CN104471044B - 织物软化剂活性组合物及其制备方法 - Google Patents
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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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Abstract
使至少一种三‑(2‑羟基乙基)‑胺脂肪酸酯与硫酸二甲酯以硫酸二甲酯与胺氮的摩尔比为0.79‑0.94进行反应,直到反应混合物的总胺数为7‑20mg KOH/g,得到具有低含量甲醇的织物软化剂活性组合物,其包含65‑98%重量的三‑(2‑羟基乙基)‑甲基甲基硫酸铵脂肪酸酯和1‑1500ppm的甲醇。
Description
本发明涉及包含三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯(tris-(2-hydroxyethyl)-methylammonium methylsulfate fatty acid esters)且具有低含量的甲醇的织物软化剂活性组合物及制备这种组合物的方法。
已发现带有两个疏水性长链烃部分的季铵盐具有作为织物软化剂活性物的广泛用途。以每分子平均两个脂肪酸部分酯化的链烷醇胺的季铵盐通常称为酯季铵盐,由于它们的生物降解能力,其已很大程度上替代了早期的烷基季铵化合物。
已发现由用硫酸二甲酯季铵化三乙醇胺的脂肪酸酯制备的三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯具有作为织物软化剂活性物的广泛用途。由于硫酸二甲酯是一种潜在致癌物,为了获得硫酸二甲酯的完全转化和胺的高转化率,进行季铵反应。现在发现如此制备的三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯包含出人意料高含量的甲醇。尽管三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯软化剂活性物已使用了超过20年,但是迄今为止这些组合物中高含量的甲醇仍然未引起注意。
由于甲醇是有毒的,且存在工作场所危害,因此需要提供包含三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的织物软化剂活性组合物,其中该组合物具有低含量的甲醇。还需要一种制备这种组合物的简单的方法。
现在发现包含三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯且具有低含量的甲醇的织物软化剂活性组合物可以通过使三乙醇胺的脂肪酸酯与硫酸二甲酯在反应条件下反应制备,在所述反应条件中在硫酸二甲酯完全转化下获得比现有技术方法更高的总胺值。
因此,本发明涉及织物软化剂活性组合物,其包含:
a)65-98%重量的至少一种三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯,
b)至少一种三-(2-羟基乙基)-胺脂肪酸酯,其含量使所述组合物的总胺数为7-20mg KOH/g,和
c)1-1500ppm的甲醇。
本发明进一步涉及制备织物软化剂活性组合物的方法,所述织物软化剂活性组合物包含65-98%重量的三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯和1-1500ppm的甲醇,其中至少一种三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯以硫酸二甲酯与胺氮的摩尔比为0.79-0.94进行反应,直到反应混合物的总胺数为7-20mg KOH/g。
本发明的织物软化剂活性组合物包含65-98%重量的至少一种三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯。所述组合物进一步包含至少一种三-(2-羟基乙基)-胺脂肪酸酯,其含量使所述组合物的总胺数为7-20mg KOH/g,优选8-13mg KOH/g,更优选9-12mgKOH/g。总胺数是根据American Oil Chemists Society的方法Tf2a-64通过用高氯酸进行非水滴定测定的,并且计算为mg KOH/g样品。
三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分可以来源于式RCOOH的纯脂肪酸或脂肪酸的混合物,其中R为烃基。所述烃基可以是带支链的或无支链的,优选为无支链的。所述三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分可以来源于相同的或不同的脂肪酸或脂肪酸的混合物。优选地,三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯和三-(2-羟基乙基)-胺脂肪酸酯具有相同的脂肪酸部分。
三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯可以包括式CH3N+(CH2CH2OH)2(CH2CH2OC(=O)R)CH3OSO3 -的单酯、式CH3N+(CH2CH2OH)(CH2CH2OC(=O)R)2CH3OSO3 -的二酯和式CH3N+(CH2CH2OC(=O)R)3CH3OSO3 -的三酯,其中R为脂肪酸部分RCOO的烃基。三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分与氮的平均摩尔比优选为1.4-2.0,更优选为1.5-1.8。特定的摩尔比在漂洗周期织物软化剂(rinse cycle fabric softener)中提供了高软化性能。
对应于所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分的脂肪酸优选地具有0.5-120,更优选1-50且最优选30-45的碘值。碘值为100g脂肪酸的双键反应消耗的以g计碘的量,通过ISO 3961的方法测定。所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分的平均链长优选为16-18、更优选16.5-17.8个碳原子。平均链长是基于脂肪酸混合物中单 个脂肪酸的重量分数计算的。对于支链脂肪酸,链长指碳原子的最长连续链。
优选的碘值和平均链长在熔点和粘度方面提供了织物软化剂组合物的良好加工性能的适当组合,且在漂洗周期织物软化剂方面提供了高织物软化效率。
为了提供所需平均链长和碘值,脂肪酸部分可以来源于包含饱和脂肪酸和不饱和脂肪酸的脂肪酸的混合物。不饱和脂肪酸优选地为单不饱和脂肪酸。三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯优选地包括少于10%重量的多不饱和脂肪酸部分,更优选地少于6%重量。适合的饱和脂肪酸的实例为棕榈酸和硬脂酸。适合的单不饱和脂肪酸的实例为油酸和反油酸。不饱和脂肪酸部分的双键的顺式-反式比例优选地高于55∶45,且更优选地高于65∶35。多不饱和脂肪酸部分的分数可以通过选择性接触氢化减少,选择性接触氢化是一种选择性地氢化-CH=CH-CH2-CH=CH-子结构中的一个双键但不氢化单不饱和的烃基的双键的氢化作用。
本发明的织物软化剂活性组合物还包含基于组合物的重量计1-1500ppm的甲醇,优选10-800ppm的甲醇。该甲醇含量低于现有技术中通过使三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯反应制备的包含相似量的三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的织物软化剂组合物。该组合物的甲醇含量可以通过用已知量的甲醇的峰校准(spiking)的顶空GLC(head space GLC)分析测定。织物软化剂组合物优选地用适合的溶剂比如二甲基甲酰胺稀释,以降低精确的顶空GLC分析的粘度。与现有技术组合物相比,本发明的织物软化剂活性组合物中甲醇的含量较低减少了工作安全预防的需要和对产品标识和分类的要求,且升高了组合物的闪点。
本发明的织物软化剂活性组合物可以进一步包含一种或多种另外的有机溶剂。所述组合物优选地包含至多35%重量的溶剂,所述溶剂选自乙醇、1-丙醇、2-丙醇、乙二醇、二乙二醇、丙二醇、二丙二醇、乙二醇的C1-C4烷基单醚和丙二醇的C1-C4-烷基单醚。另外的溶剂的量最优选地为5-20%重量。更优选的溶剂为乙醇、1-丙醇和2-丙醇,最优选乙醇或2-丙醇,尤其是2-丙醇。
本发明的织物软化剂活性组合物可以通过本发明的方法制备,其中至少一种三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯以硫酸二甲酯与胺氮的摩尔比为0.79-0.94反应,直到反应混合物的总胺数为7-20mg KOH/g。总胺数可以根据American Oil ChemistsSociety的方法Tf2a-64通过用高氯酸进行非水滴定测定,并且计算为mg KOH/g样品。一旦达到该范围中期望的总胺数,则可以通过降低温度中止反应。优选地,反应持续,直到基本上所有的硫酸二甲酯已经反应。
选择特定范围内硫酸二甲酯与胺氮的摩尔比并进行反应直到总胺数达到7-20mgKOH/g,提供了硫酸二甲酯的高转化,且同时避免了形成的甲醇量超过1500ppm。
硫酸二甲酯与胺氮的摩尔比优选地在0.85-0.90范围内选择。三-(2-羟基乙基)-胺脂肪酸酯优选地与硫酸二甲酯在60-95℃、更优选地70-90℃的温度下反应。优选地进行反应直到反应混合物具有的总胺数为8-13mg KOH/g,最优选9-12mg KOH/g。三-(2-羟基乙基)-胺脂肪酸酯可以与硫酸二甲酯在任何压力(比如环境压力或减压)下反应。三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯的反应可以在另外的溶剂存在下进行,但是优选地在不加入溶剂下进行。
在本发明的方法中使用的三-(2-羟基乙基)-胺脂肪酸酯优选地具有的脂肪酸部分与氮的平均摩尔比为1.4-2.0,更优选1.5-1.8。三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分的碘值优选地为0.5到120,更优选1-50。三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分的平均链长优选地为16-18、更优选16.5-17.8个碳原子。
三-(2-羟基乙基)-胺脂肪酸酯起始原料优选地是通过如下制备:用脂肪酸或脂肪酸混合物酯化三乙醇胺,在减压下除去酯化期间形成的水。可以使用如此制备的三-(2-羟基乙基)-胺脂肪酸酯而无需进一步纯化。期望的碘值、平均链长和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和酯化反应中使用的三乙醇胺与脂肪酸的摩尔比来容易地调节。酯化优选地在160-210℃的温度下,在环境压力下进行,蒸馏出水直到已经除去理论值60-80%的水。然后,将压力逐步降低至20-50mbar范围内的最终压力,反应继续直到达到酸值为1-10mg KOH/g,更优选2-5mg KOH/g。
通过下述非限制性实例阐述本发明,然而其并不意味着以任何方式限制本发明的范围。
实施例
实施例1:
市售三-(2-羟基乙基)-甲基甲基硫酸铵牛脂脂肪酸酯的甲醇含量
表1显示通过顶空GC测定的市售三-(2-羟基乙基)-甲基甲基硫酸铵牛脂脂肪酸酯的甲醇含量
表1
市售三-(2-羟基乙基)-甲基甲基硫酸铵牛脂脂肪酸酯的甲醇含量
实施例2:
三-(2-羟基乙基)-胺牛脂脂肪酸酯的制备
将3513g(12.82mol)碘值为38的牛脂脂肪酸和1115g(7.47mol)三乙醇胺的混合物加热至190℃,同时搅拌,从反应混合物蒸馏出水。在2小时后,在该温度下,将压力逐步降低至20mbar,并在190℃和20mbar下再搅拌该混合物3小时。此后,将反应混合物冷却至60℃。所得到的三-(2-羟基乙基)-胺牛脂脂肪酸具有3.6mg KOH/g的酸值和95.2mg KOH/g的总胺。
三-(2-羟基乙基)甲基甲基硫酸铵牛脂脂肪酸酯的制备
实施例3:
将167.7g(1.33mol)的硫酸二甲酯在搅拌下以小份加入818g(1.387mol)来自实施例 2的三-(2-羟基乙基)-胺牛脂脂肪酸酯中,冷却该反应混合 物以保持温度范围为70-90℃。在加入所有硫酸二甲酯之后,在80-90℃下搅拌反应混合物1小时。然后,加入109.5g的2-丙醇,并搅拌该混合物直至均相。基于组合物的重量计,所得到的组合物的总胺数为3.4mg KOH/g,且包含4450ppm的甲醇。
实施例4:
使用160.44g(1.272mol)的硫酸二甲酯、808.8g(1.369mol)来自实施例 2的三-(2-羟基乙基)-胺牛脂脂肪酸酯和107.47g的2-丙醇重复实施例3。基于组合物的重量计,所得到的组合物的总胺数为6.0mg KOH/g,且包含3000ppm的甲醇。
实施例5:
使用144.55g(1.146mol)的硫酸二甲酯、755.4g(1.282mol)来自实施例2的三-(2-羟基乙基)-胺牛脂脂肪酸酯和100.0g的2-丙醇重复实施例3。基于组合物的重量计,所得到的组合物的总胺数为8.9mg KOH/g,且包含1400ppm的甲醇。
实施例6:
使用135.1g(1.072mol)的硫酸二甲酯、780.1g(1.324mol)来自实施例2的三-(2-羟基乙基)-胺牛脂脂肪酸酯和102.0g的2-丙醇重复实施例3。基于组合物的重量计,所得到的组合物的总胺数为17.2mg KOH/g,且包含155ppm的甲醇。
实施例3和4(不根据本发明)及实施例5和6(根据本发明)证实如何可通过选择三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯的正确摩尔比控制织物软化剂组合物的甲醇含量并进行季铵化反应,以使反应混合物的总胺数为7-20mg KOH/g。
实施例7(比较实施例):
重复专利US 6,995,131的第43栏第37-53行描述的含有来源于部分氢化的菜籽油脂肪酸(canola fatty acid)的酰基的二(酰氧基乙基)(2-羟基乙基)甲基甲基硫酸铵的制备。基于组合物的重量计,所得到的组合物包含5500ppm的甲醇。
Claims (14)
1.织物软化剂活性组合物,其包含
a)65-98%重量的至少一种三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯,
b)至少一种三-(2-羟基乙基)-胺脂肪酸酯,其含量使所述组合物的总胺数为7-20mgKOH/g,和
c)1-1500ppm的甲醇。
2.权利要求1的织物软化剂活性组合物,其包含10-800ppm的甲醇。
3.权利要求1或2的织物软化剂活性组合物,其中所述三-(2羟基乙基)-胺脂肪酸酯的含量使所述组合物的总胺数为8-13mg KOH/g。
4.权利要求1或2的织物软化剂活性组合物,其中所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯和所述三-(2-羟基乙基)-胺脂肪酸酯具有相同的脂肪酸部分。
5.权利要求1或2的织物软化剂活性组合物,其中所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分与氮的平均摩尔比为1.4-2.0。
6.权利要求1或2的织物软化剂活性组合物,其中对应于所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分的脂肪酸的碘值为0.5-120。
7.权利要求1或2的织物软化剂活性组合物,其中所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯的脂肪酸部分的平均链长为16-18个碳原子。
8.权利要求1或2的织物软化剂活性组合物,其中所述三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯包含少于10mol%的多不饱和脂肪酸部分。
9.权利要求1或2的织物软化剂活性组合物,其进一步包含至多35%重量的溶剂,所述溶剂选自乙醇、1-丙醇、2-丙醇、乙二醇、二乙二醇、丙二醇、二丙二醇、乙二醇的C1-C4烷基单醚和丙二醇的C1-C4-烷基单醚。
10.用于制备织物软化剂活性组合物的方法,所述织物软化剂活性组合物包含65-98%重量的三-(2-羟基乙基)-甲基甲基硫酸铵脂肪酸酯和1-1500ppm的甲醇,其中至少一种三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯以硫酸二甲酯与胺氮的摩尔比为0.79-0.94进行反应,直到反应混合物的总胺数为7-20mg KOH/g。
11.权利要求10的方法,其中所述三-(2-羟基乙基)-胺脂肪酸酯与硫酸二甲酯在60-95℃的温度下反应。
12.权利要求10或11的方法,其中所述三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分与氮的平均摩尔比为1.4-2.0。
13.权利要求10或11的方法,其中所述三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分的碘值为0.5到120。
14.权利要求10或11的方法,其中所述三-(2-羟基乙基)-胺脂肪酸酯的脂肪酸部分的平均链长为16-18个碳原子。
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CN1221447A (zh) * | 1996-05-03 | 1999-06-30 | 阿克佐诺贝尔公司 | 由三乙醇胺制备高含量二(烷基脂肪酯)季铵盐化合物 |
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Also Published As
Publication number | Publication date |
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BR112014027174B1 (pt) | 2021-04-06 |
EP2847307B1 (en) | 2016-04-06 |
BR112014027174A2 (pt) | 2017-06-27 |
JP2015517610A (ja) | 2015-06-22 |
WO2013167376A1 (en) | 2013-11-14 |
US20150080286A1 (en) | 2015-03-19 |
KR101694599B1 (ko) | 2017-01-09 |
MX366465B (es) | 2019-07-10 |
JP5992605B2 (ja) | 2016-09-14 |
DK2847307T3 (en) | 2016-07-25 |
US9441187B2 (en) | 2016-09-13 |
ES2580031T3 (es) | 2016-08-18 |
KR20150013490A (ko) | 2015-02-05 |
PL2847307T3 (pl) | 2016-10-31 |
EP2847307A1 (en) | 2015-03-18 |
MX2014013397A (es) | 2015-01-19 |
CN104471044A (zh) | 2015-03-25 |
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