CN103097506B - 溶剂组合物 - Google Patents
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Abstract
本发明涉及溶剂组合物,其含有(a)羧酸二烷基酰胺、(b)脂肪酸或其盐和(c)氧化乙烯-氧化丙烯共聚物。
Description
发明领域
本发明涉及环境友好的所谓绿色溶剂的领域,以及涉及含有羧酸酰胺的溶剂组合物,其具有改进的在硬水中的溶解性。
发明背景
近年来,对于环境友好的所谓绿色溶剂的需求日益增加。尤其是,数十年来用于许多技术领域中的溶剂例如甲苯、枯烯、NMP等正等待用显示至少相当性能且同时毒性较小和具有改进的生物降解性的替代品代替。在这些溶剂中,羧酸酰胺,尤其是从可更新来源的脂肪酸获得的那些羧酸酰胺,越来越普遍,这同时是由于它们的加溶能力和它们的有利的生态毒性行为。尤其是,脂肪酸酰胺用作农业中的溶剂,用于使金属表面脱脂,用作加工助剂等。
但是,这类溶剂的主要缺点是与它们在自来水中的溶解性差有关的,自来水显示水硬度达到500ppm钙和/或镁离子。虽然所述酰胺能在不存在碱土金属离子的情况下很好地溶于水,但是其溶解性在水转变成“硬”水的情况下显著降低。所以,本发明要解决的问题是通过加入特定的乳化剂或分散剂改进羧酸酰胺的硬水溶解性,且不会降低所述酰胺的加溶能力。
本发明的详细描述
本发明涉及溶剂组合物,其含有:
(a)羧酸酰胺,
(b)脂肪酸或其盐,和
(c)氧化乙烯-氧化丙烯共聚物。
惊奇地发现,仅仅少量的含有脂肪酸或脂肪酸皂以及聚乙二醇-聚丙二醇类型且任选被烷基或烷基酚基团封端的非离子聚合物的共混物就显示出明显改进羧酸酰胺在硬水中的溶解性的能力,所述硬水显示具有钙和镁离子的浓度达到500ppm。发现含有所述酰胺、脂肪酸和聚合物的混合物非常适合作为环境友好的绿色溶剂用于各种目的,例如用于制备农用化学品、脱脂剂、工艺流体等。尤其是,本发明的混合物也允许基于具有高水硬度的自来水制备含水浓缩物,例如含水的杀微生物浓缩物。
羧酸酰胺
作为本发明组合物中的代表性组分,羧酸酰胺通常具有以下通式(I):
R1CO-NR2R3 (I)
其中R1CO表示任选被羟基取代的、饱和或不饱和的、直链或支化的具有6-22个、优选8-12个碳原子的酰基,R2表示氢或具有1-12个碳原子的烷基,R3表示具有1-12个碳原子的烷基。在第一个优选实施方案中,本发明的羧酸酰胺表示羧酸二烷基酰胺,更尤其是二甲基酰胺、二丁基酰胺、二辛基酰胺,或二-2-乙基己基酰胺。另外发现有用的是以单独或组合方式选自以下的二烷基酰胺:癸酸二甲基酰胺,癸酸二丁基酰胺,癸酸二辛基酰胺,癸酸二-2-乙基己基酰胺,辛酸二甲基酰胺,辛酸二丁基酰胺,辛酸二辛基酰胺,辛酸二-2-乙基己基酰胺,己酸二甲基酰胺,己酸二丁基酰胺,己酸二-2-乙基己基酰胺,月桂酸二甲基酰胺,月桂酸二丁基酰胺,月桂酸二-2-乙基己基酰胺,乳酸二甲基酰胺,乳酸二丁基酰胺,乳酸二-2-乙基己基酰胺,以及它们的混合物。
脂肪酸和其盐
脂肪酸或其盐(组分b)代表主要乳化剂,将其加入羧酸酰胺中以改进它们的硬水溶解性。通常,这些化合物具有以下通式(II):
R4C O-OX (II)
其中R4CO表示饱和或不饱和的、直链或支化的具有6-36个、优选12-22个碳原子的酰基,X表示氢、碱金属、碱土金属、铵或烷基铵。典型的例子是选自以下的脂肪酸:月桂酸,肉豆蔻酸,棕榈酸,硬脂酸,油酸,亚油酸(linolic acid),亚油酸(linoleic acid),山嵛酸,芥酸,或它们的工业混合物,例如可以从天然甘油三酯例如椰油、棕榈油、棕榈壳油、橄榄油、红花油、葵花油等获得。在另一个优选实施方案中,脂肪酸是衍生自松浆油(“松浆油脂肪酸”),其具有平均12-18个碳原子且碘值高于20。
氧化乙烯-氧化丙烯共聚物
氧化乙烯-氧化丙烯共聚物(组分c)表示在组合物中的助乳化组分。通常,这些聚合物具有以下通式(III):
R5O(EO)x(PO)yR6 (III)
其中R5和R6各自独立地表示氢、具有1-18个碳原子的烷基或链烯基、或者在烷基结构部分中具有1-18个碳原子的烷基酚基团,EO表示氧化乙烯单元,PO表示氧化丙烯单元,x和y各自独立地表示约10-100、优选约20-80和更优选约30-50的整数,且总和(x+y)表示约50-150的整数,条件是EO和PO单元在分子中显示嵌段分布或无规分布。在本发明的另一个优选实施方案中,所述氧化乙烯-氧化丙烯共聚物符合通式(III),其中R5表示壬基酚,R6表示氢,x和y表示约25-50的整数。最优选这样的化合物,其表示约40个氧化乙烯单元和约30个氧化丙烯单元在壬基酚上的加合物。
溶剂组合物
通常,本发明的溶剂组合物含有:
(a)约90-95重量%的羧酸二烷基酰胺,
(b)约2-4重量%的脂肪酸或其盐,和
(c)约1-3重量%的氧化乙烯-氧化丙烯共聚物,
条件是总量是100重量%。
工业应用
如上所述,本发明的组合物显示出强溶剂能力,并同时具有高的可生物降解性、优异的环境友好性和尤其是当处于含水介质中时对碱土金属的高容忍性。所以,本发明的另一个目的是含有以下组分的组合物作为溶剂的用途,
(a)羧酸酰胺,
(b)脂肪酸或其盐,和
(c)氧化乙烯-氧化丙烯共聚物,尤其用于农业组合物(例如含水杀微生物浓缩物)、脱脂剂、加工流体等的用途。本发明还包括一种改进羧酸酰胺在含有高达500ppm碱土金属阳离子的水中的溶解性的方法,其中加入基于所述酰胺计的1-5重量%的乳化剂共混物,所述乳化剂共混物含有脂肪酸或其盐以及氧化乙烯-氧化丙烯共聚物。优选,所述乳化剂共混物中所含的脂肪酸或其盐与氧化乙烯-氧化丙烯共聚物之间的重量比率是约50:50至约95:5,尤其是约60:40至约90:10,更尤其是约70:30至约80:20。
本发明的最后一个实施方案涉及含有脂肪酸或其盐以及氧化乙烯-氧化丙烯共聚物的共混物作为乳化剂用于改进羧酸酰胺在含有高达500ppm碱土金属阳离子的水中的溶解性或分散性的用途,所述共混物中所含的脂肪酸或其盐与氧化乙烯-氧化丙烯共聚物之间的重量比率通常是约50:50至约95:5,尤其是约60:40至约90:10,更尤其是约70:30至约80:20。
实施例
实施例1、对比例C1至C5
制备基于辛酸二甲基酰胺、乳化剂和助乳化剂的溶剂组合物,并在含有500ppm钙和镁离子(50:50)的水中稀释(5重量%)。将这些乳液在20℃下储存一天,并在5小时、10小时和24小时之后检测稳定性。结果列在下面的表1中,并具有以下含义:(+++)=透明乳液,(++)=轻微浑浊,(+)=浑浊,(-)=分离的。
表1
辛酸二甲基酰胺/表面活性剂浓缩物的乳液稳定性
这些实施例和对比例清楚地表明仅仅加入脂肪酸和EO/PO共聚物的共混物才获得透明和稳定的乳液。
实施例2、对比例C6至C10
制备基于乳酸二甲基酰胺、乳化剂和助乳化剂的溶剂组合物,并在含有200ppm钙和镁离子(50:50)的水中稀释(5重量%)。将这些乳液在20℃下储存一天,并在5小时、10小时和24小时之后检测稳定性。结果列在下面的表2中,并具有以下含义:(+++)=透明乳液,(++)=轻微浑浊,(+)=浑浊,(-)=分离的。
表2
乳酸二甲基酰胺/表面活性剂浓缩物的乳液稳定性
这些实施例和对比例清楚地表明仅仅加入脂肪酸和EO/PO共聚物的共混物才获得透明和稳定的乳液。
Claims (13)
1.一种溶剂组合物,其含有:
(a)羧酸酰胺,
(b)脂肪酸或其盐,和
(c)氧化乙烯-氧化丙烯共聚物,
其中所述脂肪酸或其盐具有以下通式(II):
R4CO-OX (II)
其中R4CO表示饱和或不饱和的、直链或支化的具有6-36个碳原子的酰基,X表示氢、碱金属、碱土金属、铵或烷基铵,和
其中所述氧化乙烯-氧化丙烯共聚物具有以下通式(III):
R5O(EO)x(PO)yR6 (III)
其中R5和R6各自独立地表示氢、具有1-18个碳原子的烷基或链烯基、或者在烷基结构部分中具有1-18个碳原子的烷基酚基团,EO表示氧化乙烯单元,PO表示氧化丙烯单元,x和y各自独立地表示10-100的整数,且总和(x+y)表示50-150的整数,条件是EO和PO单元在分子中显示嵌段分布或无规分布。
2.权利要求1的溶剂组合物,其特征在于所述羧酸酰胺(组分a)具有以下通式(I):
R1CO-NR2R3 (I)
其中R1CO表示任选被羟基取代的、饱和或不饱和的、直链或支化的具有6-22个碳原子的酰基,R2表示氢或具有1-12个碳原子的烷基,R3表示具有1-12个碳原子的烷基。
3.权利要求1或2的溶剂组合物,其特征在于所述羧酸酰胺(组分a)表示羧酸二甲基酰胺、羧酸二丁基酰胺、羧酸二辛基酰胺或羧酸二-2-乙基己基酰胺。
4.权利要求1或2的溶剂组合物,其特征在于所述羧酸酰胺选自以下:癸酸二甲基酰胺,癸酸二丁基酰胺,癸酸二辛基酰胺,癸酸二-2-乙基己基酰胺,辛酸二甲基酰胺,辛酸二丁基酰胺,辛酸二辛基酰胺,辛酸二-2-乙基己基酰胺,己酸二甲基酰胺,己酸二丁基酰胺,己酸二辛基酰胺,己酸二-2-乙基己基酰胺,月桂酸二甲基酰胺,月桂酸二丁基酰胺,月桂酸二-2-乙基己基酰胺,乳酸二甲基酰胺,乳酸二丁基酰胺,乳酸二-2-乙基己基酰胺,以及它们的混合物。
5.权利要求1或2的溶剂组合物,其特征在于所述脂肪酸(组分b)是选自以下:月桂酸,肉豆蔻酸,棕榈酸,硬脂酸,油酸,亚油酸,山嵛酸,芥酸,或它们的工业混合物。
6.权利要求1或2的溶剂组合物,其特征在于所述脂肪酸(组分b)表示松浆油脂肪酸。
7.权利要求1或2的溶剂组合物,其特征在于所述氧化乙烯-氧化丙烯共聚物符合通式(III),其中R5表示壬基酚,R6表示氢,x和y表示25-50的整数。
8.权利要求1或2的溶剂组合物,其特征在于其含有:
(a)90-95重量%的羧酸二烷基酰胺,
(b)2-4重量%的脂肪酸或其盐,和
(c)1-3重量%的氧化乙烯-氧化丙烯共聚物,
条件是总量是100重量%。
9.含有以下组分的组合物作为溶剂的用途,
(a)羧酸二烷基酰胺,
(b)脂肪酸或其盐,和
(c)氧化乙烯-氧化丙烯共聚物,
其中所述脂肪酸或其盐具有以下通式(II):
R4CO-OX (II)
其中R4CO表示饱和或不饱和的、直链或支化的具有6-36个碳原子的酰基,X表示氢、碱金属、碱土金属、铵或烷基铵,和
其中所述氧化乙烯-氧化丙烯共聚物具有以下通式(III):
R5O(EO)x(PO)yR6 (III)
其中R5和R6各自独立地表示氢、具有1-18个碳原子的烷基或链烯基、或者在烷基结构部分中具有1-18个碳原子的烷基酚基团,EO表示氧化乙烯单元,PO表示氧化丙烯单元,x和y各自独立地表示10-100的整数,且总和(x+y)表示50-150的整数,条件是EO和PO单元在分子中显示嵌段分布或无规分布。
10.一种改进羧酸酰胺在含有高达500ppm碱土金属阳离子的水中的溶解性的方法,其中加入基于所述酰胺计的1-5重量%的乳化剂共混物,所述乳化剂共混物含有脂肪酸或其盐以及氧化乙烯-氧化丙烯共聚物,
其中所述脂肪酸或其盐具有以下通式(II):
R4CO-OX (II)
其中R4CO表示饱和或不饱和的、直链或支化的具有6-36个碳原子的酰基,X表示氢、碱金属、碱土金属、铵或烷基铵,和
其中所述氧化乙烯-氧化丙烯共聚物具有以下通式(III):
R5O(EO)x(PO)yR6 (III)
其中R5和R6各自独立地表示氢、具有1-18个碳原子的烷基或链烯基、或者在烷基结构部分中具有1-18个碳原子的烷基酚基团,EO表示氧化乙烯单元,PO表示氧化丙烯单元,x和y各自独立地表示10-100的整数,且总和(x+y)表示50-150的整数,条件是EO和PO单元在分子中显示嵌段分布或无规分布。
11.权利要求10的方法,其特征在于所述乳化剂共混物中所含的脂肪酸或其盐与氧化乙烯-氧化丙烯共聚物之间的重量比率是50:50至95:5。
12.含有脂肪酸或其盐以及氧化乙烯-氧化丙烯共聚物的共混物作为乳化剂用于改进羧酸酰胺在含有高达500ppm碱土金属阳离子的水中的溶解性或分散性的用途,
其中所述脂肪酸或其盐具有以下通式(II):
R4CO-OX (II)
其中R4CO表示饱和或不饱和的、直链或支化的具有6-36个碳原子的酰基,X表示氢、碱金属、碱土金属、铵或烷基铵,和
其中所述氧化乙烯-氧化丙烯共聚物具有以下通式(III):
R5O(EO)x(PO)yR6 (III)
其中R5和R6各自独立地表示氢、具有1-18个碳原子的烷基或链烯基、或者在烷基结构部分中具有1-18个碳原子的烷基酚基团,EO表示氧化乙烯单元,PO表示氧化丙烯单元,x和y各自独立地表示10-100的整数,且总和(x+y)表示50-150的整数,条件是EO和PO单元在分子中显示嵌段分布或无规分布。
13.权利要求12的用途,其特征在于所述乳化剂共混物中所含的脂肪酸或其盐与氧化乙烯-氧化丙烯共聚物之间的重量比率是50:50至95:5。
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