CN116096703A - 表面活性剂和洗涤剂组合物 - Google Patents
表面活性剂和洗涤剂组合物 Download PDFInfo
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- CN116096703A CN116096703A CN202180052918.9A CN202180052918A CN116096703A CN 116096703 A CN116096703 A CN 116096703A CN 202180052918 A CN202180052918 A CN 202180052918A CN 116096703 A CN116096703 A CN 116096703A
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- Prior art keywords
- secondary alkyl
- detergent composition
- surfactant
- alkyl sulfonate
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
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Abstract
本发明涉及仲烷基磺酸盐表面活性剂,其中大于50重量%的仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐;本发明还涉及包含该仲烷基磺酸盐表面活性剂的洗涤剂组合物;本发明还涉及一种处理纺织品的方法,优选地家用方法。
Description
技术领域
本发明涉及洗涤剂组合物。更特别地,包含在直链烷烃链中具有平均17至18个碳原子的仲烷基磺酸盐(SAS)表面活性剂的洗涤剂组合物。
背景技术
表面活性剂包含具有与其连接的水增溶基团的油溶性烃链。洗涤剂组合物包含表面活性剂以从基材上除去污垢。例如,洗衣洗涤剂含有表面活性剂以在洗涤过程中从衣物上除去污垢。洗涤剂组合物中使用的一种这样的表面活性剂是仲烷基磺酸盐(SAS)。仲烷基磺酸盐表面活性剂包含主要为长度C14、C15和C16的烷基链的混合物。
希望的是含有仲烷基磺酸盐的家用洗涤剂制剂具有增强的性能。存在的问题是找到提供改进性能的表面活性剂体系。
令人惊讶的是,该问题可以通过使用C17-C18仲烷基磺酸盐(SAS)来解决,其提供增强的性能。
发明内容
在第一方面,本发明涉及仲烷基磺酸盐(SAS)表面活性剂;
其中大于50重量%,优选大于60重量%,更优选大于70重量%的仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐。
优选地至少75重量%,更优选至少80重量%,甚至更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的仲烷基磺酸盐的烷基链是C17和/或C18仲烷基磺酸盐。
优选地,C17和/或C18仲烷基磺酸盐在直链烷烃链中具有该碳原子。
优选地,仲烷基磺酸盐的烷基链获自可再生来源,优选获自甘油三酯。
本发明还涉及洗涤剂组合物,其包含:
a)1至40重量%,优选2至30重量%,最优选3至15重量%的本发明第一方面的仲烷基磺酸盐表面活性剂,其中大于50重量%,优选大于60重量%,更优选大于70重量%的仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐;和
b)1-60重量%,优选2-40重量%,更优选4-30重量%,最优选5-15重量%的选自其它阴离子表面活性剂和非离子表面活性剂的其它表面活性剂。
优选地至少75重量%,更优选至少80重量%,甚至更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的仲烷基磺酸盐的烷基链是C17和/或C18仲烷基磺酸盐。
优选地,C17和/或C18仲烷基磺酸盐在直链烷烃链中具有该碳原子。
优选地,仲烷基磺酸盐的烷基链获自可再生来源,优选获自甘油三酯。
优选地,对于洗涤剂组合物,如果存在非离子表面活性剂,则非离子表面活性剂选自饱和的和单不饱和的脂族醇乙氧基化物,优选地选自具有平均5至30个乙氧基化物的C12至C20直链伯醇乙氧基化物,更优选地具有平均5至25个乙氧基化物的C16至C18。
优选地,对于洗涤剂组合物,如果存在阴离子表面活性剂,则阴离子表面活性剂选自:鼠李糖脂、C12至C18烷基醚羧酸盐;C16-C18甘油单酯的柠檬酸酯(citrem)、C16-C18甘油单酯的酒石酸酯(tatem)和C16-C18甘油单酯的二乙酰酒石酸酯(datem);C12至C18烷基醚硫酸盐;和具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐;及其混合物;最优选地,阴离子表面活性剂选自:鼠李糖脂、C16至C18烷基醚羧酸盐;C16-C18甘油单酯的柠檬酸酯(citrem)、C16-C18甘油单酯的酒石酸酯(tatem);C12-C18烷基醚硫酸盐和C16-C18甘油单酯的二乙酰酒石酸酯(datem)及磺酸盐,例如直链烷基苯磺酸盐;及其混合物。
优选地,阴离子表面活性剂的总量与非离子表面活性剂的总量的重量比范围为4:1-1:4,优选2:1-1:2,最优选1.5:1-1:1.5。
优选地,组合物包含0.5至15重量%,更优选0.75至15重量%,甚至更优选1至12重量%,最优选1.5至10重量%的选自抗再沉积聚合物、去污聚合物、烷氧基化聚羧酸酯及其混合物的清洁增强剂。
优选地,抗再沉积聚合物是烷氧基化聚胺;和/或去污聚合物是聚酯去污聚合物。
优选地,洗涤剂组合物是洗衣洗涤剂组合物,更优选液体洗衣洗涤剂组合物或液体单位剂量洗涤剂组合物。
优选地,组合物包含一种或多种选自以下的酶:脂肪酶、蛋白酶、α-淀粉酶、纤维素酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶,或其混合物,更优选脂肪酶、蛋白酶、α-淀粉酶、纤维素酶及其混合物,其中每种酶在本发明的组合物中的含量为0.0001重量%至0.1重量%。
在第二方面,本发明提供了一种处理纺织品的方法,优选家用方法,该方法包括以下步骤:用0.5至20g/L的如权利要求5至14中任一项所述的洗涤剂组合物,优选液体洗衣洗涤剂组合物的水溶液处理纺织品,优选地其中水溶液含有0.1至1.0g/L的(a)和(b)的表面活性剂;和任选地干燥纺织品;优选地其中所述家用方法使用家用电器在家中进行,其中所述方法在280至335K的洗涤水温度下进行。
优选地,在该方法中,水溶液含有0.1至1.0g/L的(a)和(b)的表面活性剂。
该方法,优选使用家用电器在家中进行的家用方法,优选地在280至335K的洗涤水温度下进行。纺织品优选地用由于与人皮肤接触导致的皮脂玷污。
具体实施方式
除非另有说明,否则本文所用的不定冠词“一(a)”或“一个(an)”及其相应的定冠词“该”是指至少一个,或者一个或多个。
所有酶水平均指纯蛋白质。
重量%涉及基于组合物总重量以成分重量计的量。对于带电的表面活性剂(例如阴离子表面活性剂),重量%基于表面活性剂的质子化形式计算。
制剂可以是任何形式,例如液体、固体、粉末、液体单位剂量。优选地,组合物是液体洗涤剂组合物或液体单位剂量洗涤剂组合物。
在20℃下溶解于去矿物质水中时,制剂优选具有3至10,更优选4至9,更优选5至7.5,最优选7的pH。
优选地,阴离子表面活性剂的总量与非离子表面活性剂的总量的重量比范围为4:1-1:4,优选2:1-1:2,最优选1.5:1-1:1.5。
仲烷基磺酸盐(SAS)
仲烷基磺酸盐(SAS)表面活性剂如下详述。
洗涤剂组合物包含1至40重量%,优选2至30重量%,最优选3至15重量%的仲烷基磺酸盐表面活性剂,其中大于50重量%,优选大于60重量%,更优选大于70重量%的仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐。
优选地,C17和/或C18仲烷基磺酸盐在直链烷烃链中具有该碳原子。
优选地,至少75重量%,更优选至少80重量%,甚至更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的仲烷基磺酸盐的烷基链是C17和/或C18仲烷基磺酸盐。
优选地,仲烷基磺酸盐的烷基链获自可再生来源,优选获自甘油三酯。
仲烷基磺酸盐(SAS)是用于家用洗涤剂清洁产品中的表面活性剂。仲烷基磺酸盐(SAS)描述于HERA文件Secondary Alkane Sulfonate第1版,2005年4月1日和由H.W.Stache编辑的Anionic Surfactants Organic Chemistry(Surfactant Science Series vol 56,Marcel Dekker 1996)及其中的参考文献中。
SAS可以通过在水的存在下使链烷烃与二氧化硫和氧反应同时用紫外光照射来获得,如H.W.Stache编辑的Anionic Surfactants Organic Chemistry(Surfactant ScienceSeries vol 56,Marcel Dekker1996)中所述。由磺化氧化获得的仲烷基磺酸盐(SAS)是仲烷基磺酸钠盐的密切相关的异构体和同系物的混合物。伯烷基磺酸盐的含量<1%。在UV光和水存在下的磺化氧化产生约90%单磺酸和10%二磺酸的混合物。
SAS的合适供应商是Clariant和Weylchem。
链烷烃原料优选通过催化加氢处理从甘油三酯或其脂肪酸获得,如Douvartzides等人的Energies 2019,12,809Green Diesel:Biomass Feedstocks,ProductionTechnologies,Catalytic Research,Fuel Properties and Performance inCompression Ignition Internal Combustion Engines中所描述。
加氢处理涉及氢化和脱羧、脱羰或加氢脱氧反应,优选脱羧。用于这样的反应的合适的催化剂和条件在Hoassain M.K等人ACS Omega,3,7046-7060(2018)中讨论,特别是表4,和其中的参考文献。这样的原料可以从UOP Honeywell、Neste Oil和Haldor获得。
甘油三酯优选从可再生来源获得。
可再生来源是其中材料通过活物种的自然生态循环,优选通过植物、藻类、真菌、酵母或细菌,更优选植物、藻类或酵母产生的来源。脂肪酸可以通过甘油三酯的水解获得。
优选地,甘油三酯主要含有C18脂肪酸。
优选的油的植物来源是粗制棕榈油、油菜籽、向日葵、玉米、大豆、棉籽、橄榄油和树。来自树的油称为妥尔油。最优选地,棕榈油和菜籽油是来源。
藻油由Saad M.G.等人在Energies 2019,12,1920,Algal Biofuels:CurrentStatus and Key Challenges中讨论。Energy Environ.Sci.,2019,12,2717中描述了使用酵母从生物质产生甘油三酯的方法。
MasriM.A.等人提供一种用于经济地产生无废物的微生物油(其可以替代基于植物的等同物)的可持续的高性能方法。
可以使用不可食用的植物油,且优选选自麻疯树(Jatropha curcas)、红厚壳(Calophyllum inophyllum,)、香苹婆(Sterculia feotida)、印度紫荆木(Madhucaindica)(宽叶紫荆木(mahua))、无毛水黄皮(Pongamia glabra)(koroch籽)、亚麻籽、水黄皮(Pongamia pinnata)(卡兰贾树(karanja))、橡胶树(Hevea brasiliensis)(橡胶籽)、印度楝树(Azadirachta indica)(苦楝(neem))、亚麻荠(Camelina sativa)、Lesquerellafendleri、烟草(Nicotiana tabacum)(tobacco)、洋麻(Deccan hemp)、蓖麻(Ricinuscommunis L.)(castor)、油蜡树(Simmondsia chinensis)(荷荷巴(Jojoba))、芝麻菜(Eruca sativa.L.)、海檬树(Cerbera odollam)(海芒果(Sea mango))、芫荽(Coriandrumsativum L.)、大果巴豆(Croton megalocarpus)、Pilu、海甘蓝(Crambe)、丁香(syringa)、久树(Scheleichera triguga)(kusum)、乌臼(Stillingia)、婆罗树(Shorea robusta)(婆罗双树(sal))、毛诃子(Terminalia belerica roxb)、萼距花(Cuphea)、山茶花(Camellia)、黄兰花(Champaca)、夸斯苦木(Simarouba glauca)、印度藤黄(Garciniaindica)、米糠、Hingan(橡形木(balanites))、沙枣(Desert date)、刺菜蓟(Cardoon)、叙利亚马利筋(Asclepias syriaca)(乳草(Milkweed))、小葵子(Guizotia abyssinica)、埃塞俄比亚芥(Radish Ethiopian mustard)、金山葵(Syagrus)、桐树(Tung)、毛叶山桐子(Idesia polycarpa var.vestita)、藻类、蓟罂粟(Argemone mexicana L.)(墨西哥罂粟(Mexican prickly poppy))、罗氏假黄杨(Putranjiva roxburghii)(幸运豆树)、无患子(Sapindus mukorossi)(Soapnut)、楝树(M.azedarach)(syringe)、黄花夹竹桃(Thevettiaperuviana)(黄夹竹桃)、黄酒杯花(Copaiba)、白乳木(Milk bush)、月桂(Laurel)、香二翅豆(Cumaru)、大苦油楝(Andiroba)、Piqui、甘蓝型油菜(B.napus)、花椒(Zanthoxylumbungeanum)的果实和种子。
链烷烃原料优选含有大于50重量%,更优选大于80重量%,最优选大于95重量%的直链链烷烃。优选地,链烷烃是饱和链烷烃并且含有小于2重量%的不饱和链烷烃。
优选地,仲烷基磺酸盐是大于50重量%,更优选大于70重量%,最优选大于85重量%的直链仲烷基磺酸盐。
SAS优选为以下形式:-
其中大于50重量%,优选大于60重量%,更优选大于70重量%,更优选至少75重量%,更优选至少80重量%,甚至更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的SAS表面活性剂为C17 SAS(n+m=14)和/或C18 SAS(n+m=15)。
SAS的重量%作为质子化物质计算。
优选地,仲烷基磺酸盐的烷基链获自可再生来源,优选获自甘油三酯。
其它表面活性剂
洗涤剂组合物包含1至60重量%,优选2至40重量%,更优选4至30重量%,最优选5至15重量%的选自其它阴离子(除SAS之外)表面活性剂和非离子表面活性剂的其它表面活性剂。
优选地,分数[总非离子表面活性剂的重量%]/[总阴离子表面活性剂的总和重量%]为0至2,优选地0至1.5,最优选地0.5至1.5,其中总阴离子表面活性剂的重量%的总和为SAS加上任何进一步的阴离子表面活性剂。阴离子表面活性剂的所有重量作为质子化物质计算。
优选地,分数[SAS的重量%]/[总阴离子表面活性剂的总和重量%]为0至5,更优选0至1。
优选地,其它表面活性剂是饱和或单不饱和的,其中多不饱和烷基链的含量低于10重量%,优选低于5重量%。
通常,另外的表面活性剂的非离子表面活性剂和阴离子表面活性剂可以选自M.R.Porter的“Handbook of Surfactants”Springer,1991,Biobased Surfactants(第二版)Synthesis,Properties,and Applications第287-301页(AOCS Press 2019),“SurfaceActive Agents”第1卷,Schwartz&Perry,Interscience 1949,第2卷,Schwartz,Perry&Berch,Interscience 1958,在Manufacturing Confectioners Company出版的“McCutcheon's Emulsifiers and Detergents”当前版本或“Tenside-Taschenbuch”,H.Stache,第2版,Carl Hauser Verlag,1981中描述的表面活性剂。
可以使用的阴离子洗涤剂化合物通常是具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐,术语烷基用于包括高级酰基的烷基部分。合适的合成阴离子洗涤剂化合物的实例是烷基硫酸钠和烷基硫酸钾,尤其是通过硫酸化例如由牛脂或椰油制备的醇获得的那些,烷基C10至C20苯磺酸钠和烷基C10至C20苯磺酸钾,特别是直链仲烷基C10至C15苯磺酸钠;和烷基甘油醚硫酸钠,尤其是衍生自牛脂或椰油的高级醇和衍生自石油的合成醇的那些醚。可存在具有摩尔平均7至9个乙氧基基团的短链(C12至15)醇乙氧基化物。
优选的另外的表面活性剂是醇乙氧基化物、醇醚硫酸盐、甲基酯乙氧基化物、鼠李糖脂、C16至C18甘油单酯的柠檬酸酯(citrem)、C16至C18甘油单酯的酒石酸酯(tatem)和C16至C18甘油单酯的二乙酰酒石酸酯(datem)。
醇乙氧基化物在Non-Lonic Surfactant Organic Chemistry(N.M.Van Os编辑),Surfactant Science Series Volume 72,CRC Press中讨论。优选的是具有摩尔平均6至14个乙氧基的(C16-18)醇乙氧基化物。
醇醚硫酸盐在H.W Stache编辑的Anionic Surfactants:Organic Chemistry(Marcel Dekker 1996)中讨论,优选以下形式:-
R2-(OCH2CH2)nOSO3H
其中R2为具有8至18个碳原子,优选C8、C10、C12、C14、C16和/或C18烷基的饱和或单不饱和直链的链,并且其中n为1至20,优选3至10。更优选地,醇醚硫酸盐是C16-18醚硫酸盐,最优选鲸蜡基(直链C16)和硬脂基(直链C18)的混合物;C18:1(Δ9)醚硫酸盐;及其混合物,最优选具有摩尔平均4至8个乙氧基。
鼠李糖脂描述于WO2020/016097(Unilever)中。优选的是单鼠李糖脂和二鼠李糖脂。优选的烷基链长度为C8至C12。烷基链可以是饱和的或不饱和的。优选地,鼠李糖脂是下式的二鼠李糖脂:Rha2C8-12C8-12。
citrem、tatem和datem描述于WO2020/058088(Unilever)、Hasenhuettl,G.L.和Hartel,R.W.(编辑)Food Emulsifiers and Their Application 2008(Springer)和Whitehurst,R.J.(编辑)Emulsifiers in Food Technology 2008(Wiley-VCH)中。
最优选的是每摩尔表面活性剂具有1至2个二乙酰酒石酸单元的基于甘油单酯的datem。
进一步的优选成分
清洁增强剂
组合物优选包含0.5至15重量%,更优选0.75至15重量%,甚至更优选1至12重量%,最优选1.5至10重量%的清洁增强剂,其选自抗再沉积聚合物;去污聚合物;如WO/2019/008036和WO/2019/007636中所述的烷氧基化多羧酸酯;及其混合物。
抗再沉积聚合物
优选的抗再沉积聚合物包括烷氧基化多胺。
优选的烷氧基化多胺包含烷氧基化聚乙烯亚胺和/或烷氧基化聚丙烯亚胺。多胺可以是线性或分支的。它可以支化到其为树状聚合物的程度。烷氧基化通常可以是乙氧基化或丙氧基化,或两者的混合。在氮原子被烷氧基化的情况下,优选的平均烷氧基化度为10至30,优选15至25。优选的材料是乙氧基化聚乙烯亚胺,其中平均乙氧基化度为10至30,优选15至25,其中氮原子是乙氧基化的。
去污聚合物
优选地,去污聚合物是聚酯去污聚合物。
优选的去污聚合物包括WO 2014/029479和WO 2016/005338中描述的那些。
优选地,基于聚酯的去污聚合物是根据下式(I)的聚酯:
其中
R1和R2彼此独立地为X-(OC2H4)n-(OC3H6)m,其中X为C1-4烷基并且优选为甲基,-(OC2H4)基团和-(OC3H6)基团逐嵌段排列并且由-(OC3H6)基团组成的嵌段与COO基团结合,或者是HO-(C3H6),并且优选彼此独立地为X-(OC2H4)n-(OC3H6)m,
n基于12至120并且优选40至50的摩尔平均数,
m基于1至10和优选1至7的摩尔平均数,和
a基于4至9的摩尔平均数。
优选地,聚酯作为活性共混物提供,所述活性共混物包含:
A)活性共混物的45至55重量%的一种或多种根据下式(I)的聚酯
其中
R1和R2彼此独立地为X-(OC2H4)n-(OC3H6)m,其中X为C1-4烷基并且优选甲基,-(OC2H4)基团和-(OC3H6)基团逐嵌段排列并且由-(OC3H6)基团组成的嵌段与COO基团结合,或者是HO-(C3H6),并且优选彼此独立地为X-(OC2H4)n-(OC3H6)m,
n基于12至120并且优选40至50的摩尔平均数,
m基于1至10和优选1至7的摩尔平均数,和
a基于4-9的摩尔平均数,和
B)活性共混物的10至30重量%的一种或多种醇,所述醇选自乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇和丁基二醇,和
C)活性共混物的24至42%重量的水。
烷氧基化多羧酸酯
烷氧基化多羧酸酯可通过以下方式获得:首先使含有至少三个羧酸单元的芳族多羧酸或由其衍生的酸酐,优选含有三个或四个羧酸单元的芳族多羧酸或由其衍生的酸酐,更优选含有三个羧酸单元的芳族多羧酸或由其衍生的酸酐,甚至更优选偏苯三酸或偏苯三酸酐,最优选偏苯三酸酐,与醇烷氧基化物反应,并且在第二步中使所得产物与醇或醇的混合物,优选与C16/C18醇反应。
酶
优选地,酶,如脂肪酶、蛋白酶、α-淀粉酶、纤维素酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶或其混合物可存在于制剂中。
如果存在酶,则优选地它们选自:脂肪酶、蛋白酶、α-淀粉酶、纤维素酶及其混合物。
如果存在,则本发明的洗衣组合物中每种酶的水平为0.0001重量%至0.1重量%。
组合物中存在的酶的水平优选地涉及作为纯蛋白质的酶的水平。
合适的脂肪酶包括细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的脂肪酶的实例包括来自腐质霉属(Humicola)(同义词嗜热真菌属(Thermomyces))的脂肪酶,例如来自如EP 258 068和EP 305 216中所述的疏棉状腐质霉(H.lanuginosa)(疏绵状嗜热丝孢菌(T.lanuginosus))或来自如WO96/13580中所述的特异腐质霉(H.insolens),假单胞菌脂肪酶,例如来自产碱假单胞菌(P.alcaligenes)或类产碱假单胞菌(P.pseudoalcaligenes)(EP 218272)、洋葱假单胞菌(P.cepacia)(EP 331 376)、施氏假单胞菌(P.stutzeri)(GB 1,372,034)、荧光假单胞菌(P.fluorescens)、假单胞菌属菌株SD 705(WO95/06720和WO96/27002)、威斯康辛假单胞菌(P.wisconsinensis)(WO96/12012),芽孢杆菌(Bacillus)脂肪酶,例如,来自枯草芽孢杆菌(B.Subtilis)(Dartois等(1993),Biochemica et Biophysica Acta,1131,253-360),嗜热脂肪芽孢杆菌(B.stearothermophilus)(JP 64/744992)或短小芽孢杆菌(B.pumilus)(WO91/16422)。其他实例是脂肪酶变体,如WO92/05249、WO94/01541、EP 407 225、EP 260 105、WO95/35381、WO96/00292、WO95/30744、WO94/25578、WO95/14783、WO95/22615、WO97/04079和WO97/07202、WO00/60063中所述的那些。
优选的市售脂肪酶包括LipolaseTM和Lipolase UltraTM、LipexTM和LipocleanTM(Novozymes A/S)。
本发明可以在分类为EC 3.1.1.4和/或EC 3.1.1.32的磷脂酶的存在下进行。如本文所用,术语磷脂酶是对磷脂具有活性的酶。
磷脂,如卵磷脂或磷脂酰胆碱,由在外部(sn-1)和中间(sn-2)位置用两个脂肪酸酯化并在第三位置用磷酸酯化的甘油组成;磷酸又可以酯化成氨基醇。磷脂酶是参与磷脂水解的酶。可以区分几种类型的磷脂酶活性,包括磷脂酶A1和A2,其水解一个脂肪酰基(分别在sn-1和sn-2位)以形成溶血磷脂;和溶血磷脂酶(或磷脂酶B),其可以水解溶血磷脂中剩余的脂肪酰基。磷脂酶C和磷脂酶D(磷酸二酯酶)分别释放二酰基甘油或磷脂酸。
蛋白酶水解肽和蛋白质内的键,在洗衣情况下,这导致增强的含蛋白质或肽的污渍的去除。合适的蛋白酶家族的实例包括天冬氨酸蛋白酶;半胱氨酸蛋白酶;谷氨酸蛋白酶;天冬酰胺肽裂解酶;丝氨酸蛋白酶和苏氨酸蛋白酶。此类蛋白酶家族描述于MEROPS肽酶数据库(http://merops.sanger.ac.uk/)中。优选的是丝氨酸蛋白酶。更优选的是枯草杆菌酶型丝氨酸蛋白酶。术语“枯草杆菌酶”是指根据Siezen等,ProteinEngng.Med.Chem.Lett.,2001,31,43-5和Siezen等,Protein Science 6(1997)501-523中所述的丝氨酸蛋白酶的亚组。丝氨酸蛋白酶是蛋白酶的亚组,其特征在于在活性位点中具有丝氨酸,其与底物形成共价加合物。枯草杆菌酶可以分为6个亚部,即枯草杆菌蛋白酶家族、嗜热蛋白酶家族、蛋白酶K家族、Lantibiotic肽酶家族、Kexin家族和Pyrolysin家族。
枯草杆菌酶的实例是源自芽孢杆菌属(Bacillus)的那些,如迟缓芽孢杆菌(Bacillus lentus)、嗜碱芽孢杆菌(B.alkalophilus)、枯草芽孢杆菌(B.subtilis)、解淀粉芽孢杆菌(B.amyloliquefaciens)、短小芽孢杆菌(B.pumilus)和吉氏芽孢杆菌(B.gibsonii),描述于US7262042和WO09/021867中,以及枯草杆菌蛋白酶lentus、枯草杆菌蛋白酶Novo、枯草杆菌蛋白酶Carlsberg、地衣芽孢杆菌(Bacillus licheniformis)、枯草杆菌蛋白酶BPN’、枯草杆菌蛋白酶309、枯草杆菌蛋白酶147和枯草杆菌蛋白酶168,描述于WO89/06279中,以及蛋白酶PD138,描述于(WO93/18140)。其他有用的蛋白酶可以是WO92/175177、WO01/016285、WO02/026024和WO02/016547中描述的那些。胰蛋白酶样蛋白酶的实例是胰蛋白酶(例如猪或牛来源的)和描述于WO89/06270、WO94/25583和WO05/040372中的镰孢菌属蛋白酶,以及描述于WO05/052161和WO05/052146中的源自纤维单胞菌属(Cellumonas)的胰凝乳蛋白酶。
最优选地,蛋白酶是枯草杆菌蛋白酶(EC 3.4.21.62)。
枯草杆菌蛋白酶的实例是源自芽孢杆菌属的那些,如迟缓芽孢杆菌、嗜碱芽孢杆菌、枯草芽孢杆菌、解淀粉芽孢杆菌、短小芽孢杆菌(Bacillus pumilus)和吉氏芽孢杆菌(Bacillus gibsonii),描述于US7262042和WO09/021867中,以及枯草杆菌蛋白酶lentus、枯草杆菌蛋白酶Novo、枯草杆菌蛋白酶Carlsberg、地衣芽孢杆菌、枯草杆菌蛋白酶BPN’、枯草杆菌蛋白酶309、枯草杆菌蛋白酶147和枯草杆菌蛋白酶168,描述于WO89/06279中,以及蛋白酶PD138,描述于(WO93/18140)中。优选地,枯草杆菌蛋白酶源自芽孢杆菌属,优选迟缓芽孢杆菌、嗜碱芽孢杆菌、枯草芽孢杆菌、解淀粉芽孢杆菌、短小芽孢杆菌和吉氏芽孢杆菌,描述于US 6,312,936 Bl、US 5,679,630、US 4,760,025、US7,262,042和WO09/021867中。最优选地,枯草杆菌蛋白酶源自吉氏芽孢杆菌或迟缓芽孢杆菌。
本发明可以使用分类为EC 3.1.1.74的角质酶。根据本发明使用的角质酶可以是任何来源的。优选地,角质酶是微生物来源的,特别是细菌、真菌或酵母来源的。
合适的淀粉酶(α和/或β)包括细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。淀粉酶包括,例如,获自芽孢杆菌属的α-淀粉酶,例如在GB 1,296,839中更详细描述的地衣芽孢杆菌(B.licheniformis)的特殊菌株,或WO95/026397或WO00/060060中公开的芽孢杆菌属菌株。可商购获得的淀粉酶是DuramylTM、TermamylTM、TermamylUltraTM、NatalaseTM、StainzymeTM、FungamylTM和BANTM(Novozymes A/S)、RapidaseTM和PurastarTM(来自Genencor International Inc.)。
合适的纤维素酶包括细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。合适的纤维素酶包括来自芽孢杆菌属、假单胞菌属、腐质霉属、镰孢菌属(Fusarium)、梭孢壳属(Thielavia)、支顶孢属(Acremonium)的纤维素酶,例如US 4,435,307、US 5,648,263、US 5,691,178、US 5,776,757、WO89/09259、WO96/029397和WO98/012307中公开的由特异腐质霉(Humicola insolens)、土生梭孢壳(Thielaviaterrestris)、嗜热毁丝霉(Myceliophthora thermophila)和尖孢镰孢菌(Fusariumoxysporu)产生的真菌纤维素酶。可商购获得的纤维素酶包括CelluzymeTM、CarezymeTM、CellucleanTM、EndolaseTM、RenozymeTM(Novozymes A/S)、ClazinaseTM和Puradax HATM(Genencor International Inc.)和KAC-500(B)TM(Kao Corporation)。优选的是CellucleanTM。
合适的过氧化物酶/氧化酶包括植物、细菌或真菌来源的那些。包括化学修饰的或蛋白质工程化的突变体。有用的过氧化物酶的实例包括来自鬼伞属(Coprinus),例如来自灰盖鬼伞(C.cinereus)的过氧化物酶及其变体,如WO93/24618、WO95/10602和WO98/15257中所述的那些。可商购的过氧化物酶包括GuardzymeTM和NovozymTM51004(Novozymes A/S)。
适合使用的其他酶在WO2009/087524、WO2009/090576、WO2009/107091、WO2009/111258和WO2009/148983中讨论。
酶稳定剂
组合物中存在的任何酶可以使用常规稳定剂稳定,例如多元醇,如丙二醇或甘油、糖或糖醇、乳酸、硼酸或硼酸衍生物(例如芳族硼酸酯)或苯基硼酸衍生物(例如4-甲酰基苯基硼酸),并且组合物可以如例如WO92/19709和WO92/19708中所述的配制。
其他成分
制剂可含有其他成分。
助洗剂或络合剂
组合物可包含助洗剂或络合剂。
助洗剂材料可选自1)钙螯合剂材料,2)沉淀材料,3)钙离子交换材料和4)其混合物。
钙螯合剂助洗剂材料的实例包括碱金属多磷酸盐,例如三聚磷酸钠,和有机螯合剂,如乙二胺四乙酸。
组合物还可以含有0-10重量%的助洗剂或络合剂,如乙二胺四乙酸、二亚乙基三胺-五乙酸、柠檬酸、烷基-或烯基琥珀酸、次氮基三乙酸或下文提及的其他助洗剂。
更优选地,洗衣洗涤剂制剂是非磷酸盐助洗的洗衣洗涤剂制剂,即含有小于1重量%的磷酸盐。最优选地,洗衣洗涤剂制剂不是助洗的,即含有小于1重量%的助洗剂。
如果洗涤剂组合物是水性液体洗衣洗涤剂,则优选单丙二醇或甘油以1至30重量%,最优选2至18重量%的水平存在,以提供具有适当的可倾倒粘度的制剂。
荧光剂
组合物优选包含荧光剂(荧光增白剂)。
荧光剂是众所周知的,并且许多这样的荧光剂可商购获得。通常,这些荧光剂以其碱金属盐(例如钠盐)的形式提供和使用。
组合物中使用的一种或多种荧光剂的总量通常为0.0001至0.5重量%,优选0.005至2重量%,更优选0.01至0.1重量%。荧光剂的优选类别是:二苯乙烯基联苯化合物,例如Tinopal(商标)CBS-X,二胺芪二磺酸化合物,例如Tinopal DMS pure Xtra和Blankophor(商标)HRH,以及吡唑啉化合物,例如Blankophor SN。优选的荧光剂是具有CAS-No 3426-43-5;CAS-No 35632-99-6;CAS-No 24565-13-7;CAS-No 12224-16-7;CAS-No 13863-31-5;CAS-No 4193-55-9;CAS-No 16090-02-1;CAS-No 133-66-4;CAS-No 68444-86-0;CAS-No27344-41-8的荧光剂。
最优选的荧光剂是:2(4-苯乙烯基-3-磺基苯基)-2H-萘酚并[1,2-d]***钠、4,4'-双{[(4-苯胺基-6-(N-甲基-N-2羟乙基)氨基1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠、4,4'-双{[(4-苯胺基-6-吗啉代-1,3,5-三嗪-2-基)]氨基}二苯乙烯-2-2'二磺酸二钠和4,4'-双(2-磺基苯乙烯基)联苯二钠。
调色(shading)染料
在制剂中存在调色染料是有利的。
染料描述于Color Chemistry Synthesis,Properties and Applications ofOrganic Dyes and Pigments,(H Zollinger,Wiley VCH,Zürich,2003)和IndustrialDyes Chemistry,Properties Applications(K Hunger(编辑),Wley-VCH Weinheim 2003)中。
用于洗衣组合物中的调色染料优选在可见光范围(400至700nm)中的最大吸收处具有大于5000L mol-1cm-1,优选大于10000L mol-1cm-1的消光系数。
优选的染料发色团是偶氮、吖嗪、蒽醌、酞菁和三苯甲烷。偶氮、蒽醌、酞菁和三苯甲烷染料优选带有净阴离子电荷或不带电荷。吖嗪染料优选带有净阴离子或阳离子电荷。
最优选的是蓝色或紫色调色染料。在洗涤过程的洗涤或漂洗步骤期间,调色染料沉积到织物上,从而为织物提供可见的色调。在这方面,染料对白色布赋予蓝色或紫色,色调角为240至345,更优选260至320,最优选270至300。在这个测试中使用的白色布是漂白的非丝光编织棉片材。
调色染料在WO2005/003274、WO2006/032327(Unilever)、WO2006/032397(Unilever)、WO2006/045275(Unilever)、WO2006/027086(Unilever)、WO2008/017570(Unilever)、WO2008/141880(Unilever)、WO2009/132870(Unilever)、WO2009/141173(Unilever)、WO2010/099997(Unilever)、WO2010/102861(Unilever)、WO2010/148624(Unilever)、WO2008/087497(P&G)、WO2011/011799(P&G)、WO2012/054820(P&G)、WO2013/142495(P&G)和WO2013/151970(P&G)、WO2018085311(P&G)和WO2019075149(P&G)中讨论。
可以使用调色染料的混合物。
调色染料发色团最优选选自单偶氮、双偶氮和吖嗪。
单偶氮染料优选含有杂环的环,且最优选噻吩染料。单偶氮染料优选是烷氧基化的,并且优选在pH=7下不带电荷或带阴离子电荷。在WO2013/142495和WO2008/087497中讨论了烷氧基化噻吩染料。噻吩染料的优选实例如下所示:
双偶氮染料优选为磺化双偶氮染料。磺化双偶氮化合物的优选实例是直接紫7、直接紫9、直接紫11、直接紫26、直接紫31、直接紫35、直接紫40、直接紫41、直接紫51、直接紫66、直接紫99及其烷氧基化形式。
烷氧基化双偶氮染料在WO2012/054058和WO/2010/151906中讨论。
烷氧基化双偶氮染料的实例是:
吖嗪染料优选选自磺化吩嗪染料和阳离子吩嗪染料。优选的实例是酸性蓝98、酸性紫50、CAS-No 72749-80-5的染料、酸性蓝59和选自以下的吩嗪染料:
其中:
X3选自:-H;-F;-CH3;-C2H5;-OCH3;和-OC2H5;
X4选自:-H;-CH3;-C2H5;-OCH3;和-OC2H5;
Y2选自:-OH;-OCH2CH2OH;-CH(OH)CH2OH;-OC(O)CH3;和C(O)OCH3。
可以使用与乙氧基化物或丙氧基化聚乙烯亚胺共价结合的蒽醌染料,如WO2011/047987和WO 2012/119859中所述。
调色染料优选以0.0001至0.1重量%的范围存在于组合物中。根据调色染料的性质,存在根据调色染料的功效的优选范围,所述功效取决于类别和任何特定类别内的特定功效。如上所述,调色染料优选为蓝色或紫色调色染料。
香料
组合物优选包含香料。香料的许多合适的实例提供于由CFTA Publications出版的CTFA(Cosmetic,Toiletry and Fragrance Association)1992International BuyersGuide和由Schnell Publishing Co.出版的OPD 1993Chemicals Buyers Directory 80thAnnual Edition中。
优选地,香料包含至少一种选自以下的香调(化合物):α-异甲基紫罗兰酮、水杨酸苄酯;香茅醇;香豆素;己基肉桂醛;芳樟醇;2-甲基戊酸乙酯;辛醛;乙酸苄酯;1,6-辛二烯-3-醇,3,7-二甲基-,3-乙酸酯;2-(1,1-二甲基乙基)-1-乙酸环己醇酯;δ-二氢大马酮;β-紫罗兰酮;醋酸维地尔(verdyl acetate);十二醛;己基肉桂醛;环十五内酯;苯乙酸,2-苯基乙基酯;水杨酸戊酯;β-石竹烯;十一烯酸乙酯;邻氨基苯甲酸香叶酯;α-鸢尾酮;苯甲酸β-苯基乙酯;α-白檀油烯醇;雪松醇;乙酸柏木酯;甲酸柏木酯;水杨酸环己酯;γ-十二内酯;和β-苯基乙基苯基乙酸酯。
香料的有用组分包括天然和合成来源的材料。它们包括单一化合物和混合物。此类组分的具体实例可以在现有文献中找到,例如Fenaroli's Handbook of FlavourIngredients,1975,CRC Press;Synthetic Food Adjuncts,1947,M.B.Jacobs,VanNostrand编辑;或S.Arctander的Perfume and Flavour Chemicals,1969,Montclair,N.J.(USA)。
在制剂中存在多种香料组分是常见的。在本发明的组合物中,设想将存在四种或更多种,优选五种或更多种,更优选六种或更多种或甚至七种或更多种不同的香料组分。
在香料混合物中,优选15至25重量%是头香。头香由Poucher定义(Journal ofthe Society of Cosmetic Chemists 6(2):80[1955])。优选的头香选自柑橘油、芳樟醇、乙酸芳樟酯、薰衣草、二氢月桂烯醇、玫瑰醚和顺式-3-己醇。
国际香料协会在2011年公布了香料成分(香料)的列表。(http://www.ifrao.g.org/en-us/Ingredients#.U7Z4HPLDWZK)
香料研究所提供了具有安全信息的香料(香味)数据库。
香料头香可用于提示本发明的白度和亮度益处。
一些或所有香料可以被包封,包封有利的典型香料组分包括具有相对低沸点的那些,优选沸点小于300℃,优选100-250℃的那些。包封具有低CLog P的香料组分(即,将具有更大的分配到水中的倾向的那些)也是有利的,优选具有小于3.0的CLog P的香料组分。具有相对低沸点和相对低CLog P的这些材料被称为“延迟释香”香料成分,并且包括以下材料中的一种或多种:己酸烯丙酯、乙酸戊酯、丙酸戊酯、茴香醛、苯甲醚、苯甲醛、乙酸苄酯、苄基丙酮、苯甲醇、甲酸苄酯、异戊酸苄酯、丙酸苄酯、βγ-己烯醇、樟脑胶、左旋香芹酮、d-香芹酮、肉桂醇、甲酸肉桂酯、顺式-茉莉酮、顺式-3-己烯乙酸酯、枯茗醇、cyclal c、二甲基苄基甲醇、二甲基苄基甲醇乙酸酯、乙酸乙酯、乙酰乙酸乙酯、乙基戊基酮、苯甲酸乙酯、丁酸乙酯、乙基己基酮、乙基苯基乙酸酯、桉油精、丁子香酚、乙酸葑酯、醋酸flor(乙酸三环癸烯酯)、frutene(丙酸三环癸烯酯)、香叶醇、己烯醇、乙酸己烯酯、乙酸己酯、甲酸己酯、龙葵醇(hydratropic alcohol)、羟基香茅醛、茚酮、异戊醇、异薄荷酮、乙酸异蒲勒酯、异喹诺酮、女贞醛、芳樟醇、芳樟醇氧化物、甲酸芳樟酯、薄荷酮、薄荷基乙酰苯酮、甲基戊基酮、邻氨基苯甲酸甲酯、苯甲酸甲酯、甲基苯基乙酸酯、甲基丁子香酚、甲基庚烯酮、甲基庚炔碳酸酯、甲基庚基酮、甲基己基酮、乙酸甲基苯基原酯、水杨酸甲酯、邻氨基苯甲酸甲基-n-甲酯、橙花醇、辛内酯、辛醇、对甲酚、对甲酚甲醚、对甲氧基苯乙酮、对甲基苯乙酮、苯氧基乙醇、苯基乙醛、苯基乙基乙酸酯、苯乙醇、苯乙基二甲基甲醇、乙酸异戊二烯酯、杀虫丙酯(propylbornate)、长叶薄荷酮、玫瑰醚、黄樟素、4-萜品烯醇、α-萜品烯醇和/或绿草啶(viridine)。在制剂中存在多种香料组分是常见的。在本发明的组合物中,设想在香料中存在四种或更多种,优选五种或更多种,更优选六种或更多种或甚至七种或更多种来自上文给出的延迟释香香料的列表的不同香料组分。
本发明可以应用的另一组香料是所谓的“芳香疗法”材料。这些包括也用于香水制造中的许多组分,包括精油的组分,如鼠尾草、桉树、天竺葵、薰衣草、肉豆蔻(Mace)提取物、橙花油、肉豆蔻、留兰香、甜紫罗兰叶和缬草。
优选的是洗衣处理组合物不含过氧漂白剂,例如过碳酸钠、过硼酸钠和过酸。
聚合物
组合物可包含一种或多种另外的聚合物。实例是羧甲基纤维素、聚(乙二醇)、聚(乙烯醇)、聚羧酸酯,如聚丙烯酸酯、马来酸/丙烯酸共聚物和甲基丙烯酸月桂酯/丙烯酸共聚物。
在烷基足够长以形成支链或环状链的情况下,烷基包括支链、环状和直链烷基链。烷基优选是直链或支链的,最优选是直链的。
助剂成分
洗涤剂组合物任选地包含一种或多种洗衣助剂成分。
为了防止制剂的氧化,抗氧化剂可以存在于制剂中。
术语“助剂成分”包括:香料、分散剂、稳定剂、pH控制剂、金属离子控制剂、着色剂、增白剂、染料、气味控制剂、前香料、环糊精、香料、溶剂、去污聚合物、防腐剂、抗微生物剂、氯清除剂、抗皱缩剂、织物卷曲剂、去斑剂、抗氧化剂、抗蚀剂、稠化剂、悬垂和形状控制剂、平滑剂、静电控制剂、皱褶控制剂、卫生处理剂、消毒剂、病菌控制剂、霉菌控制剂、霉变控制剂、抗病毒剂、抗微生物剂、干燥剂、防污剂、去污剂、异味控制剂、织物清新剂、氯漂白剂气味控制剂、固色剂、染料转移抑制剂、调色染料、颜色保持剂、颜色恢复剂、更新剂、抗褪色剂、白度增强剂、抗磨损剂、耐磨剂、织物完整性剂、抗磨剂和漂洗助剂、UV防护剂、防晒褪色抑制剂、驱虫剂、抗过敏剂、酶、阻燃剂、防水剂、织物柔顺剂、水调理剂、抗收缩剂、抗拉伸剂及其组合。如果存在,此类助剂可以按组合物重量的0.1%至5%的含量使用。
将通过以下非限制性实施例进一步描述本发明。
实施例
实施例1
参考样品SAS由衍生自石油化工产品的(Euro cut)正链烷烃的C14-17混合物产生。磺化通过如H.W.Stache编辑的Anionic Surfactants Organic Chemistry第146-149页(Surfactant Science Series vol 56,Marcel Dekker 1996)和H.Ramloch u.G.Tauber,Chem.Unserer Zeit 13,157-162(1979)中所述的Hoechst磺化氧化工艺实现。
油酸(>90重量%)获自油菜籽油并根据Yang,L.Carreon,M.A.Effect ofreaction parameters on the decarboxylation of oleic acid over Pt/ZIF-67membrane/zeolite 5A bead catalysts.J.Chem.Technol.Biotechnol.92,52-58(2017)中描述的方法转化为正链烷烃。0.5重量%的Pt负载量用于以下反应条件:温度320℃、H2气氛下压力20Br和反应时间2小时。
根据在P.;B.;Lestari,S.;Simakova,O.;K.;Salmi,T.;Murzin,D.Y.Catalytic deoxygenation of tall oilfatty acidover palladium supported on mesoporous carbon,Energy Fuels 25,2815-2825(2011)中描述的方法,将由C18:0(1.5重量%)、C18:1(25.1重量%)、C18:2(53.4重量%)和C18:3(10.1重量%),连同痕量的C17:0和C20:3脂肪酸和未知的脂肪酸组成的蒸馏的妥尔油脂肪酸(TOFA),其给出高达97重量%的脂肪酸和3%的其他化合物(松香酸和甾醇),作为在负载在合成碳上的介孔1wt%Pd上的催化脱氧的原料应用。气氛为100%氢气(17巴),350℃及反应时间330分钟。
反应后,未反应的脂肪酸使用甲醇萃取,然后链烷烃氢化以除去残留的不饱和链烷烃。
然后通过用于参考样品的Hoechst磺化氧化工艺将链烷烃磺化。
所得SAS表面活性剂确定为具有下表中的碳链分布:-
碳链 | 参考 | 油酸 | TOFA |
C13 | 1.5 | ||
C14 | 32.0 | ||
C15 | 30.0 | ||
C16 | 22.0 | ||
C17 | 15.0 | 80 | >90 |
C18 | 0.8 | 18 |
可以看出,参考SAS具有≤50重量%的作为C17和/或C18仲烷基磺酸盐的仲烷基磺酸盐;而通过油酸途径和TOFA途径产生的SAS具有>50重量%的作为C17和/或C18仲烷基磺酸盐的仲烷基磺酸盐。
实施例2
将实施例1的SAS样品配制成液体洗涤剂产品。
成分 | 重量% |
油醇乙氧基化物,具有10摩尔平均的乙氧基化物 | 6.0 |
SAS | 4.0 |
柠檬酸 | 3.0 |
聚酯去污聚合物 | 0.25 |
水和碱(NaOH/三乙醇胺),至pH 7 | 剩余部分 |
Claims (15)
1.一种仲烷基磺酸盐(SAS)表面活性剂;
其中大于50重量%,优选大于60重量%,更优选大于70重量%的所述仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐。
2.根据权利要求1所述的仲烷基磺酸盐(SAS)表面活性剂,其中至少75重量%,优选至少80重量%,更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的所述仲烷基磺酸盐的烷基链为C17和/或C18仲烷基磺酸盐。
3.根据权利要求1或权利要求2所述的仲烷基磺酸盐(SAS)表面活性剂,其中所述C17和/或C18仲烷基磺酸盐在直链烷烃链中具有该碳原子。
4.根据前述权利要求中任一项所述的仲烷基磺酸盐(SAS)表面活性剂,其中所述仲烷基磺酸盐的烷基链从可再生来源获得,优选从甘油三酯获得。
5.一种洗涤剂组合物,其包含:
a)1至40重量%,优选2至30重量%,最优选3至15重量%的根据权利要求1所述的仲烷基磺酸盐表面活性剂,其中大于50重量%,优选大于60重量%,更优选大于70重量%的所述仲烷基磺酸盐为C17和/或C18仲烷基磺酸盐;和
b)1至60重量%,优选2至40重量%,更优选4至30重量%,最优选5至15重量%的选自其它阴离子表面活性剂和非离子表面活性剂的其它表面活性剂。
6.根据权利要求5所述的洗涤剂组合物,其中至少75重量%,优选至少80重量%,更优选至少85重量%,甚至更优选至少90重量%,最优选至少95重量%的所述仲烷基磺酸盐的烷基链为C17和/或C18仲烷基磺酸盐。
7.根据权利要求5或权利要求6所述的洗涤剂组合物,其中所述C17和/或C18仲烷基磺酸盐在直链烷烃链中具有该碳原子。
8.根据权利要求5至7中任一项所述的洗涤剂组合物,其中所述仲烷基磺酸盐的烷基链从可再生来源获得,优选从甘油三酯获得。
9.根据权利要求5至8中任一项所述的洗涤剂组合物,其中所述非离子表面活性剂选自饱和的和单不饱和的脂族醇乙氧基化物,优选地选自具有平均5至30个乙氧基化物的C12至C20直链伯醇乙氧基化物,更优选地具有平均5至25个乙氧基化物的C16至C18。
10.根据权利要求5至9中任一项所述的洗涤剂组合物,其中所述阴离子表面活性剂选自:鼠李糖脂、C12至C18烷基醚羧酸盐;C16-C18甘油单酯的柠檬酸酯(citrem)、C16-C18甘油单酯的酒石酸酯(tatem)和C16-C18甘油单酯的二乙酰酒石酸酯(datem);C12至C18烷基醚硫酸盐;和具有含约8至约22个碳原子的烷基的有机硫酸和磺酸的水溶性碱金属盐;及其混合物;最优选地,所述阴离子表面活性剂选自:鼠李糖脂、C16至C18烷基醚羧酸盐;C16-C18甘油单酯的柠檬酸酯(citrem)、C16-C18甘油单酯的酒石酸酯(tatem);C12-C18烷基醚硫酸盐,和C16-C18甘油单酯的二乙酰酒石酸酯(datem)和磺酸盐,例如直链烷基苯磺酸盐;及其混合物。
11.根据权利要求5至10中任一项所述的洗涤剂组合物,其中所述组合物包含0.5重量%至15重量%,更优选0.75重量%至15重量%,甚至更优选1重量%至12重量%,最优选1.5重量%至10重量%的清洁增强剂,其选自抗再沉积聚合物、去污聚合物、烷氧基化聚羧酸酯及其混合物。
12.根据权利要求11所述的洗涤剂组合物,其中所述清洁增强剂选自:抗再沉积聚合物,优选烷氧基化聚胺;和去污聚合物,优选聚酯去污聚合物。
13.根据如权利要求5至12中任一项所述的洗涤剂组合物,其中所述组合物包含选自下组的一种或多种酶:脂肪酶、蛋白酶、α-淀粉酶、纤维素酶、过氧化物酶/氧化酶、果胶酸裂解酶和甘露聚糖酶,或它们的混合物,优选脂肪酶、蛋白酶、α-淀粉酶、纤维素酶及其混合物,其中在本发明的组合物中每种酶的水平为0.0001重量%至0.1重量%。
14.根据权利要求5至13中任一项所述的洗涤剂组合物,其中阴离子表面活性剂的总量与非离子表面活性剂的总量的重量比在4:1至1:4,优选2:1至1:2,最优选1.5:1至1:1.5的范围内。
15.一种处理纺织品的方法,优选家用方法,所述方法包括以下步骤:用0.5至20g/L的如权利要求5至14中任一项所述的洗涤剂组合物,优选液体洗衣洗涤剂组合物的水溶液处理纺织品,优选地其中所述水溶液含有0.1至1.0g/L的(a)和(b)的表面活性剂;和任选地干燥所述纺织品;优选地其中所述家用方法使用家用电器在家中进行,其中所述方法在280至335K的洗涤水温度下进行。
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EP4204526A1 (en) | 2023-07-05 |
EP4204526B1 (en) | 2024-04-24 |
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