxyanisole; as the initiator is a group consisting of one or an aqueous solution of one or more of: potassium persulfate, sodium persulfate and ammonium persulfate.
CN 200610032978 2006-01-16 2006-01-16 Liquid detergent viscosity-increasing agent CN100451094C (en)

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Publication number Priority date Publication date Assignee Title
CN101591411B (en) 2008-05-30 2011-11-30 清远市灵捷制造化工有限公司 Acrylic acid copolymer and its preparation method and use containing macromer
CN101781613B (en) 2009-01-19 2012-03-21 浙江传化股份有限公司 Acid soaping agent
CN102027075B (en) 2008-05-14 2012-11-21 可泰克斯有限合伙公司 Use of an acrylic dispersant/associative thickener pairing in an alkyd paint for enhancing the gloss retention
CN104082290A (en) * 2014-06-09 2014-10-08 长兴德源环保助剂有限公司 A thickening synergistic emulsifier and a preparing method thereof
CN105154245A (en) * 2015-08-05 2015-12-16 张宏格 Comb-shaped polyether composition, manufacturing method thereof, and application of comb-shaped polyether composition to liquid detergent
CN105555817A (en) * 2013-07-03 2016-05-04 巴斯夫欧洲公司 Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing
CN105623931A (en) * 2016-02-27 2016-06-01 云南涵昶鑫科技有限公司 Cleaning agent for chemical industry laboratory experiment instruments and preparation method thereof
CN106590984A (en) * 2016-11-29 2017-04-26 威莱(广州)日用品有限公司 Concentrated tableware detergent

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CN1140668C (en) 2000-01-25 2004-03-03 沈阳化工研究院 Composite thickening agent for printing with reactive dye
CN1231565C (en) 2003-09-10 2005-12-14 清远市灵捷制造化工有限公司 Thickening agent for liquid lotion and its preparation method and application

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102027075B (en) 2008-05-14 2012-11-21 可泰克斯有限合伙公司 Use of an acrylic dispersant/associative thickener pairing in an alkyd paint for enhancing the gloss retention
CN101591411B (en) 2008-05-30 2011-11-30 清远市灵捷制造化工有限公司 Acrylic acid copolymer and its preparation method and use containing macromer
CN101781613B (en) 2009-01-19 2012-03-21 浙江传化股份有限公司 Acid soaping agent
CN105555817A (en) * 2013-07-03 2016-05-04 巴斯夫欧洲公司 Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing
CN104082290A (en) * 2014-06-09 2014-10-08 长兴德源环保助剂有限公司 A thickening synergistic emulsifier and a preparing method thereof
CN104082290B (en) * 2014-06-09 2016-03-16 长兴德源环保助剂有限公司 A synergistic thickening emulsifier and a preparation method
CN105154245A (en) * 2015-08-05 2015-12-16 张宏格 Comb-shaped polyether composition, manufacturing method thereof, and application of comb-shaped polyether composition to liquid detergent
CN105623931A (en) * 2016-02-27 2016-06-01 云南涵昶鑫科技有限公司 Cleaning agent for chemical industry laboratory experiment instruments and preparation method thereof
CN106590984A (en) * 2016-11-29 2017-04-26 威莱(广州)日用品有限公司 Concentrated tableware detergent
CN106590984B (en) * 2016-11-29 2018-03-09 威莱(广州)日用品有限公司 A concentrate dishwashing detergent

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