CN104610102B - 制备三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的方法 - Google Patents
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Abstract
在通过用硫酸二甲酯季铵化三‑(2‑羟乙基)‑胺脂肪酸酯以制备三‑(2‑羟乙基)‑甲基硫酸甲酯铵脂肪酸酯的方法中,所述季铵化是在固体酸清除剂存在的情况下进行的。所述方法可以提供织物柔软剂活性组合物,其包括65‑98重量%的至少一种三‑(2‑羟乙基)‑甲基硫酸甲酯铵脂肪酸酯、相应的非季铵化三‑(2‑羟乙基)‑胺脂肪酸酯以及1‑1500ppm的甲醇,所述非季铵化三‑(2‑羟乙基)‑胺脂肪酸酯的量使所述组合物的总胺值为2至低于7mgKOH/g。
Description
技术领域
本发明涉及一种制备低甲醇含量的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的方法,以及涉及通过该方法获得的织物柔软活性组合物。
背景技术
含有两个疏水长链烃部分的季铵盐已被广泛用作织物柔软剂活性物。平均每分子被两个脂肪酸部分酯化的烷醇胺的季铵盐,通常被称为酯基季铵盐,由于它们的生物可降解性,已广泛替代早期的烷基季铵化合物。
通过用硫酸二甲酯季铵化三乙醇胺的脂肪酸酯而制备的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐已被广泛用作织物柔软剂活性物。因为硫酸二甲酯是潜在的致癌物质,所以季铵化的进行要使硫酸二甲酯转化完全且得到高的胺转化。已发现通过此方法制备的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐包含不希望的高含量甲醇。虽然三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐柔软剂活性物质已经使用超过20年,但在这些组合物中的高甲醇含量还没有被注意到。
因为甲醇有毒性且存在工作危害,由此需要使包含三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的织物柔软剂活性组合物具有低的甲醇含量。同样也需要以简单的方法制备这样的组合物。
已发现包含三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐和具有低甲醇含量的织物柔软剂活性组合物可以在固体酸清除剂存在的情况下,通过用硫酸二甲酯季铵化三乙醇胺来制备。
发明内容
由此本发明涉及制备三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的方法,所述方法包括用甲基硫酸季铵化三-(2-羟乙基)-胺脂肪酸酯的步骤,其中所述季铵化是在固体酸清除剂存在的情况下进行的。
本发明另外涉及一种织物柔软剂活性组合物,其包括65-98重量%的至少一种三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐、相应的非季铵化的三-(2-羟乙基)-胺脂肪酸酯、和1-1500ppm的甲醇,所述非季铵化的三-(2-羟乙基)-胺脂肪酸酯的量使该组合物的总胺值为2至低于7mg KOH/g。
本发明的方法包括在固体酸清除剂存在的情况下,用硫酸二甲酯季铵化三-(2-羟乙基)-胺脂肪酸酯的步骤。术语酸清除剂表示与季铵化反应混合物中存在的或季铵化反应中形成的布朗斯台德酸(acid)反应的材料,但是所述材料在季铵化反应中在很大程度上不与硫酸二甲酯反应。优选低于10%,更优选低于5%且最优选低于2%的所用硫酸二甲酯被与所述酸清除剂的反应消耗。
所述固体酸清除剂可以是金属碳酸盐、金属碳酸氢盐、金属氧化物、金属氢氧化物、碱性硅酸盐或碱性铝硅酸盐。所述的固体酸清除剂优选选自碱金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸盐、碱土金属氧化物和碱土金属氢氧化物。所述的碱金属优选为锂、钠或钾,最优选钠。所述的碱土金属优选为镁或钙或其混合物。适宜的固体酸清除剂为例如碳酸钠、碳酸氢钠、倍半碳酸钠、碳酸钙、碳酸镁、白云石、氢氧化镁碳酸镁复盐(magnesiumhydroxyl carbonates)、氧化钙、氧化镁、氢氧化钙或氢氧化镁。最优选的固体酸清除剂是碳酸钠或碳酸氢钠。
所述固体酸清除剂的用量优选高于季铵化反应混合物中存在的以及在季铵化反应中形成的布朗斯台德酸。更优选地,基于季铵化反应混合物的重量,固体酸清除剂的使用量是1-3重量%。
在固体酸清除剂存在的情况下,用硫酸二甲酯进行三-(2-羟乙基)-胺脂肪酸酯的季铵化使得即使在高度季铵化反应中,三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐具有低含量的甲醇。因此,本发明的方法可以提供包括三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的组合物,其同时具有低甲醇含量和低总胺值。
所述固体酸清除剂优选由平均颗粒尺寸至少为100μm的颗粒,特别是平均颗粒尺寸为100μm-5mm的颗粒组成。平均颗粒尺寸的测量是通过筛分析法测量颗粒尺寸分布的质量中值直径。使用具有优选颗粒尺寸的固体酸清除剂会促进未反应的固体酸清除剂从季铵化反应所产生的粘性反应混合物中分离出来。
优选通过过滤或离心将所述固体酸清除剂从季铵化所产生的反应混合物中分离出。通过过滤或离心分离固体酸清除剂使得包含三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的组合物仅含有少量的酸性和碱性化合物。
季铵化的步骤可以在溶剂存在的情况下进行,所述溶剂优选选自乙醇、1-丙醇、2-丙醇、乙二醇、二甘醇、丙二醇、二丙醇醚、乙二醇的C1-C4烷基单醚、丙二醇的C1-C4烷基单醚以及它们的混合物。然而,季铵化的步骤优选在没有溶剂的情况下进行。
在本发明所述方法的优选实施方案中,在通过过滤和离心分离固体酸清除剂之前,将选自以下的溶剂加入到由季铵化得到的反应混合物中:乙醇、1-丙醇、2-丙醇、乙二醇、二甘醇、丙二醇、二丙醇醚、乙二醇的C1-C4烷基单醚、丙二醇的C1-C4烷基单醚以及它们的混合物。在过滤或离心之前添加溶剂可以通过降低混合物的粘性而促进未反应的固体酸清除剂从反应混合物中分离。在其他的优选实施方案中,所分离的固体酸清除剂用该溶剂洗涤,由此生产洗涤液,且该洗涤液重新用于在季铵化所得到的反应混合物中添加溶剂。
用溶剂洗涤并重复利用洗涤液,可降低在过滤或离心分离中黏附在未反应的固体酸清除剂上的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的损失。
所述季铵化的步骤优选在硫酸二甲酯和三-(2-羟乙基)-胺脂肪酸酯的摩尔比为0.9-0.98,更优选在0.92-0.97时进行。所述季铵化的步骤优选在60-95℃,更优选70-90℃的温度下进行。季铵化可以在任何压力下进行,例如环境压力或降低压力下。季铵化优选进行至基本上所有的硫酸二甲酯已反应。
作为起始材料的三-(2-羟乙基)-胺脂肪酸酯的脂肪酸部分可以衍生于纯的脂肪酸或结构式为RCOOH的脂肪酸的混合物,其中R是烃基。所述的烃基可以是支链的或直链的,优选是直链的。
所述三-(2-羟乙基)-胺脂肪酸酯可以包括结构式为N(CH2CH2OH)2(CH2CH2OC(=O)R)的单酯、结构式为N(CH2CH2OH)(CH2CH2OC(=O)R)2的二酯、以及结构式为N(CH2CH2OC(=O)R)3的三酯,其中R是脂肪酸部分RCOO的烃基。所述的三-(2-羟乙基)-胺脂肪酸酯中脂肪酸部分和氮的平均摩尔比优选为1.4-2.0,更优选为1.5-1.8。在漂洗周期循环织物柔软剂(rinse cycle fabric softener)中,所规定的摩尔比使季铵化产品具有高柔软性能。
与所述三-(2-羟乙基)-胺脂肪酸酯的脂肪酸部分相应的脂肪酸优选的碘值为0.5-120,更优选为1-50,且最优选为30-45。所述碘值是指通过100克脂肪酸的双键反应所消耗的碘的总克数,其由ISO 3961所述方法测得。
三-(2-羟乙基)-胺脂肪酸酯的脂肪酸部分优选具有16-18个碳原子,更优选具有16.5-17.8个碳原子的平均链长。所述的平均链长是基于脂肪酸混合物中单独脂肪酸的重量分数来计算得到的。对于支链脂肪酸,链长是指碳原子最长的连续链。
优选的碘值和平均链长可提供如下合适组合:季铵化反应产物在熔点和粘性方面上具有良好的可加工性,以及在漂洗循环织物柔软剂中具有高的织物软化效率。
为了提供所需的平均链长和碘值,所述脂肪酸部分可以衍生于同时包括饱和及不饱和脂肪酸的脂肪酸混合物。所述的不饱和脂肪酸混合物优选单不饱和脂肪酸。所述三-(2-羟乙基)-胺脂肪酸酯包括低于10重量%,优选低于6重量%的多不饱和脂肪酸部分。适宜的饱和脂肪酸的例子是棕榈酸和硬脂酸。适宜的单不饱和脂肪酸的例子是油酸和反油酸。所述不饱和脂肪酸部分的双键中顺式和反式比例优选高于55:45,且更优选高于65:35。所述多不饱和脂肪酸部分的分数可以通过选择性接触氢化作用降低,所述选择性接触氢化作用是指选择性氢化-CH=CH-CH2-CH=CH-子结构中的一个双键但不氢化单不饱和烃基的双键的氢化反应。
所述的三-(2-羟乙基)-胺脂肪酸酯起始材料优选通过以下方法来制备的:用脂肪酸或脂肪酸混合物酯化三乙醇胺,然后减压移除在酯化期间形成的水。以此类方法制备的三-(2-羟乙基)-胺脂肪酸酯可以不进行进一步提纯使用。所希望的碘值、平均链长、以及脂肪酸部分与氮的摩尔比可以通过选择脂肪酸或脂肪酸混合物,以及选择在酯化反应中所用的三乙醇胺和脂肪酸的摩尔比来轻易调整。所述酯化优选在160-210℃的温度下,在蒸馏出水的环境压力下进行,直到理论水量的60-80%被移除。然后逐步地降低压力,直至最终压力在5-50mbar的范围内,反应继续直至达到1-10mg KOH/g,优选2-8mg KOH/g,和更优选2-5mg KOH/g的酸值。
本发明的方法容许制备本发明所述的具有低含量未季铵化的三-(2-羟乙基)-胺脂肪酸酯和低含量甲醇的织物柔软剂活性组合物。
本发明的织物柔软剂活性组合物包括65-98重量%的至少一种三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐。所述组合物另外包括相应的未季铵化三-(2-羟乙基)-胺脂肪酸酯,其含量总共提供2至低于7mg KOH/g,优选4至低于7mg KOH/g,更优选5至低于7mg KOH/g的组合物总胺值。所述总胺值是通过以下方法测定的:根据美国石油化学家协会的Tf 2a-64方法,利用高氯酸进行非水滴定测定,并以每克样品的mgKOH计算总胺值。
基于组合物的重量,本发明所述的织物柔软剂活性组合物还包括1-1500ppm的甲醇,优选10-1000ppm的甲醇,更优选10-800ppm的甲醇,最优选是100-800ppm的甲醇。该甲醇含量比现有技术中通过三-(2-羟乙基)-胺脂肪酸酯与硫酸二甲酯反应制备的且含有相似量的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐和三-(2-羟乙基)-胺脂肪酸酯的织物柔软剂组合物的要低。所述组合物的甲醇含量可以通过用提高已知甲醇量以校准的顶空GLC分析法来测定。为了精确的顶空GLC分析法,所述织物柔软剂组合物优选用适当的溶剂(例如二甲基甲酰胺)稀释以降低其粘度。在本发明所述织物柔软剂活性组合物中的低甲醇含量可以降低对安全保护措施的需要,以及对产品标记和分类的需要,并相比较于现有技术的组合物可以提高组合物的闪点。
本发明所述的织物柔软剂活性组合物还可以包括一种或多种其它的有机溶剂。所述的组合物优选包括最高35重量%的溶剂,所述溶剂选自乙醇、1-丙醇、2-丙醇、乙二醇、二甘醇、丙二醇、二丙醇醚、乙二醇的C1-C4烷基单醚、丙二醇的C1-C4烷基单醚以及其混合物。其它溶剂的量最优选是5-20重量%。更优选的溶剂是乙醇、1-丙醇和2-丙醇,最优选乙醇或2-丙醇,且特别是2-丙醇。
本发明所述织物柔软剂活性组合物的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐优选与上述的本发明方法中优选作为起始材料的三-(2-羟乙基)-胺脂肪酸酯相对应。这意味着优选的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐可以通过用硫酸二甲酯季铵化三-(2-羟乙基)-胺脂肪酸酯来制备。
具体实施方式
实施例
实施例1
市售三-(2-羟乙基)-甲基铵牛油脂肪酸酯甲基硫酸盐的甲醇含量
表1显示了通过顶空GC测量的市售三-(2-羟乙基)-甲基铵牛油脂肪酸酯甲基硫酸盐的甲醇含量。
表1:市售三-(2-羟乙基)-甲基铵牛油脂肪酸酯甲基硫酸盐的甲醇含量
实施例2
三-(2-羟乙基)-胺牛油脂肪酸酯的制备。
将碘值为36的2006g(6.44mol)的牛油脂肪酸和632g(4.26mol)的三乙醇胺的混合物随着搅拌加热至180℃,从反应混合物中蒸馏出水。在此温度下1个小时以后,压力逐步降低至10mbar,且所述混合物在180℃的温度和10mbar下被另外搅拌2个小时。所得到的三-(2-羟乙基)-胺牛油脂肪酸酯的酸值为7.0mg KOH/g,且总胺值为93.7mg KOH/g。
三-(2-羟乙基)-甲基铵牛油脂肪酸酯甲基硫酸盐的制备
实施例3(对比例)
将111.7g(0.89mol)的硫酸二甲酯随着搅拌以小部分加入563g(0.94mol)的来自实施例2的三-(2-羟乙基)-胺牛油脂肪酸酯,将反应混合物冷却至维持温度在60-90℃的范围内。在加入所有硫酸二甲酯后,在85℃下搅拌反应混合物1个小时。然后加入75.1g的2-丙醇并将混合物搅拌均匀。基于组合物的重量,所得组合物的总胺值为4.6mg KOH/g且包含3200ppm的甲醇。
实施例4
将92.2g(0.73mol)的硫酸二甲酯随着搅拌以小部分加入465.6g(0.78mol)的来自实施例2的三-(2-羟乙基)-胺牛油脂肪酸酯和14g(0.17mol)碳酸氢钠的混合物中,将反应混合物冷却至维持温度在60-90℃的范围内。在加入全部硫酸二甲酯后,在85℃下搅拌反应混合物1个小时。然后加入62.0g的2-丙醇,将混合物搅拌至均匀并用压力过滤器过滤以移除未反应的碳酸氢钠。基于所述组合物的重量,所得组合物的总胺值为9.1mg KOH/g,且包含190ppm的甲醇。
实施例5(对比例)
将114.7g(0.91mol)的硫酸二甲酯随着搅拌以小部分加入563g(0.94mol)的来自实施例2的三-(2-羟乙基)-胺牛油脂肪酸酯,将反应混合物冷却至维持温度在60-90℃的范围内。在加入全部硫酸二甲酯后,在85℃下搅拌反应混合物1个小时。然后加入75.3g的2-丙醇并将混合物搅拌至均匀。基于组合物的重量,所得组合物的总胺值为3.1mg KOH/g,且包含4000ppm的甲醇。
实施例6
将86.9g(0.69mol)的硫酸二甲酯随着搅拌以小部分加入428.9g(0.716mol)的来自实施例2的三-(2-羟乙基)-胺牛油脂肪酸酯和10.6g(0.13mol)碳酸氢钠的混合物中,将反应混合物冷却至维持温度在60-90℃的范围内。在加入全部硫酸二甲酯后,在85℃下搅拌反应混合物1个小时。然后加入57.9g的2-丙醇,将所述混合物搅拌至均匀并用压力过滤器过滤以移除未反应的碳酸氢钠。基于组合物的重量,所得组合物的总胺值为6.4mg KOH/g,且包含1100ppm的甲醇。
实施例7
将94.6g(0.75mol)的硫酸二甲酯随着搅拌以小部分加入466.6g(0.78mol)的来自实施例2的三-(2-羟乙基)-胺牛油脂肪酸酯和8.6g(0.147mol)氢氧化镁的混合物中,将反应混合物冷却至维持温度在60-90℃的范围内。在加入全部硫酸二甲酯后,在85℃下搅拌反应混合物1个小时。然后加入63.0g的2-丙醇,将所述混合物搅拌至均匀并用压力过滤器过滤以移除未反应的氢氧化镁。基于组合物的重量,所得组合物的总胺值为6.9mg KOH/g,且包含610ppm的甲醇。
Claims (19)
1.一种制备三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐的方法,其包括用硫酸二甲酯将三-(2-羟乙基)-胺脂肪酸酯季铵化的步骤,所述三-(2-羟乙基)-胺脂肪酸酯包括结构式为N(CH2CH2OH)2(CH2CH2OC(=O)R)的单酯、结构式为N(CH2CH2OH)(CH2CH2OC(=O)R)2的二酯、以及结构式为N(CH2CH2OC(=O)R)3的三酯,其中R是脂肪酸部分RCOO的烃基;其中所述季铵化是在固体酸清除剂存在的情况下进行的,其中所述固体酸清除剂选自:碱金属碳酸盐、碱金属碳酸氢盐、碱土金属碳酸盐、碱土金属氧化物和碱土金属氢氧化物。
2.如权利要求1所述的方法,其中所述固体酸清除剂是碳酸钠或碳酸氢钠。
3.如权利要求1所述的方法,其中所述固体酸清除剂是由平均颗粒尺寸至少为100μm的颗粒组成的。
4.如权利要求1至3中任意一项所述的方法,其中所述固体酸清除剂是通过过滤或离心而从季铵化所产生的反应混合物中分离的。
5.如权利要求4所述的方法,其中在分离固体酸清除剂之前,将选自以下的溶剂加入季铵化所产生的反应混合物中:乙醇、1-丙醇、2-丙醇、乙二醇、二甘醇、丙二醇、二丙醇醚、乙二醇的C1-C4烷基单醚、丙二醇的C1-C4烷基单醚以及它们的混合物。
6.如权利要求5所述的方法,其中用所述溶剂清洗分离的固体酸清除剂,由此产生洗涤液,且所述洗涤液重新用于在季铵化所产生的反应混合物中添加溶剂。
7.如权利要求1至3中任意一项所述的方法,其中硫酸二甲酯和三-(2-羟乙基)-胺脂肪酸酯的摩尔比为0.9-0.98。
8.如权利要求1至3中任意一项所述的方法,其中所述季铵化是在60-95℃的温度下进行的。
9.如权利要求1至3中任意一项所述的方法,其中所述三-(2-羟乙基)-胺脂肪酸酯中脂肪酸部分和氮的平均摩尔比为1.4-2.0。
10.如权利要求1至3中任意一项所述的方法,其中所述三-(2-羟乙基)-胺脂肪酸酯的脂肪酸部分的碘值为0.5-120。
11.如权利要求1至3中任意一项所述的方法,其中所述三-(2-羟乙基)-胺脂肪酸酯的脂肪酸部分具有16-18个碳原子的平均链长。
12.如权利要求1至3中任意一项所述的方法,其中所述三-(2-羟乙基)-胺脂肪酸酯包括低于10摩尔%的多不饱和脂肪酸部分。
13.一种织物柔软剂活性组合物,包括:
65-98重量%的至少一种三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐,
相应的非季铵化三-(2-羟乙基)-胺脂肪酸酯,所述三-(2-羟乙基)-胺脂肪酸酯包括结构式为N(CH2CH2OH)2(CH2CH2OC(=O)R)的单酯、结构式为N(CH2CH2OH)(CH2CH2OC(=O)R)2的二酯、以及结构式为N(CH2CH2OC(=O)R)3的三酯,其中R是脂肪酸部分RCOO的烃基;其量使该组合物的总胺值为2至低于7mg KOH/g,和
1-1500ppm的甲醇。
14.如权利要求13所述的织物柔软剂活性组合物,其包含10-800ppm的甲醇。
15.如权利要求13或14所述的织物柔软剂活性组合物,其另外包括最高35重量%的选自以下的溶剂:乙醇、1-丙醇、2-丙醇、乙二醇、二甘醇、丙二醇、二丙醇醚、乙二醇的C1-C4烷基单醚、丙二醇的C1-C4烷基单醚以及它们的混合物。
16.如权利要求13所述的织物柔软剂活性组合物,其包括65-98重量%的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐,其中的三-(2-羟乙基)-胺脂肪酸酯中脂肪酸部分和氮的平均摩尔比为1.4-2.0。
17.如权利要求13所述的织物柔软剂活性组合物,其包括65-98重量%的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐,其中的脂肪酸部分的碘值为0.5-120。
18.如权利要求13所述的织物柔软剂活性组合物,其包括65-98重量%的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐,其中的脂肪酸部分具有16-18个碳原子的平均链长。
19.如权利要求13所述的织物柔软剂活性组合物,其包括65-98重量%的三-(2-羟乙基)-甲基铵脂肪酸酯甲基硫酸盐,其中的三-(2-羟乙基)-胺脂肪酸酯包括低于10摩尔%的多不饱和脂肪酸部分。
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BR102014025172B1 (pt) * | 2013-11-05 | 2020-03-03 | Evonik Degussa Gmbh | Método para fabricação de um éster de ácido graxo de metisulfato de tris-(2-hidroxietil)-metilamônio, e composição ativa de amaciante de roupa |
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CA3014810A1 (en) | 2016-02-26 | 2017-08-31 | Evonik Degussa Gmbh | Amides of aliphatic polyamines and 12-hydroxyoctadecanoic acid and lipase stable thickener compositions |
RU2740475C2 (ru) | 2016-12-06 | 2021-01-14 | Эвоник Корпорейшн | Органофильные глины и буровые растворы, содержащие их |
Family Cites Families (120)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2430140C3 (de) | 1974-06-24 | 1979-10-04 | Rewo Chemische Werke Gmbh, 6497 Steinau | Kationaktive Bis-(2-Acyloxypropyl)ammonium-Salze, Verfahren zu deren Herstellung und Mittel auf deren Basis |
US4234627A (en) | 1977-02-04 | 1980-11-18 | The Procter & Gamble Company | Fabric conditioning compositions |
GB2007734B (en) | 1977-10-22 | 1983-04-07 | Cargo Fleet Chemical Co | Fabric softeners |
FR2440433A1 (fr) | 1978-11-03 | 1980-05-30 | Unilever Nv | Composition d'assouplissement des etoffes et procede pour la preparer |
USRE32713E (en) | 1980-03-17 | 1988-07-12 | Capsule impregnated fabric | |
US4514461A (en) | 1981-08-10 | 1985-04-30 | Woo Yen Kong | Fragrance impregnated fabric |
DE3402146A1 (de) | 1984-01-23 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | Neue quartaere ammoniumverbindungen, deren herstellung und verwendung als textilweichmacher |
CS246532B1 (cs) | 1984-08-01 | 1986-10-16 | Dagmar Mikulcova | Avivážní prostředek s antistatickým a změkčujícím účinkem |
US4747880A (en) | 1984-12-12 | 1988-05-31 | S. C. Johnson & Son, Inc. | Dry, granular maintenance product reconstitutable to an aqueous clean and shine product |
DE3608093A1 (de) | 1986-03-12 | 1987-09-17 | Henkel Kgaa | Konfektioniertes textilweichmacher-konzentrat |
DE3710064A1 (de) | 1987-03-27 | 1988-10-06 | Hoechst Ag | Verfahren zur herstellung von quaternaeren esteraminen und ihre verwendung |
ATE84566T1 (de) | 1987-05-01 | 1993-01-15 | Procter & Gamble | Quaternaere isopropylesterammonium-verbindungen als faser- und gewebebehandlungsmittel. |
US4789491A (en) | 1987-08-07 | 1988-12-06 | The Procter & Gamble Company | Method for preparing biodegradable fabric softening compositions |
US4882220A (en) | 1988-02-02 | 1989-11-21 | Kanebo, Ltd. | Fibrous structures having a durable fragrance |
US4954285A (en) | 1988-03-07 | 1990-09-04 | The Procter & Gamble Company | Perfume, particles, especially for use in dryer released fabric softening/antistatic agents |
US5002681A (en) | 1989-03-03 | 1991-03-26 | The Procter & Gamble Company | Jumbo particulate fabric softner composition |
US5137646A (en) | 1989-05-11 | 1992-08-11 | The Procter & Gamble Company | Coated perfume particles in fabric softener or antistatic agents |
ES2021900A6 (es) | 1989-07-17 | 1991-11-16 | Pulcra Sa | Procedimiento de obtencion de tensioactivos cationicos derivados de amonio cuaternario con funcion amino-ester. |
DE3932004A1 (de) | 1989-09-26 | 1991-04-04 | Dursol Fabrik Otto Durst Gmbh | Trocknungsmittel fuer lackoberflaechen |
US5185088A (en) | 1991-04-22 | 1993-02-09 | The Procter & Gamble Company | Granular fabric softener compositions which form aqueous emulsion concentrates |
WO1994007979A1 (en) | 1992-09-28 | 1994-04-14 | The Procter & Gamble Company | Method for using solid particulate fabric softener in automatic dosing dispenser |
DE4243701A1 (de) | 1992-12-23 | 1994-06-30 | Henkel Kgaa | Wäßrige Textilweichmacher-Dispersionen |
WO1994019439A1 (en) | 1993-02-25 | 1994-09-01 | Unilever Plc | Use of fabric softening composition |
US5827451A (en) | 1993-03-17 | 1998-10-27 | Witco Corporation | Microemulsion useful as rinse aid |
DE69406797T2 (de) | 1993-08-06 | 1998-06-10 | Procter & Gamble | Trocken-aktivierte gewebekonditionierungs- und antistatische zusammensetzungen die biologisch abbaubare, ungesättigte verbindungen enthalten |
US5391325A (en) | 1993-09-29 | 1995-02-21 | Exxon Chemical Patents Inc. | Non-toxic biodegradable emulsion compositions for use in automatic car washes |
US5427697A (en) | 1993-12-17 | 1995-06-27 | The Procter & Gamble Company | Clear or translucent, concentrated fabric softener compositions |
US5480567A (en) | 1994-01-14 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | Surfactant mixtures for fabric conditioning compositions |
US5869716A (en) * | 1994-03-18 | 1999-02-09 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of esterquats |
US5474691A (en) | 1994-07-26 | 1995-12-12 | The Procter & Gamble Company | Dryer-added fabric treatment article of manufacture containing antioxidant and sunscreen compounds for sun fade protection of fabrics |
DE4430721A1 (de) | 1994-08-30 | 1996-03-07 | Hoechst Ag | Autoglanztrocknungsmittel |
US5830845A (en) | 1996-03-22 | 1998-11-03 | The Procter & Gamble Company | Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor |
AR006355A1 (es) | 1996-03-22 | 1999-08-25 | Procter & Gamble | Activo suavizante biodegradable y composicion que lo contiene |
US5759990A (en) | 1996-10-21 | 1998-06-02 | The Procter & Gamble Company | Concentrated fabric softening composition with good freeze/thaw recovery and highly unsaturated fabric softener compound therefor |
US5916863A (en) | 1996-05-03 | 1999-06-29 | Akzo Nobel Nv | High di(alkyl fatty ester) quaternary ammonium compound from triethanol amine |
GB9617612D0 (en) | 1996-08-22 | 1996-10-02 | Unilever Plc | Fabric conditioning composition |
CN1238000A (zh) | 1996-09-19 | 1999-12-08 | 普罗格特-甘布尔公司 | 含有阳离子聚合物的浓缩型季铵织物柔软剂组合物 |
DE19708133C1 (de) | 1997-02-28 | 1997-12-11 | Henkel Kgaa | Mittel für die Avivage von Textil- und Keratinfasern sowie die Verwendung von Hydroxycarbonsäureestern zur Herstellung von Avivagemitteln |
US5874396A (en) | 1997-02-28 | 1999-02-23 | The Procter & Gamble Company | Rinse added laundry additive compositions having color care agents |
KR100531564B1 (ko) | 1997-05-01 | 2005-11-29 | 시바 스페셜티 케미칼스 홀딩 인크. | 폴리디오가노실록산을 포함하는 직물 유연제 조성물 |
US6645479B1 (en) | 1997-09-18 | 2003-11-11 | International Flavors & Fragrances Inc. | Targeted delivery of active/bioactive and perfuming compositions |
WO1999035120A1 (en) | 1998-01-09 | 1999-07-15 | Witco Corporation | Novel quaternary ammonium compounds, compositions containing them, and uses thereof |
ZA991635B (en) | 1998-03-02 | 1999-09-02 | Procter & Gamble | Concentrated, stable, translucent or clear, fabric softening compositions. |
GB9816659D0 (en) | 1998-07-30 | 1998-09-30 | Dow Europ Sa | Composition useful for softening, cleaning, and personal care applications and processes for the preparation thereof |
EP0990695A1 (de) | 1998-09-30 | 2000-04-05 | Witco Surfactants GmbH | Weichspülmittel mit farberhaltender Wirkung |
DE19855366A1 (de) * | 1998-12-01 | 2000-06-08 | Witco Surfactants Gmbh | Niedrigkonzentrierte, hochviskose wäßrige Weichspülmittel |
EP1018541A1 (de) | 1999-01-07 | 2000-07-12 | Goldschmidt Rewo GmbH & Co. KG | Klare Weichspülmittelformulierungen |
DE19906367A1 (de) | 1999-02-16 | 2000-08-17 | Clariant Gmbh | Verwendung von Kammpolymeren als Schutzablösepolymere |
US6916781B2 (en) | 1999-03-02 | 2005-07-12 | The Procter & Gamble Company | Concentrated, stable, translucent or clear, fabric softening compositions |
US6458343B1 (en) | 1999-05-07 | 2002-10-01 | Goldschmidt Chemical Corporation | Quaternary compounds, compositions containing them, and uses thereof |
US6995131B1 (en) | 1999-05-10 | 2006-02-07 | The Procter & Gamble Company | Clear or translucent aqueous fabric softener compositions containing high electrolyte and optional phase stabilizer |
US6235914B1 (en) | 1999-08-24 | 2001-05-22 | Goldschmidt Chemical Company | Amine and quaternary ammonium compounds made from ketones and aldehydes, and compositions containing them |
JP2003511572A (ja) | 1999-10-05 | 2003-03-25 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | 布地柔軟剤組成物 |
JP4024438B2 (ja) | 1999-11-01 | 2007-12-19 | 花王株式会社 | 第4級アンモニウム塩組成物 |
DE69924623T2 (de) | 1999-12-07 | 2006-03-09 | The Procter & Gamble Company, Cincinnati | Verfahren zum Schaffen von Tragekomfort |
US6200949B1 (en) | 1999-12-21 | 2001-03-13 | International Flavors And Fragrances Inc. | Process for forming solid phase controllably releasable fragrance-containing consumable articles |
GB0002877D0 (en) | 2000-02-08 | 2000-03-29 | Unilever Plc | Fabric conditioning composition |
FR2806307B1 (fr) | 2000-03-20 | 2002-11-15 | Mane Fils V | Preparation parfumee solide sous forme de microbilles et utilisation de ladite preparation |
MXPA02011555A (es) | 2000-05-24 | 2003-04-25 | Procter & Gamble | Una composicion suavizante de telas que comprende un agente de control del mal olor. |
GB0012958D0 (en) | 2000-05-26 | 2000-07-19 | Unilever Plc | Fabric conditioning composition |
EP1199340B1 (en) | 2000-10-19 | 2005-03-09 | Soft99 Corporation | Paintwork coating composition and coating cloth |
DE60204549T2 (de) | 2001-03-07 | 2006-03-23 | The Procter & Gamble Company, Cincinnati | Weichspülmittelzusammensetzung für die anwendung in anwesenheit von waschmittelrückständen |
GB0106560D0 (en) | 2001-03-16 | 2001-05-02 | Quest Int | Perfume encapsulates |
ES2258506T3 (es) | 2001-12-24 | 2006-09-01 | Cognis Ip Management Gmbh | Composiciones cationicas para la limpieza de superficies duras. |
WO2003061817A1 (de) | 2002-01-24 | 2003-07-31 | Bayer Aktiengesellschaft | Mikrokapseln enthaltende koagulate |
US20030158344A1 (en) | 2002-02-08 | 2003-08-21 | Rodriques Klein A. | Hydrophobe-amine graft copolymer |
US7381697B2 (en) | 2002-04-10 | 2008-06-03 | Ecolab Inc. | Fabric softener composition and methods for manufacturing and using |
US7087572B2 (en) | 2002-04-10 | 2006-08-08 | Ecolab Inc. | Fabric treatment compositions and methods for treating fabric in a dryer |
US20060277689A1 (en) | 2002-04-10 | 2006-12-14 | Hubig Stephan M | Fabric treatment article and methods for using in a dryer |
US7053034B2 (en) | 2002-04-10 | 2006-05-30 | Salvona, Llc | Targeted controlled delivery compositions activated by changes in pH or salt concentration |
US20030216488A1 (en) | 2002-04-18 | 2003-11-20 | The Procter & Gamble Company | Compositions comprising a dispersant and microcapsules containing an active material |
US20030215417A1 (en) | 2002-04-18 | 2003-11-20 | The Procter & Gamble Company | Malodor-controlling compositions comprising odor control agents and microcapsules containing an active material |
US6740631B2 (en) | 2002-04-26 | 2004-05-25 | Adi Shefer | Multi component controlled delivery system for fabric care products |
MXPA04011328A (es) | 2002-05-16 | 2005-02-14 | Procter & Gamble | Composicion que se agrega en el enjuague para el tratamiento de telas y metodos y usos del mismo. |
EP1393706A1 (en) | 2002-08-14 | 2004-03-03 | Quest International B.V. | Fragranced compositions comprising encapsulated material |
US7125835B2 (en) | 2002-10-10 | 2006-10-24 | International Flavors & Fragrances Inc | Encapsulated fragrance chemicals |
US7585824B2 (en) | 2002-10-10 | 2009-09-08 | International Flavors & Fragrances Inc. | Encapsulated fragrance chemicals |
US20040071742A1 (en) | 2002-10-10 | 2004-04-15 | Popplewell Lewis Michael | Encapsulated fragrance chemicals |
US7659238B2 (en) | 2002-11-29 | 2010-02-09 | Ciba Specialty Chemicals Corp. | Fabric softener compositions comprising homo- and/or copolymers |
KR20050099508A (ko) | 2003-02-03 | 2005-10-13 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | 세탁제 및 직물 유연제 제제 |
US7135451B2 (en) | 2003-03-25 | 2006-11-14 | The Procter & Gamble Company | Fabric care compositions comprising cationic starch |
US20050014672A1 (en) | 2003-07-18 | 2005-01-20 | Shoaib Arif | Rinse aid additive and composition containing same |
JP4633722B2 (ja) * | 2003-10-16 | 2011-02-16 | ザ プロクター アンド ギャンブル カンパニー | 特定の小胞透過性を有する小胞を含む水性組成物 |
US7977303B2 (en) | 2004-02-27 | 2011-07-12 | The Procter & Gamble Company | Multiple use fabric conditioning block with indentations |
EP1584674B1 (en) | 2004-03-29 | 2007-08-15 | Clariant Produkte (Deutschland) GmbH | Easy-dispersible concentrate ester quat compositions |
US7704940B2 (en) | 2004-04-09 | 2010-04-27 | The Sun Products Corporation | Granulate for use in a cleaning product and process for its manufacture |
EP1838827A1 (en) | 2004-10-18 | 2007-10-03 | The Procter and Gamble Company | Concentrated fabric softener active compositions |
DE102005020551A1 (de) | 2005-05-03 | 2006-11-09 | Degussa Ag | Feste, redispergierbare Emulsion |
US20060252669A1 (en) | 2005-05-06 | 2006-11-09 | Marija Heibel | Fabric care composition comprising polymer encapsulated fabric or skin beneficiating ingredient |
JP4757711B2 (ja) * | 2005-06-01 | 2011-08-24 | 花王株式会社 | 透明又は半透明の液体柔軟剤組成物 |
US20070054835A1 (en) | 2005-08-31 | 2007-03-08 | The Procter & Gamble Company | Concentrated fabric softener active compositions |
DE602006004426D1 (de) | 2005-09-06 | 2009-02-05 | Clariant Brazil S A | Stabile wässrige Esterquat-Zusammensetztungen |
DE602006021041D1 (de) | 2005-09-22 | 2011-05-12 | Procter & Gamble | Weichspülerzusammensetzung mit verringerter stoffeinfärbung |
US7572761B2 (en) | 2005-11-14 | 2009-08-11 | Evonik Degussa Gmbh | Process for cleaning and softening fabrics |
WO2007092020A1 (en) * | 2006-02-10 | 2007-08-16 | Stepan Company | Fabric conditioning active compositions |
WO2007099505A1 (en) | 2006-02-28 | 2007-09-07 | The Procter & Gamble Company | Fabric care compositions comprising cationic starch |
ES2294923B1 (es) | 2006-03-31 | 2009-02-16 | Kao Corporation, S.A. | Composicion para el enjuague y secado de vehiculos. |
EP1849855A1 (de) | 2006-04-27 | 2007-10-31 | Degussa GmbH | Thixotrope Weichspülmittel |
EP1876223B1 (en) | 2006-07-06 | 2009-02-18 | Clariant (Brazil) S.A. | Concentrated esterquat composition |
WO2008021892A1 (en) | 2006-08-08 | 2008-02-21 | The Procter & Gamble Company | Fabric enhancers comprising nano-sized lamellar vesicle |
ES2479116T3 (es) | 2007-02-28 | 2014-07-23 | Unilever N.V. | Composiciones de tratamiento de telas, su fabricación y uso |
US20080242584A1 (en) | 2007-04-02 | 2008-10-02 | Errol Hoffman Wahl | Fabric care composition |
US20110237667A1 (en) | 2007-08-06 | 2011-09-29 | Clariant Finance (Bvi) Limited | Compositions Containing Diethanol Amine Esterquats |
MY151001A (en) * | 2007-12-28 | 2014-03-31 | Malaysian Palm Oil Board Mpob | Fatty acid compositions of methyl ester for esterquats production suitable for fabric softener |
US8080513B2 (en) | 2008-01-11 | 2011-12-20 | The Procter & Gamble Company | Method of shipping and preparing laundry actives |
US8361953B2 (en) | 2008-02-08 | 2013-01-29 | Evonik Goldschmidt Corporation | Rinse aid compositions with improved characteristics |
ES2647570T3 (es) | 2009-11-06 | 2017-12-22 | The Procter & Gamble Company | Cápsulas de alta eficacia que comprenden agente beneficioso |
JP5431619B2 (ja) * | 2010-04-01 | 2014-03-05 | ザ プロクター アンド ギャンブル カンパニー | 柔軟仕上げ剤 |
MY160707A (en) | 2010-04-01 | 2017-03-15 | Evonik Degussa Gmbh | Fabric softener active composition |
US8183199B2 (en) | 2010-04-01 | 2012-05-22 | The Procter & Gamble Company | Heat stable fabric softener |
US20110239377A1 (en) | 2010-04-01 | 2011-10-06 | Renae Dianna Fossum | Heat Stable Fabric Softener |
ES2536849T3 (es) | 2010-04-01 | 2015-05-29 | Evonik Degussa Gmbh | Composición de sustancia activa suavizante de tejidos |
MX2012012340A (es) | 2010-04-28 | 2012-11-21 | Evonik Degussa Gmbh | Composicion suavizante de telas. |
US8507425B2 (en) | 2010-06-29 | 2013-08-13 | Evonik Degussa Gmbh | Particulate fabric softener comprising ethylenediamine fatty acid amides and method of making |
EP2632893B1 (en) * | 2010-10-25 | 2018-12-05 | Stepan Company | Esteramines and derivatives from natural oil metathesis |
JP5897321B2 (ja) * | 2011-12-26 | 2016-03-30 | 花王株式会社 | 袋状柔軟剤物品 |
WO2013113453A1 (en) | 2012-01-30 | 2013-08-08 | Evonik Industries Ag | Fabric softener active composition |
JP6233303B2 (ja) * | 2012-03-30 | 2017-11-22 | 三菱ケミカル株式会社 | エポキシ化合物の製造方法及びエポキシ化反応用触媒組成物 |
DK2847307T3 (en) * | 2012-05-07 | 2016-07-25 | Evonik Degussa Gmbh | ACTIVE SOFT COMPOSITION FOR TEXTILES AND PROCEDURES FOR MANUFACTURING THEREOF |
BR102014025172B1 (pt) * | 2013-11-05 | 2020-03-03 | Evonik Degussa Gmbh | Método para fabricação de um éster de ácido graxo de metisulfato de tris-(2-hidroxietil)-metilamônio, e composição ativa de amaciante de roupa |
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- 2014-10-09 BR BR102014025172-3A patent/BR102014025172B1/pt active IP Right Grant
- 2014-10-10 CN CN201410531796.3A patent/CN104610102B/zh active Active
- 2014-10-15 PL PL14188997T patent/PL2868654T3/pl unknown
- 2014-10-15 EP EP14188997.2A patent/EP2868654B1/en active Active
- 2014-10-15 ES ES14188997T patent/ES2703113T3/es active Active
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- 2014-10-17 MX MX2014012611A patent/MX363849B/es active IP Right Grant
- 2014-10-31 KR KR1020140149959A patent/KR102234671B1/ko active IP Right Grant
- 2014-11-03 US US14/531,507 patent/US10011806B2/en active Active
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BR102014025172A2 (pt) | 2015-09-29 |
MX2014012611A (es) | 2016-06-30 |
US10011806B2 (en) | 2018-07-03 |
BR102014025172B1 (pt) | 2020-03-03 |
PL2868654T4 (pl) | 2019-05-31 |
CN104610102A (zh) | 2015-05-13 |
MX2019001375A (es) | 2019-06-24 |
PL2868654T3 (pl) | 2019-05-31 |
KR20150051889A (ko) | 2015-05-13 |
US20150126431A1 (en) | 2015-05-07 |
JP2015089889A (ja) | 2015-05-11 |
EP2868654A1 (en) | 2015-05-06 |
MX363849B (es) | 2019-04-05 |
KR102234671B1 (ko) | 2021-04-02 |
EP2868654B1 (en) | 2018-09-19 |
JP6347723B2 (ja) | 2018-06-27 |
ES2703113T3 (es) | 2019-03-07 |
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