CN101287771A - 生产水乳液和水分散体的方法 - Google Patents
生产水乳液和水分散体的方法 Download PDFInfo
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- CN101287771A CN101287771A CNA200680037888XA CN200680037888A CN101287771A CN 101287771 A CN101287771 A CN 101287771A CN A200680037888X A CNA200680037888X A CN A200680037888XA CN 200680037888 A CN200680037888 A CN 200680037888A CN 101287771 A CN101287771 A CN 101287771A
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- polysiloxane
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- water
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Abstract
本发明涉及可由以下物质自由基共聚并且如果合适的话水解获得的三元共聚物的用途,(a)至少一种C3-C10二羧酸的酸酐,(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯,其用于使用基于水乳液或水分散体总量计最多2重量%的另外乳化剂制备疏水物质的水乳液或水分散体。
Description
本发明涉及可由以下物质自由基共聚并且如果合适的话水解获得的三元共聚物(A)用于制备聚硅氧烷(B)的水乳液或水分散体的用途,
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯,制备中使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂。
本发明另外涉及一种使用三元共聚物(A)和使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂制备聚硅氧烷(B)的水乳液或水分散体的方法,所述三元共聚物(A)可由以下物质自由基共聚并且如果合适的话水解获得:
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯。
聚硅氧烷是种被广泛使用的物质。因此多数情况下希望应用聚硅氧烷。举例来说可以提到赋予表面防水性和对表面涂油、润滑或浸渍,以及另外赋予纤维基底防水性和对其涂油,特别是可水溶胀基底,如鞣制的动物皮革。然而由于这些情况,企图在水相中并且不使用有机溶剂进行应用,因为有机溶剂例如非常易燃或具有生理上不利的性能。因此必需将待应用的疏水物质分散或乳化。这种乳液应该具有包括尤其是稳定性在内的有利性能,即它们不应呈现明显分离或应该仅在长时间内才分离。因此制备所谓稳定的聚硅氧烷乳液和分散体是一项重要的工作范畴。
为了制备稳定的乳液和分散体,因此选择乳化剂起着关键的作用。与此同时,许多惯用的乳化剂是不合需要的,因为他们不利地影响废水并且可具有例如高COD(化学需氧量)或BOD(生物需氧量),这使得废水处理更加昂贵。
US 3,004,950提出了乙烯基聚硅氧烷化合物与例如N-乙烯基吡咯烷酮的特定嵌段共聚物作为乳化剂。US 6,239,290提出了含聚硅氧烷基的脱水山梨糖醇衍生物作为乳化剂。然而,这些化合物在每种情况下都不便于合成。
因此本发明的目的是提供一种方法,通过该方法可以将聚硅氧烷在水中乳化或分散并且避免了上述缺点。
因此,发现了在开头定义的用途和在开头定义的方法。
本发明涉及可由以下物质自由基共聚获得的三元共聚物(A)用于制备聚硅氧烷(B)的水乳液或水分散体的用途,
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯,
所述获得的三元共聚物(A)在本发明范围内还简称为三元共聚物(A),制备中使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂。
本发明另外涉及一种使用三元共聚物(A)和使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂制备聚硅氧烷(B)的水乳液或水分散体的方法,所述三元共聚物(A)可由以下物质自由基共聚获得:
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯。
在本发明的范围内,聚硅氧烷(B)意指在室温下为固体或优选为液体,并且基本上由相同或不同的式I基团组成的化合物:
在此,R1和R2不同或优选相同且选自苯基,(CH2)n-COOH,(CH2)n-CH(COOH)-CH2-COOH,n是1-30的整数,优选为11-25,全氟烷基如三氟甲基、n-C3F7和n-C4F9,并且特别是C1-C20烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基(isopentyl)、仲戊基、新戊基、1,2-二甲基丙基、异戊基(isoamyl)、正己基、异己基、仲己基、正庚基、正辛基、正壬基、正癸基、正二十烷基;优选为直链C1-C4烷基如甲基、乙基、正丙基、正丁基,非常特别为甲基。
如果至少一个R1或R2选自(CH2)n-COOH,则优选不是所有的R1和R2相同。
在本发明的一个实施方案中,聚硅氧烷(B)的平均分子量Mw在500-100000g/mol范围内,优选2500-25000g/mol。
聚硅氧烷(B)可以是环状、支链或优选直链;在后一情形中,自由价由R1饱和,特别是由甲基饱和。
在本发明的一个实施方案中,聚硅氧烷(B)的平均分子量Mw在8000-11000g/mol范围内。
在本发明的一个实施方案中,聚硅氧烷(B)平均每分子带有一个羧基。在本发明的另一个实施方案中,聚硅氧烷(B)平均每分子带有两个或三个或四个羧基。在本发明的另一个实施方案中,聚硅氧烷(B)不带有羧基。
在本发明的一个实施方案中,聚硅氧烷(B)的羧基可以由例如碱金属如钾或钠中和。
根据本发明,一种或多种可由以下物质自由基共聚获得的三元共聚物(A)用于使具有上述特征的聚硅氧烷(B)分散或优选乳化:
(a)至一种C3-C10二羧酸的酸酐,例如柠康酸酐、衣康酸酐,特别是马来酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,例如2-甲基-1-丁烯、2-乙基-1-丁烯、二异丁烯(2,4,4-三甲基-1-戊烯和2,4,4-三甲基-2-戊烯的混合物)、2-乙基戊-1-烯和2-乙基己-1-烯以及特别是异丁烯,
(c)平均分子量Mn在200-10000g/mol范围内,优选500-1000g/mol的聚异丁烯。聚异丁烯的每分子具有一个末端烯属不饱和基团,例如乙烯基、亚乙烯基或烷基亚乙烯基。
在本发明的一个实施方案中,三元共聚物(A)的平均分子量Mn在500-50000g/mol范围内,优选1500-20000g/mol,例如通过凝胶渗透色谱法(GPC)测定。
在本发明的一个实施方案中,三元共聚物(A)的多分散性在1.1-10范围内,优选1.5-3.0。
在本发明的一个实施方案中,引入到三元共聚物(A)中且平均分子量Mn在200-10000g/mol范围内的聚异丁烯(c)的多分散性在1.1-3范围内,优选1.5-2.0。
平均分子量Mn在200-10000g/mol范围内的聚异丁烯(c)及其制备由例如DE-A 27 02 604已知。
在本发明的一个实施方案中,三元共聚物(A)是一种准交替三元共聚物,即在此情形下两个C3-C10二羧酸的酸酐(a)单元并不是直接相邻引入到三元共聚物(A)聚合物链中,而是在每种情形下,在下一个C3-C10二羧酸的酸酐单元(a)引入到三元共聚物(A)中之前,被至少一个1,1-二(C1-C3烷基)取代的C4-C8烯烃(b)单元或至少一个平均分子量Mn在200-10000g/mol范围内的聚异丁烯(c)单元间断。
以下物质的自由基共聚可以在有或者没有稀释剂如一种或多种溶剂或一种或多种沉淀剂的条件下进行:
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯。适合于自由基共聚的溶剂为对酸酐呈惰性的极性溶剂,例如丙酮、四氢呋喃和1,4-二噁烷或甲苯、邻二甲苯、间二甲苯和脂族烃。
以下物质的自由基共聚优选使用引发剂或引发剂体系进行:
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯。适合的引发剂为例如有机过氧化物或氢过氧化物。举例来说可以提到过氧化二叔丁基、过新戊酸叔丁基酯、过-2-乙基己酸叔丁基酯、过马来酸叔丁基酯、过异丁酸叔丁基酯、过氧化苯甲酰、过氧化二乙酰、过氧化琥珀酰、过氧化对氯苯甲酰和过二碳酸二环己基酯。使用引发剂体系例如氧化还原引发剂也是适合的,例如过氧化氢或过二硫酸钠或上述过氧化物之一与还原剂的组合。适合的还原剂的实例为抗坏血酸、酒石酸、铁(II)盐例如FeSO4、亚硫酸氢钠和亚硫酸氢钾。
其它适合的引发剂为偶氮化合物,如2,2’-偶氮二异丁腈、2,2’-偶氮双(2-甲基丙脒)二盐酸盐和2,2’-偶氮双(4-甲氧基-2,4-二甲基戊腈)。
一般而言,相对于所有共聚单体(a)至(c)的质量计,引发剂的用量为0.1-20重量%,优选为0.2-15重量%。
在自由基共聚以后,可以通过例如加水进行水解,如果合适,水中可以包含一种或多种布朗斯台德碱。布朗斯台德碱的实例为碱金属氢氧化物如NaOH和KOH,碱金属碳酸盐如Na2CO3和K2CO3,碱金属碳酸氢盐如NaHCO3和KHCO3,氨,胺如三甲胺、三乙胺、二乙胺、乙醇胺、N,N-二乙醇胺、N,N,N-三乙醇胺和N-甲基乙醇胺。
为了实施本发明方法,三元共聚物(A)可以以未水解过或优选水解过的形式使用。
根据本发明,基于水乳液或水分散体的总量计,可以使用不超过2重量%、优选0.0001-1.5重量%的另外乳化剂,所述乳化剂选自例如离子乳化剂即阴离子或阳离子乳化剂,并优选非离子乳化剂、特别是N-甲基-N-酰基牛磺酸钠和N-酰基肌氨酸,和单或多烷氧基化磷酸酯、特别是乙氧基化度为3-100的磷酸酯,醇,脱水山梨糖醇酯,脂肪酸,脂肪胺,脂肪酰胺或酯,以及聚乙二醇酯。
优选多烷氧基化C10-C40脂肪醇,特别是乙氧基化度为至多100的那些,并且优选多烷氧基化C11-C31羰基合成醇,特别是乙氧基化度为至多100的那些。
特别适合的脂肪醇和多烷氧基化羰基合成醇的实例为通式II的那些
其中变量定义如下:
R3为支链或直链C6-C30烷基或C6-C30链烯基,优选为C8-C20烷基或C8-C20链烯基,C6-C30链烯基可具有一个或多个可优选为(Z)-构型的C-C双键,AO是相同或不同的C2-C4氧化烯,例如氧化丁烯CH(C2H5)CH2O,氧化丙烯CH(CH3)CH2O和特别是氧化乙烯CH2CH2O,
x是2-100的数,作为平均值(数均)的x还可以是非整数,优选2-90,特别是2.5-80。
若AO是不同的氧化烯,则不同的氧化烯可以以嵌段或无规排列。
特别适合的多烷氧基化脂肪醇和羰基合成醇的实例为
正-C18H37O-(CH2CH2O)80-H、
正-C18H37O-(CH2CH2O)70-H、
正-C18H37O-(CH2CH2O)60-H、
正-C18H37O-(CH2CH2O)50-H、
正-C18H37O-(CH2CH2O)25-H、
正-C18H37O-(CH2CH2O)12-H、
正-C16H33O-(CH2CH2O)80-H、
正-C16H33O-(CH2CH2O)70-H、
正-C16H33O-(CH2CH2O)60-H、
正-C16H33O-(CH2CH2O)50-H、
正-C16H33O-(CH2CH2O)25-H、
正-C16H33O-(CH2CH2O)12-H、
正-C12H25O-(CH2CH2O)11-H、
正-C12H25O-(CH2CH2O)18-H、
正-C12H25O-(CH2CH2O)25-H、
正-C12H25O-(CH2CH2O)50-H、
正-C12H25O-(CH2CH2O)80-H、
正-C30H61O-(CH2CH2O)8-H、
正-C10H21O-(CH2CH2O)9-H、
正-C10H21O-(CH2CH2O)7-H、
正-C10H21O-(CH2CH2O)5-H、
正-C10H21O-(CH2CH2O)3-H、
和上述乳化剂的混合物,例如正-C18H37O-(CH2CH2O)50-H和正-C16H33O-(CH2CH2O)50-H的混合物,其中指数在每种情况下被认为是平均值(数均)。
特别适合的N-酰基肌氨酸的实例是N-油酰基-N-肌氨酸。
在本发明的一个特定实施方案中,没有另外使用乳化剂来使聚硅氧烷(B)乳化或分散。
在本发明的一个优选实施方案中,没有使用阴离子乳化剂来使聚硅氧烷(B)乳化或分散。
在本发明的一个实施方案中,本发明方法通过其中使用两种或更多种另外乳化剂来使聚硅氧烷(B)乳化或分散的程序进行,要确保基于水乳液或水分散体的总量计,另外乳化剂的总和不超过2重量%。
在本发明的一个实施方案中,根据本发明制备的水乳液或水分散体的含水量在40-95重量%范围内,优选60-90重量%。
在本发明的一个实施方案中,在0-100℃、优选在20-50℃范围内的温度下进行混合。
可以在任何所需压力下进行混合,优选大气压。
在本发明的一个实施方案中,通过其中将三元共聚物(A)、聚硅氧烷(B)和不超过2重量%的乳化剂与水混合(例如振摇或优选搅拌)的程序进行本发明方法。
在本发明的一个实施方案中,通过其中将三元共聚物(A)、聚硅氧烷(B)和不超过2重量%的乳化剂混合,特别是通过施加超声波或借助于间隙均化器(spalthomogenisator)均化的程序进行本发明方法。
在本发明的一个实施方案中,通过其中将三元共聚物(A)、聚硅氧烷(B)和零至不超过2重量%的乳化剂与水和一种或更多种有机溶剂混合,然后分离出有机溶剂的程序进行本发明方法,所述有机溶剂选自室温下为液体的脂族和芳族烃。室温下为液体的脂族溶剂可以选自例如环己烷、环庚烷、正己烷、正庚烷、异十二烷、正癸烷、正辛烷和异辛烷。室温下为液体的芳族溶剂可以选自例如苯、优选甲苯、乙苯、异丙基苯、邻二甲苯、间二甲苯、对二甲苯和二甲苯的异构体混合物。例如可以通过蒸馏特别是通过蒸汽蒸馏将有机溶剂分离出。
在本发明的一个实施方案中,基于水使用10-40重量%的有机溶剂。
在本发明的一个实施方案中,可以使用至少一种另外疏水物质(C)来进行混合。适合的另外疏水物质为例如聚烯烃,特别是例如分子量Mn在500-20000g/mol范围内的聚异丁烯。
在本发明的一个实施方案中,根据本发明制备的水乳液或水分散体包含
1-60重量%、优选2-20重量%的三元共聚物(A),
1-60重量%、优选2-40重量%的聚硅氧烷(B),
总共0-50重量%、优选2-30重量%的另外疏水物质(C),
0至不超过2重量%的另外乳化剂,
其余优选为水。
本发明另外涉及通过上述本发明方法制备的水分散体或水乳液。根据本发明的水分散体和水乳液以极好的稳定性而著名。此外,使用根据本发明的分散体或乳液,可以将聚硅氧烷(B)完全消耗。因此,根据本发明的分散体或乳液的废料可以被容易地处理,并且其化学或生物需氧量低。
根据本发明的水分散体或水乳液优选不包含有机溶剂。在本发明的范围内,这意指基于根据本发明的水分散体或水乳液计,有机溶剂如脂族或芳族有机溶剂的含量小于0.1重量%、优选小于0.01重量%。
在本发明的一个实施方案中,根据本发明的分散体或乳液的pH在4-10范围内,优选6-7。
此外,可以向根据本发明的乳液或分散体中添加一种或多种生物杀伤剂。例如异噻唑啉酮,例如BIT:1,2-苯并异噻唑-3(2H)-酮,CIT:5-氯-2-甲基-2H-异噻唑-3-酮;和MIT:2-甲基-2H-异噻唑-3-酮,对羟基苯甲酸酯,例如对羟基苯甲酸甲酯,对羟基苯甲酸乙酯或对羟基苯甲酸丙酯。
在本发明的一个实施方案中,根据本发明的水乳液或水分散体包含
1-60重量%、优选2-20重量%的三元共聚物(A),
1-60重量%、优选2-40重量%的聚硅氧烷(B),
总共0-50重量%、优选2-30重量%的另外疏水物质(C),
0至不超过2重量%的另外乳化剂,
其余优选为为水。
本发明另外涉及根据本发明的分散体或乳液的用途,其用于生产纤维基底、用作脱模剂、用作润滑剂、用作清洁剂、用于处理或加工建筑材料或者用作化妆品制剂或用在化妆品制剂中。
本发明另外涉及使用根据本发明的分散体或乳液生产纤维基底的方法和清洁表面、分离制品、处理或加工建筑材料或者用作化妆品制剂或用在化妆品制剂中的方法。
纤维基底可以选自例如纸、木材、织物、板和优选皮革。
本发明另外涉及一种使用根据本发明的分散体或乳液例如作为润滑剂来减少运动部件(例如包括金属)间摩擦的方法。借助于减少运动部件(例如包括金属)间摩擦的本发明方法,还减少了所述部件受到腐蚀的趋向并延长了寿命。
如果希望使用根据本发明的乳液或分散体生产纤维基底,则可以采用例如以下程序,其中使皮革、纸、木材、板或织物与根据本发明的乳液或分散体本身或用水稀释过的形式接触,例如涂敷、喷雾或浸渍,然后使其干燥。
如果希望使用根据本发明的乳液或分散体生产皮革,则优选在例如鞣制或优选在复鞣或疏水化中使用一种或多种根据本发明的乳液或分散体。根据本发明的用于鞣制、复揉或皮革疏水化的此类方法以下还分别称作根据本发明的鞣制法,根据本发明的复鞣法和根据本发明的皮革疏水化法。
根据本发明的鞣制法通常可按照这样的方式进行:将根据本发明的乳液或分散体以一份或多份在紧临鞣制前加入或在鞣制期间加入。根据本发明的鞣制法优选在pH 2.5-4下进行,经常观察到在进行根据本发明的鞣制法时pH升高大约0.3-3个单位。pH还可以通过添加碱化剂升高大约0.3-3个单位。
根据本发明的鞣制法通常在10-45℃、优选在20-30℃的温度下进行。已证明10分钟至12小时的持续时间是有用的、优选1-3小时。根据本发明的鞣制法可以在鞣制中常见的任何所需容器中进行,例如通过在筒或在转筒中转鼓而进行。
在根据本发明鞣制法的一个方案中,将根据本发明的乳液或分散体与一种或多种常规鞣剂一起使用,例如与铬鞣剂、或矿物鞣剂、优选与合成鞣剂、聚合物鞣剂或植物鞣剂一起使用,它们例如描述在Ulmann’sEncyclopedia of Industrial Chemistry,A15卷,第259-282页,特别是268页及随后内容,第5版(1990)Verlag Chemie Weiheim中。
在根据本发明的鞣制法的一个实施方案中,根据本发明的乳液或分散体可以与一种或多种乳液加油剂和防水剂一起使用。
在根据本发明的鞣制法的另一个实施方案中,无需使用乳液加油剂和防水剂。
根据本发明的处理皮革的方法可以优选作为使用根据本发明的乳液或分散体复鞣皮革的方法进行。根据本发明的复鞣法是从常规鞣制半成品,即例如用铬鞣剂或矿物鞣剂、优选用聚合物鞣剂、醛、合成鞣剂或树脂鞣剂鞣制的半成品起始。根据本发明,为了实施根据本发明的复鞣法,将根据本发明的乳液或分散体本身或优选用水稀释过的形式作用于半成品上。
根据本发明的复鞣法可以在其它常规鞣制条件下进行。方便地选取一个或多个、即2-6个浸泡步骤,并在这些浸泡步骤之间可用水洗涤。各浸泡步骤期间的温度在每一情况下在5-60℃范围内,优选20-45℃。
在根据本发明的复鞣法的一个实施方案中,可以使用另外的乳液加油剂和防水剂。
在根据本发明的复鞣法的另一实施方案中,无需使用另外的乳液加油剂和防水剂。可以计量加入0.5-10重量%的根据本发明的乳液或分散体,重量%基于根据本发明处理的皮革或根据本发明处理的半成品的削匀重。
为了实施根据本发明的鞣制法或复鞣法,在鞣制或复鞣期间当然可以添加常用试剂,例如加油乳液、聚合物鞣剂、基于丙烯酸酯和/或甲基丙烯酸酯或基于聚硅氧烷的乳液加油剂、基于树脂的复鞣剂以及植物鞣剂、填料或皮革染料或至少上述两种物质的组合。
在本发明的一个实施方案中,基于削匀重,使用0.01-10重量%的根据本发明的分散体或乳液。
如果希望根据本发明的乳液或分散体用作清洁剂或用于清洁表面,则可以从任何所需的表面例如皮革、塑料或其它表面开始。例如,可以采用以下程序,其中例如使用清洁工具如填絮、海绵、纸质布、抹布或布料或借助于喷淋装置(如喷壶)施加根据本发明的乳液或水分散体,然后使其作用例如10秒至一天,然后例如使用清洁工具如填絮、海绵、纸质布、抹布或布除去浮在表面的根据本发明的乳液或分散体。获得了发光的、清洁的表面。
如果希望根据本发明的乳液或分散体用于处理或加工建筑材料,则优选石膏、石头、渣块和混凝土的疏水化。为此,可以将根据本发明的分散体或乳液加入到混凝土原料中或随后例如通过涂覆、喷雾或浸渍施加到相关建筑材料上,然后使其干燥。
本发明另外涉及使用至少一种根据本发明的分散体或乳液生产的建筑材料。
如果希望根据本发明的乳液或分散体用作化妆品制剂或用在化妆品制剂中,则优选软膏、霜、肥皂、露、洗发剂和毛发护理组合物以及洗涤、淋浴和沐浴制剂。本发明另外涉及使用至少一种根据本发明的乳液或分散体制备的化妆品制剂。根据本发明的化妆品制剂包含根据本发明的乳液或分散体。
根据本发明的化妆品制剂除了水和根据本发明的分散体或乳液之外还可以包含油或脂相(D)。油或脂相(D)例如可以由一种或多种天然或合成油、脂肪或蜡形成。
在本发明的一个实施方案中,油或脂相(D)由一种或优选多种以下所提及的成分组成。
油和/或脂相(D)的成分可以选自例如卵磷脂和甘油三脂肪酸脂,例如链长为8-24、特别是12-18个碳原子的饱和和/或不饱和的、支链和/或直链烷烃羧酸的甘油三酯。甘油三脂肪酸脂可以有利地选自例如合成、半合成和天然油,例如橄榄油,葵花油,大豆油,花生油,菜子油,杏仁油,棕榈油,椰子油,蓖麻油,小麦胚芽油,葡萄子油,红花油,月见草油和澳洲坚果油。
油和/或脂相(D)的另外成分可以选自链长为3-30个碳原子的饱和和/或不饱和的、支链和/或直链烷烃羧酸与链长为3-30个碳原子的饱和和/或不饱和的、支链和/或直链醇的酯,以及可以选自芳族羧酸与链长为3-30个碳原子的饱和和/或不饱和、支链和/或直链醇的酯。优选的实例为肉豆蔻酸异丙酯,棕榈酸异丙酯,硬脂酸异丙酯,油酸异丙酯,硬脂酸正丁基酯,月桂酸正己基酯,油酸正癸基酯,硬脂酸异辛基酯,硬脂酸异壬基酯,异壬酸异壬基酯,棕榈酸2-乙基己基酯,月桂酸2-乙基己基酯,硬脂酸2-己基癸基酯,棕榈酸2-辛基十二烷基酯,油酸油基酯,芥酸油基酯,芥酸芥基酯,碳酸二辛酯(cetiol CC)和椰油甘油脂(例如Myritol 331),丁二醇二辛酸酯/二癸酸酯和己二酸二正丁基酯,以及这些酯的合成、半合成和天然混合物,例如霍霍巴油。
油或脂相(D)的另外成分可以选自支链和直链烃和烃蜡以及二C5-C20烷基醚,和选自饱和或不饱和的、支链或直链的C12-C30醇,其也起着泡沫形成剂的作用。
上述成分的任何所需混合物同样可用作根据本发明的化妆品制剂中的油或脂相(D)。
使用蜡例如棕榈酸鲸蜡酯作为油相的唯一脂质组分是有利的。
油或脂相(D)的优选成分选自异硬脂酸2-乙基己基酯,辛基十二烷醇,异壬酸异十三烷基酯、异二十烷、椰油酸2-乙基己基酯、苯甲酸C12-C15烷基酯、甘油三辛酸/癸酸脂和二辛酰醚。
油或脂相(D)成分的优选混合物的实例选自苯甲酸C12-C15烷基酯和异硬脂酸2-乙基己基酯的混合物、苯甲酸C12-C15烷基酯和异壬酸异十三烷基酯的混合物和苯甲酸C12-C15烷基酯、异硬脂酸2-乙基己基酯和/或异壬酸异十三烷酯的混合物。
根据本发明,特别优选作为极性为5-50mN/m的油的甘油三脂肪酸脂,特别是大豆油和/或杏仁油。
选自烃,例如液体石蜡、角鲨烷、角鲨烯以及特别是任选氢化的聚异丁烯的物质可用作油或脂相(D)。
在本发明的一个实施方案中,油或脂相(D)可选自格尔伯特(Guerbet)醇。格尔伯特醇本身是已知的,并且其可以例如通过在Na和/或Cu的存在下,加热两当量通式R4-CH2-CH2-OH的醇以产生式R4-CH2-CH2-CHR4-CH2-OH的醇而获得。在此,R4为C2-C20烷基,支链或优选直链、特别是直链C3-C14烷基,例如在每种情况下为直链丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基或十四烷基。特别优选的适合作为油或脂相(D)的格尔伯特醇为2-正丁基辛醇(R4=n-C4H9)和2-正己基癸醇(R4=n-C6H13)和上述格尔伯特醇的混合物。
根据本发明的化妆品制剂可另外包含一种或多种香料或香精(E)。
适合的香料或香精(E)可以是产生气味的天然或合成挥发性化合物的纯物质或混合物。天然香料是花(百合、熏衣草、玫瑰、茉莉、橙花、依兰)提取物,茎和叶(如老鹳草、广藿香、苦橙叶)提取物,果实(如茴香子、芫荽、枯茗、刺柏)提取物,皮(如香柠檬、柠檬、橙)提取物,根(如肉豆蔻、当归、芹菜、小豆蔻、闭鞘姜、鸢尾、石菖蒲)提取物,木(如松木、檀香木、愈创木、雪松木、蔷薇木)提取物,香草和禾草(如龙蒿、香茅草、鼠尾草、百里香)提取物,针和枝(如云杉、冷杉、松树、矮松)提取物,树脂和香脂(如古蓬香脂、榄香脂、安息香、没药、乳香、红没药)提取物。动物原料也是合适的,例如麝猫香和海狸香。典型的合成香料是酯、醚、醛、酮、醇和烃类产品。酯类香料例如是乙酸苄酯、异丁酸苯氧基乙酯、乙酸4-叔丁基环己酯、乙酸芳樟酯、乙酸二甲基苄基甲酯、乙酸苯基乙酯、苯甲酸芳樟酯、甲酸苄酯、甲基苯基甘氨酸乙酯、环己基丙酸烯丙酯、丙酸苏合香酯和水杨酸苄酯。醚类香料例如包括苄基乙基醚,醛类香料例如包括具有8-18个碳原子的链烷醛、柠檬醛、香茅醛、香茅基含氧乙醛、仙客来醛、羟基香茅醛、铃兰醛和波洁洪醛(Bourgeonal),酮类香料例如包括紫罗兰酮、cc-异甲基紫罗兰酮和甲基柏木酮,醇类香料包括茴香脑、香茅醇、丁子香酚、异丁子香酚、香叶醇、芳樟醇、苄基醇、苯基乙基醇和松油醇,烃类香料主要包括萜和香脂。然而优选使用在一起产生令人愉快的香味的不同香料的混合物。通常用作香精的低挥发性的精油也适合作为香料,例如鼠尾草油、春黄菊油、丁子香油、峰花油、薄荷油、肉桂叶子油、白柠檬花油()、刺柏油、岩兰油、乳香油、古蓬油、和薰衣草油。优选单独或以混合物使用香柠檬油、二氢月桂烯醇、铃兰醛、新铃兰醛(lyral)、香茅醇、苯基乙基醇、α-己基肉桂醛、α-戊基肉桂醛、香叶醇、苄基丙酮、仙客来醛、芳樟醇、BoisambreneForte、龙涎呋喃(Ambroxan)、吲哚、二氢茉莉酮酸甲酯(hedione)、Sandelice、柑桔油、橘子油、橙子油、戊基甘醇酸烯丙酯、Cyclovertal、薰衣草油、麝香葡萄油(Muskateller)、鼠尾草油、β-突厥酮、波旁香叶油、水杨酸环己酯、合成橡苔(evernyl)、Iraldein gamma、苯基乙酸、乙酸香叶酯、乙酸苄酯、玫瑰氧化物、Romillate、Irotyl和Floramate。
根据本发明的化妆品制剂可另外包含一种或多种添加剂(F)。添加剂(F)可选自调理剂、抗氧化剂、乙氧基化甘油基单或二脂肪酸酯、增稠剂、泡沫形成剂、润湿剂和保湿剂、生物杀伤剂、有机溶剂如乙醇或异丙醇、闪光剂和/或其它效应物质(例如色矿粉(Farbschlieren))和研磨剂。闪光剂及其它效果物质(例如色矿粉)基本上具有美学价值。
调理剂的实例记载在International Cosmetic Ingredient Dictionaryand Handbook(第4卷,编者:R.C.Pepe,J.A.Wenninger,G.N.McEwen,The Cosmetic,Toiletry,and Fragrance Association,2002年第9版)中的第4部分,关键词Hair Conditioning Agents、Humectants、Skin-ConditioningAgents、Skin-Conditioning Agents-Emollient、Skin-ConditioningAgents-Humectant、Skin-Conditioning Agents-Miscellaneous、Skin-Conditioning Agents-Occlusive和Skin Protectants。另外调理剂的实例是在EP-A 0934956(11-13页),“water soluble conditioning agent”和“oilsoluble conditioning agent”下提及的化合物。另外有利的调理剂为例如根据INCI命名为聚季铵盐的化合物(特别是聚季铵盐-1至聚季铵盐-56)。一种非常特别优选的调理剂为N,N-二甲基-N-2-丙烯基-2-丙烯氯化铵(聚季铵盐-7)。
有利的调理剂的其它实例为纤维素衍生物和季铵化的瓜尔胶衍生物,特别是瓜尔胶羟丙基氯化铵(例如JaguarJaguar C(Rhodia),CAS 65497-29-2,CAS 39421-75-5)。根据本发明,非离子聚-N-乙烯基吡咯烷酮/聚乙酸乙烯酯共聚物(例如VA 64(BASF))、阴离子丙烯酸酯共聚物(例如Soft(BASF))、和/或两性酰胺/丙烯酸酯/甲基丙烯酸酯共聚物(例如(National Starch))也可有利地用作调理剂。另外有利的调理剂的实例为季铵化的聚硅氧烷。
乙氧基化甘油基单或二脂肪酸酯的实例为PEG-10橄榄油甘油酯、PEG-11鳄梨油甘油酯、PEG-11椰子油甘油酯、PEG-13葵花油甘油酯、PEG-15甘油异硬脂酸酯、PEG-9椰油脂肪酸甘油酯、PEG-54氢化蓖麻油、PEG-7氢化蓖麻油、PEG-60氢化蓖麻油、霍霍巴油乙氧基化物(PEG-26霍霍巴脂肪酸、PEG-26霍霍巴醇)、甘油聚氧乙烯(5)醚椰油酸酯、PEG-9椰油脂肪酸甘油酯、PEG-7甘油椰油酸酯、PEG-45棕榈仁油甘油酯、PEG-35蓖麻油、橄榄油-PEG-7酯、PEG-6辛酸/癸酸甘油酯、PEG-10橄榄油甘油酯、PEG-13葵花油甘油酯、PEG-7氢化蓖麻油、氢化棕榈仁油甘油酯-PEG-6酯、PEG-20玉米油甘油酯、PEG-18甘油油酸酯椰油酸酯、PEG-40氢化蓖麻油、PEG-40蓖麻油、PEG-60氢化蓖麻油、PEG-60玉米油甘油酯、PEG-54氢化蓖麻油、PEG-45棕榈仁油甘油酯、PEG-80甘油椰油酸酯、PEG-60杏仁油甘油酯、PEG-60″月见草″甘油酯、PEG-200氢化甘油棕榈酸酯、和PEG-90甘油异硬脂酸酯。在本发明的范围内,PEG为聚乙二醇,PEG后面的数字为相关聚乙二醇的乙二醇单元的平均数。
优选的乙氧基化甘油单或二脂肪酸酯为PEG-7甘油椰油酸酯、PEG-9椰油甘油酯、PEG-40氢化蓖麻油和PEG-200氢化甘油棕榈酸酯。
在根据本发明的化妆品制剂中,乙氧基化甘油单或二脂肪酸酯可以用于不同目的。每分子具有3-12个氧化乙烯单元的乙氧基化甘油单或二脂肪酸酯用作加脂剂,以改善皮肤干后的感觉,每分子具有30-50个氧化乙烯单元的乙氧基化甘油单或二脂肪酸酯用作非极性物质如香料的增溶剂。每分子具有大于50个氧化乙烯单元的乙氧基化甘油单或二脂肪酸酯用作增稠剂。
适合的抗氧化剂的实例为所有适合于或常用于化妆品和/或皮肤学应用的抗氧化剂。
优选抗氧化剂选自氨基酸(例如甘氨酸、组氨酸、酪氨酸、色氨酸),咪唑(例如尿刊酸),肽如D,L-肌肽、D-肌肽、L-肌肽及其衍生物(例如鹅肌肽),类胡萝卜素,胡萝卜素(例如α-胡萝卜素,β-胡萝卜素,γ-番茄红素),绿原酸及其衍生物,脂酮酸及其衍生物(例如二氢脂酮酸),硫金代葡萄糖(Aurothioglucose),丙基硫尿嘧啶及其它硫醇(例如硫氧还蛋白、谷胱甘肽、半胱氨酸、胱氨酸、胱胺和糖基、N-乙酰基、甲基、乙基、丙基、戊基、丁基和十二烷基、棕榈酰、油基、γ-亚油基、胆甾烯基和甘油基酯)及其盐,硫代二丙酸二月桂基酯,硫代二丙酸二硬脂基酯,硫代二丙酸及其衍生物(酯、醚、肽、类脂、核苷酸、核苷和盐)和磺酰亚胺(Sulfoximin)化合物(例如丁硫堇(Buthionin)磺酰亚胺、高半胱氨酸磺酰亚胺、丁硫堇(Buthionin)砜、五-、六-和七硫堇磺酰亚胺),(都是以非常少的剂量(例如pmol-mmol/kg本发明混合物)),此外,金属螯合剂(例如α-羟基-脂肪酸、棕榈酸、植酸、乳铁蛋白),α-羟基酸(例如柠檬酸、乳酸、苹果酸),腐殖酸,胆汁酸、胆汁萃取物,胆红素,胆绿素,EDTA,EGTA,不饱和脂肪酸(例如γ-亚麻酸、亚油酸、油酸),叶酸,亚糠基山梨糖醇,泛醌和泛醌醇,维生素C及其衍生物(例如抗坏血酰棕榈酸酯、抗坏血酰磷酸镁、抗坏血酰乙酸酯),生育酚及其衍生物(例如维生素E乙酸酯),维生素A及其衍生物(维生素A棕榈酸酯)和来自苯偶姻树脂的苯甲酸松柏酯,芸香亭酸及其衍生物,α-糖基芸香苷,阿魏酸,亚糠基葡萄糖醇,肌肽,丁基羟基甲苯,丁基羟基茴香醚,去甲二氢愈创木脂酸,去甲二氢愈创木酸,三羟基丁酰苯,尿酸及其衍生物,甘露糖及其衍生物,锌及其衍生物(例如ZnO、ZnSO4),硒及其衍生物(例如硒代蛋氨酸),均二苯乙烯及其衍生物(例如均二苯乙烯氧化物,特别是反式均二苯乙烯氧化物)及其适合的衍生物(盐、酯、醚、糖、核苷酸、核苷、肽和类脂)。
适用于根据本发明的化妆品制剂的增稠剂为交联聚丙烯酸及其衍生物,角叉菜胶,黄原胶,多糖如黄原酸胶,瓜尔胶,琼脂,藻酸盐或甲基纤维素,纤维素衍生物,例如羧甲基纤维素、羟基羧甲基纤维素、羟乙基丙基纤维素,羟丁基甲基纤维素和羟丙基甲基纤维素,和更高分子量的脂肪酸的聚乙二醇单和二酯,脂肪醇,单甘油酯和脂肪酸,聚乙烯醇和聚乙烯吡咯烷酮。
此外,适合的增稠剂为例如亲水性热解法硅胶,聚丙烯酰胺,聚乙烯醇,聚乙烯吡咯烷酮,脂肪酸与多元醇如季戊四醇或三羟甲基丙烷的酯,具有窄的C1-C20烷基寡糖同系物分布的脂肪醇乙氧基化物和电解质如氯化钠和氯化铵。
适用于根据本发明的化妆品制剂的生物杀伤剂是对革兰氏阳性细菌具有特效的试剂,例如三氯生(2,4,4’-三氯-2’-羟基二苯醚),洗必泰(1,1’-六亚甲基双[5-(4-氯苯基)二胍]和TTC(3,4,4’-三氯对称二苯脲)。适合的生物杀伤剂还有异噻唑酮,例如5-氯-2-甲基-3(2H)异噻唑酮和2-甲基-3(2H)异噻唑酮。季铵化合物原则上同样是合适的,但优选用于消毒皂和洗涤液。许多香料也具有抗菌性能。大量精油或其特征性成分,例如丁子香油(丁子香酚)、薄荷油(薄荷醇)或百里香油(麝香草酚)也表现出显著的抗菌效果。另外的适合的生物杀伤剂为适用于防龋的氟化合物,例如NaF和氟化胺。
泡沫形成剂可以是例如含砜基团的表面活性剂,特别是月桂基硫酸钠。
保湿剂的实例为山梨糖醇、丙三醇、例如分子量Mn在200-1000g/mol范围内的聚乙二醇。
根据本发明的化妆品制剂可另外包含着色剂如染料或颜料、闪光剂和/或其它效应物质(例如色矿粉)。
根据本发明的化妆品制剂可包含例如一种或多种研磨剂,例如聚乙二醇、硅胶或碳酸钙。
可以例如通过将根据本发明的分散体或乳液与一种或多种来自油或脂相树脂(D)、香料和香精(E)和添加剂(F)的上述物质以及,如果合适,与水混合来制备根据本发明的化妆品制剂。
如果希望根据本发明的分散体或乳液用作脱模剂或用在分离制品的方法中,则它们可用于例如生产可剥薄膜或张贴物或用在注塑成型机中用于注塑部件的简化脱模。例如,可以使薄膜状材料如含聚酯、聚乙烯、聚丙烯或聚氨酯的聚合物薄膜的一面或两面接触根据本发明的分散体或乳液,然后在例如空气中干燥。优选将根据本发明的分散体或乳液与另外材料如硅胶混合,然后使其接触薄膜状材料。
通过实施例解释本发明。
根据H.Fikentischer,Cellulose-Chemie,第13卷,58-64和761-774(1932),在25℃且聚合物浓度为2重量%的环己烷中测量根据本发明使用的三元共聚物的K值。
1.制备三元共聚物(A.1)和三元共聚物(A.2)
首先将206g分子量Mn为550g/mol的聚异丁烯和185g二异丁烯置于4升容器中,并在温和氮气流中加热至110℃。达到110℃的温度后,在5小时过程中计量加入184g在70℃为熔体的液态马来酸酐,并在5.5小时过程中计量加入溶于25g二异丁烯(2,4,4-三甲基-1-戊烯和2,4,4-三甲基-2-戊烯的混合物)中的5.5g过辛酸叔丁基酯。然后在120℃下持续搅拌一小时。获得三元共聚物(A.1)。
将得到的反应混合物冷却至90℃,同时添加2400g水和140g 50重量%的氢氧化钠水溶液。之后,在90℃下进行搅拌4小时,接着冷却至室温。获得了水分散体形式的三元共聚物(A.2),其pH为6.5以及含水量为80重量%。K值为14.7。
2.制备根据本发明的水乳液
2.1制备根据本发明的水乳液WE-1
在4升搅拌容器中搅拌200g 60重量%邻二甲苯溶液形式的三元共聚物(A.1)和220g硅油(线性聚二甲基硅氧烷,25℃下v=350mm2/s),并在搅拌同时加热至90℃。添加700g水和15mgH(OCH2CH2)3O-(CH2)3-Si(CH3)[OSi(CH3)3]2[OSi(CH3)2OSi(CH3)3],然后通过蒸汽蒸馏除去邻二甲苯。然后添加82g 25重量%的氢氧化钠水溶液。获得根据本发明的水乳液WE-1,其含水量为70%。
2.2制备根据本发明的水乳液WE-2
在4升搅拌容器中搅拌250g 60重量%邻二甲苯溶液形式的三元共聚物(A.1)、91g聚异丁烯(Mn=1000g/mol)和180克硅油(线性聚二甲基硅氧烷,25℃下v=350mm2/s),并在搅拌同时加热至90℃。添加220g水和18mg
H(OCH2CH2)3O-(CH2)3-Si(CH3)[OSi(CH3)3]2[OSi(CH3)2OSi(CH3)3],然后通过蒸汽蒸馏除去邻二甲苯。之后,添加102g 25重量%的氢氧化钠水溶液,并使用1000g热(90℃)水进行稀释。然后将混合物冷却至室温。获得根据本发明的水乳液WE-1,其含水量为80%。
2.3制备根据本发明的水乳液WE-3
将120g水添加到在搅拌容器中的250g 30重量%水分散体形式的三元共聚物(A.2)和200g硅油(线性聚二甲基硅氧烷,25℃下v=1000mm2/s)中,并使用Ultraturrax在25℃下以15000rpm搅拌2分钟。获得根据本发明的水乳液WE-3,其含水量为50%。
2.4制备根据本发明的水乳液WE-4
将120g水添加到250g 30重量%水分散体形式的三元共聚物(A.2)和200g硅油(平均每分子具有无规分布的两个(CH2)10-COOH基团,官能化的聚二甲基硅氧烷,25℃下v=1000mm2/s)中,使用Ultraturrax在25℃下以15000rpm搅拌2分钟。获得根据本发明的水乳液WE-4,其含水量为50%。
3.根据本发明的水乳液在皮革生产中的应用和对比例。
预先说明:除非另有说明,重量%数据表示活性物质的量并基于削匀重。
将100重量份削匀厚度为1.8-2.0mm铬鞣牛皮切割成各自2000g的三条,并在30℃下,经90分钟,在具有挡板的旋转筒(50升)中,用200重量%的水、2重量%的甲酸钠、0.4重量%的NaHCO3和2重量%的萘磺酸/甲醛缩合物(根据US 5,186,846实施例“Dispergiermittel 1”制备)转鼓加工。然后排出液体。将每条分别连同100重量%的水(30℃)放入旋转筒1至3中,并在每种情况下添加具有下列组成的1重量%的染料混合物:
70重量份染料,来自EP-B 0 970 148,实施例2.18,
30重量份萘胺棕75(铁络合物),颜色指数(Colour Index)1.7.16。
在10rpm下转鼓加工10分钟(30℃)后,添加6重量%的来自EP-B 0459 168、实施例K1的砜鞣剂和2重量%的树脂鞣剂(三聚氰胺/甲醛缩合物),并在筒中在15rpm下再转鼓加工45分钟。之后,添加4重量%的可从BASF Aktiengesellschaft买到的植物鞣剂Mimosa和3重量%的根据
4.(参见下文)的加油乳液FL-1,并进行转鼓加工45分钟。
之后,计量加入另外4重量%的加油乳液FL-1,并且如果合适,计量加入1重量%的如表1所示的根据本发明的水乳液。然后计量加入另外2重量%的棕色染料(参见上面)。
转鼓加工另外45分钟后,用甲酸进行酸化至pH 3.6-3.8。另外20分钟后,排出液体并用200重量%的水进行洗涤。之后,计量加入100重量%的水、2重量%的加油乳液FL-1和如表1所示的根据本发明的水乳液。用1重量%的甲酸进行酸化,排除液体并用水再洗涤一次。
将洗涤过的皮革均湿、干燥并根据表1中所列的测试标准评估。
表1:生产皮革
筒 | 乳液 | 丰满度 | 柔软度 | 粒面紧密度 | 手感 | 颜色渗透性 | 匀度 |
1 | WE-3 | 2 | 2 | 2 | 丝滑 | 3 | 2.5 |
2 | - | 2.5 | 3 | 2 | 干涩 | 3 | 2.5 |
3 | WE-4 | 1.5 | 1.5 | 2 | 丝滑 | 2.5 | 1.5 |
丝滑的手感令人感觉满意,而干涩的手感通常令人感觉不满意。
说明:
根据从1(非常好)至5(差)的等级体系进行评定。
4.制备加油乳液
在搅拌容器中,将2.3g聚异丁烯(Mn:1000g/mol)与300g正-C18H37O(CH2CH2O)25H、400克油酸以及2.3kg亚硫酸化的氧化三油精混合,并加热至60℃。然后添加4.7升水和100g正-C18H37O(CH2CH2O)7H。然后使得到的乳液经过间隙均化器并冷却至室温。获得了加油乳液FL-1。
5.制备根据本发明的乳液和对比乳液及其稳定性研究。
一般方法:
使用水将根据表2的30重量%水分散体形式的三元共聚物(A.2)、100g硅油(线性聚二甲基硅氧烷,25℃下v=350mm2/s)、根据表2的N-油基肌氨酸的钠盐补充至1Kg,并使用Ultraturrax在25℃下以15000rpm搅拌2分钟。获得了根据本发明的水乳液WE-5或WE-6。
为了制备对比乳液WE-7,省去了三元共聚物(A.2)并使用根据表2的乳化剂混合物。
在每种情况下,在室温储存以进行稳定性研究。
表2:根据本发明的乳液稳定性的比较(基于制备的乳液计,所有数据以重量%表示):
+:乳液,-:破乳
Claims (16)
1、可由以下物质自由基共聚并且如果合适的话水解获得的三元共聚物(A)用于制备聚硅氧烷(B)的水乳液或水分散体的用途,
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯,制备中使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂。
2、一种使用至少一种三元共聚物(A)和使用基于水乳液或水分散体总量计不超过2重量%的另外乳化剂制备聚硅氧烷(B)的水乳液或水分散体的方法,所述三元共聚物(A)可由以下物质自由基共聚并且如果合适的话水解获得:
(a)至少一种C3-C10二羧酸的酸酐,
(b)至少一种1,1-二(C1-C3烷基)取代的C4-C8烯烃,
(c)平均分子量Mn在200-10000g/mol范围内的聚异丁烯。
3、根据权利要求2的方法,其中1,1-二(C1-C3烷基)取代的C4-C8烯烃(b)为异丁烯。
4、根据权利要求2或3的方法,其中至少一种C3-C10二羧酸的酸酐(a)为马来酸酐。
5、根据权利要求2-4中任一项的方法,其使用基于水乳液或水分散体总量计不超过2重量%的多烷氧基化C10-C40脂肪醇作为另外的乳化剂。
6、根据权利要求2-5中任一项的方法,其中聚硅氧烷(B)是在室温下为液体的聚硅氧烷。
7、根据权利要求2-6中任一项的方法,其中聚硅氧烷是平均每分子具有至少一个羧基的聚硅氧烷。
8、根据权利要求2-6中任一项的方法,其中聚硅氧烷(B)是不具有羧基的聚硅氧烷。
9、根据权利要求2-8中任一项的方法,其中将聚硅氧烷(B)与使用的三元共聚物、基于水乳液或水分散体总量计至多2重量%的乳化剂和另外至少一种有机溶剂混合,然后分离出有机溶剂,所述有机溶剂选自在室温下为液体的脂族和芳族烃。
10、可通过根据权利要求2-9中任一项的方法获得的分散体或乳液。
11、根据权利要求10的分散体或乳液的用途,其用于生产纤维基底、用作脱模剂、用作清洁剂、用作润滑剂、用于处理或加工建筑材料或用在化妆品制剂中。
12、根据权利要求11的用途,其中纤维基底选自皮革、纸、木材、织物和板。
13、使用根据权利要求10的分散体或乳液生产纤维基底、清洁表面、分离制品、处理或加工建筑材料或生产化妆品制剂的方法。
14、根据权利要求13的方法,其中纤维基底选自皮革、纸、木材、织物和板。
15、使用根据权利要求10的分散体或乳液减少运动部件间摩擦的方法。
16、使用根据权利要求10的分散体或乳液生产的皮革、化妆品制剂或建筑材料。
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EP (1) | EP1937735A1 (zh) |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102892830A (zh) * | 2010-05-12 | 2013-01-23 | 巴斯夫欧洲公司 | 聚异丁烯的乳液、物质和方法 |
CN104479834A (zh) * | 2014-12-18 | 2015-04-01 | 蒙城县科技创业服务中心 | 一种耐寒抗裂性混凝土脱模剂及其制备方法 |
CN115012224A (zh) * | 2022-05-20 | 2022-09-06 | 苍南县永顺毛绒有限公司 | 一种防水毛绒及其表面处理工艺 |
CN115305298A (zh) * | 2022-08-30 | 2022-11-08 | 齐河力厚化工有限公司 | 一种纤维基材润滑剂微乳液及其制备方法和应用 |
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WO2008125628A2 (de) * | 2007-04-13 | 2008-10-23 | Basf Se | Verfahren zur formierung von organischen pigmenten |
US20100050904A1 (en) * | 2007-04-13 | 2010-03-04 | Basf Se | Production of finely divided pigments |
CN102333851B (zh) * | 2009-02-27 | 2016-06-15 | Ntn株式会社 | 润滑脂组合物、润滑脂封入轴承、推进器轴用万向联轴器、润滑油组合物及烧结含油轴承 |
EP2569408A1 (en) | 2010-05-12 | 2013-03-20 | The Procter and Gamble Company | Care polymers |
KR20140096112A (ko) | 2011-11-11 | 2014-08-04 | 바스프 에스이 | 자가-유화성 폴리올레핀 조성물 |
BR112014010971A2 (pt) | 2011-11-11 | 2017-06-06 | Basf Se | emulsão, processo para fabricar uma emulsão, uso de uma emulsão, e, polímero |
US8759274B2 (en) | 2011-11-11 | 2014-06-24 | Basf Se | Self-emulsifiable polyolefine compositions |
WO2013068272A1 (en) | 2011-11-11 | 2013-05-16 | Basf Se | Self-emulsifiable polyolefine compositions |
US20130118531A1 (en) | 2011-11-11 | 2013-05-16 | The Procter & Gamble Company | Emulsions containing polymeric cationic emulsifiers, substance and process |
EP2872557B1 (en) * | 2012-07-16 | 2016-09-07 | Emulco Laboratories C.V.B.A. | Method for the preparation of stable emulsions of polyisobutene |
MY171477A (en) * | 2012-07-16 | 2019-10-15 | Emulco Laboratories C V B A | Stable emulsions of polyisobutene and their use |
WO2014032920A1 (en) * | 2012-08-28 | 2014-03-06 | Basf Se | Carrier system for fragrances |
US20210340335A1 (en) | 2018-10-11 | 2021-11-04 | Emulco Laboratories C.V.B.A. | Method for producing emulsions and aqueous polyisobutene emulsion |
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US544657A (en) * | 1895-08-20 | Territory | ||
US2004950A (en) * | 1932-03-12 | 1935-06-18 | Bernard F Jenkins | Torque-measuring device |
US5229022A (en) * | 1988-08-01 | 1993-07-20 | Exxon Chemical Patents Inc. | Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920) |
FR2706469B1 (fr) * | 1993-06-16 | 1995-10-13 | Inst Francais Du Petrole | Polyisobutènes polyfonctionnels, leur préparation, leur formulation et leur utilisation. |
DE10003297C2 (de) * | 2000-01-27 | 2003-08-21 | Clariant Gmbh | Sprengstoffe, enthaltend modifizierte Copolymere aus Polyisobutylen, Vinylestern und Maleinsäureanhydrid als Emulgatoren |
US6239290B1 (en) * | 2000-09-08 | 2001-05-29 | Charles W. Buffa | Silicone Functionalized sorbitan esters |
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2006
- 2006-10-05 BR BRPI0617244A patent/BRPI0617244A2/pt not_active IP Right Cessation
- 2006-10-05 WO PCT/EP2006/067072 patent/WO2007042454A1/de active Application Filing
- 2006-10-05 US US12/090,160 patent/US20080274073A1/en not_active Abandoned
- 2006-10-05 AR ARP060104381A patent/AR058479A1/es unknown
- 2006-10-05 CN CNA200680037888XA patent/CN101287771A/zh active Pending
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102892830A (zh) * | 2010-05-12 | 2013-01-23 | 巴斯夫欧洲公司 | 聚异丁烯的乳液、物质和方法 |
CN104479834A (zh) * | 2014-12-18 | 2015-04-01 | 蒙城县科技创业服务中心 | 一种耐寒抗裂性混凝土脱模剂及其制备方法 |
CN115012224A (zh) * | 2022-05-20 | 2022-09-06 | 苍南县永顺毛绒有限公司 | 一种防水毛绒及其表面处理工艺 |
CN115012224B (zh) * | 2022-05-20 | 2023-08-01 | 苍南县永顺毛绒有限公司 | 一种防水毛绒及其表面处理工艺 |
CN115305298A (zh) * | 2022-08-30 | 2022-11-08 | 齐河力厚化工有限公司 | 一种纤维基材润滑剂微乳液及其制备方法和应用 |
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BRPI0617244A2 (pt) | 2016-08-23 |
US20080274073A1 (en) | 2008-11-06 |
EP1937735A1 (de) | 2008-07-02 |
WO2007042454A1 (de) | 2007-04-19 |
DE102005049327A1 (de) | 2007-04-19 |
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