CN105209585A - 通过特定碳二亚胺制备稳定的油配制品的方法 - Google Patents

通过特定碳二亚胺制备稳定的油配制品的方法 Download PDF

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CN105209585A
CN105209585A CN201480026303.9A CN201480026303A CN105209585A CN 105209585 A CN105209585 A CN 105209585A CN 201480026303 A CN201480026303 A CN 201480026303A CN 105209585 A CN105209585 A CN 105209585A
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ester
carbodiimide
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威廉·劳弗
阿明·埃克特
西格弗里德·金策尔
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Lanxess Deutschland GmbH
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Rhein Chemie Rheinau GmbH
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Abstract

本发明涉及一种通过特定碳二亚胺来制备稳定的油配制品的新颖方法。

Description

通过特定碳二亚胺制备稳定的油配制品的方法
技术领域
本发明涉及一种通过特定碳二亚胺来制备稳定的油配制品的新颖方法。
背景技术
一系列基础油和润滑剂基础成分,例如甘油三酸酯、合成羧酸酯、磷酸三酯、烯烃-二羧酸聚合物和硅油,会受到水或氧化剂的侵蚀,从而形成酸性分解产物和醇。这些酸性分解产物是分解程度的一种量度。可以将这些产物以酸值的形式进行定量规定,将其作为润滑油老化程度的量度。
酸和酸性分解产物的存在自动催化地加速了水解。由于在工业条件下总有少量水存在,由此限制了润滑剂的寿命。如在DE4435548A1所描述的,添加油溶性碳二亚胺可以有效地防止水解分解。然而,现有技术中记载的制备使用碳二亚胺稳定的油配制品的方法都具有使用固体碳二亚胺的缺点。固体碳二亚胺必须首先熔融并且随后被搅拌入加热的油配制品中。这个过程非常不便并且也不经济。理想地,首先在低温下搅拌这些碳二亚胺。此外,在这个过程中,碳二亚胺易于在所使用温度下消除有毒异氰酸酯和异氰酸酯的挥发物。
因此,本发明的目的包括提供不具有现有技术的这些缺点的方法。
发明内容
现在已经出人意料地发现油配制品可以通过本发明的方法按一种简单的方式进行稳定,并且从而让这一过程在润滑油工业中更加经济。此外,根据本发明的方法还在职业卫生和环境保护方面做出了显著的改善。
因此,本发明涉及一种制备油配制品的新颖方法,其中将至少一种具有式(I)的碳二亚胺
其中
R1=CH3或CH(CH3)2并且R2=H或CH(CH3)2
在10℃至40℃、优选15℃至30℃下添加到至少一种油中。
在本发明一个特别优选的实施例中,R1=CH3并且R2=H。
在本发明另一个优选的实施例中,R1=R2=CH(CH3)2
具有式(I)的碳二亚胺是可以从例如曼海姆的莱茵化学莱脑股份有限公司(RheinChemieRheinauGmbH)商购的、商品名为的化合物。
给予特别优选的是二邻甲苯基碳二亚胺,可从曼海姆的莱茵化学莱脑股份有限公司以商品名MTC商购。
在本发明的上下文中,所述油优选采取为矿物油的形式,特别优选为低硫环烷基油和/或天然脂肪、油或蜡——甘油三酸酯,优选大豆油、菜籽油或葵花子油,并且还可以是合成制备的酯,例如由甲醇、2-乙基己醇、乙二醇、丙三醇、三羟甲基丙烷(TMP)、季戊四醇或新戊二醇与例如硬脂酸、油酸、己二酸、对苯二甲酸和苯三甲酸进行酯化制备。
在本发明的一个优选的实施例中,该油是具有以下通式(II)的一种三羟甲基丙烷酯(TMP)
适合的三羟甲基丙烷酯是从德国专利申请DE102004025939A已知的。在以上通式(II)中,残基R3、R4和R5各自可以相同或不同,并且具有5到22个碳原子的直链或支链烷基。在本发明一个另外的优选实施例中,残基R3、R4和R5各自可以相同或不同,限定了具有7到18个碳原子的直链或支链烷基。
在此给予特别优选的是三羟甲基丙烷三油酸酯(TMP油酸酯)。
对于基于甲醇合成制备的酯,优选菜籽油甲基酯。
在本发明的另一个优选实施例中,使用一种油混合物。
通过根据本发明的方法稳定的油配制品还可以进一步包括本应用领域的惯用添加剂。例如,这些可以是抗氧化剂或金属减活化剂。
在一个另外的实施例中,该油配制品因此额外地包含在每种情况下都基于该油配制品按重量计0.005%至1.0%的抗氧化剂和/或按重量计0.01%至2.0%的金属减活化剂。
抗氧化剂的优选的量是基于该油配制品在按重量计0.1%与0.5%之间、并且特别是按重量计0.1%与0.2%之间。
金属减活化剂的优选的量是基于该油配制品在按重量计0.1%与1.0%之间、并且特别是按重量计0.1%与0.2%之间。
抗氧化剂优选是选自下组,该组由以下各项组成:二羟基甲苯、氢醌、4-叔丁基邻苯二酚、萘酚、苯基萘胺、二苯胺、苯基硫醚、生育酚以及所列的这些物质的混合物。
金属减活化剂优选选自由有机杂原子化合物,特别优选三唑、甲苯基三唑、二巯基噻二唑以及所列的这些物质的混合物组成的组。
为了稳定根据本发明制备的油配制品,基于该油配制品,使用按重量计0.05%至2%,优选按重量计0.1%至1%并且特别优选按重量计0.2%至0.5%的碳二亚胺。
优选地将碳二亚胺添加到一个混合或者储存容器中,特别优选直接添加到容器——优选圆筒或容器中。
在本发明一个优选的实施例中,碳二亚胺被倾倒入或是用管道泵入油中。通常混合在计量添加的时候就已经开始了,但可以通过搅拌单元例如桨式搅拌器、螺旋搅拌器或锚式搅拌器,分散剂,圆筒或容器搅拌器来加强混合。
在本发明的另一个优选实施例中,将碳二亚胺进料到混合或储存容器中,特别优选直接进料到容器——优选圆筒或容器中,并且随后倾倒入油。在倾倒入油的过程中,通常发生充分的混合。
本发明还进一步涉及通过本发明的方法制备的油配制品及其作为工艺用油、燃料、导热油、车用机油、油脂、金属加工液、涡轮和变压器用油的用途。
以下实例用于描述本发明,但是不具有限制性作用。
具体实施方式
工作实例:
在以下实例中,使用以下物质:
SXLMTC=MTC,具有式(I)的液态碳二亚胺,其中R1=CH3、R2=H,来自莱茵化学莱脑股份有限公司。
SXLILiq=ILiq,具有式(I)的碳二亚胺,其中R1=R2=CH(CH3)2
SXLI=I,基于2,6-二异丙基苯基异氰酸酯的固态单体碳二亚胺,来自莱茵化学莱脑有限公司。
TMP油酸酯=ESTMP05,来自巴斯夫股份公司。
菜籽油甲基酯(RME),来自ADM德国公司(ADMHamburgAG)。
实例1:
“饮料瓶试验”ASTMD2619是国际认可的油配制品规格的一部分,用于测试液体的水解稳定性。检测酸值的增加值,作为水解稳定性的量度。
测试条件:
-75ml测试油(菜籽油甲基酯),以下简称RME
-25ml蒸馏水
-温度:95℃。
评价标准:作为时间的函数(h):
-油相的酸值(AN)(mgKOH/g)
-水相的酸度(mgKOH/25ml)。
表1:
对于本发明的实例,在30℃下在一小时内将按重量计0.5%或按重量计1%的SXLMTC搅拌入菜籽油甲基酯中。对于对比实例,需要将温度提高到80℃以融化SXLI并且因此能够使其溶解于该油中。因此,在80℃下在一小时内将按重量计0.5%或按重量计1%的SXLI搅拌入。
(C)=对比实例,(I)=本发明的
表1中的结果显示根据本发明的方法制备的油配制品的水解稳定性在即使使用低浓度碳二亚胺的情况下也得到了提高。此外,对于现有技术中的化合物来说,温度必须提高到80℃才能完全制备的溶液,这样很不方便并且会伴有释放有毒物质的令人不希望的分解过程。
表2在30℃降低酸值:
MTC(本发明的)与SXLI(对比实例)的比较
实验步骤:
将298.5gTMP油酸酯在30℃加热。随后,加入1.5g(按重量计0.5%)的SXLMTC或1.5g(按重量计0.5%)的SXLI粉末其中之一,并且将该混合物在30℃下搅拌48h。分别在0、6、24、48h时移出一个样品并测量其酸值。
该表显示出根据本发明的混合物即使在30℃的温度下也具有明显降低的酸值。

Claims (9)

1.用于制备油配制品的方法,其特征在于将至少一种具有式(I)的碳二亚胺
其中
R1=CH3或CH(CH3)2并且
R2=H或CH(CH3)2
在10℃至40℃、优选15℃至30℃的温度下添加到至少一种油中。
2.根据权利要求1所述的方法,其特征在于该油是基于环烷矿物油和/或基于酯的一种油。
3.根据权利要求2所述的方法,其特征在于该基于酯的油采用甘油三酸酯、三羟甲基丙烷酯(TMP)和/或季戊四醇酯的形式。
4.根据权利要求2所述的方法,其特征在于该基于酯的油是菜籽油甲基酯。
5.根据权利要求1至4中任一项所述的方法,其特征在于使用的该碳二亚胺是一种具有式I的化合物
其中
R1=CH3并且
R2=H。
6.根据权利要求1至4中任一项所述的方法,其特征在于使用的该碳二亚胺是一种具有式I的化合物
其中
R1=CH(CH3)2并且
R2=CH(CH3)2
7.根据权利要求1至6中任一项所述的方法,其特征在于该具有式I的碳二亚胺是以0.1%至0.5%的浓度来使用的。
8.根据权利要求1至7所述的方法制备的油配制品。
9.根据权利要求8所述的油配制品作为工艺用油、燃料、导热油、车用机油、油脂、金属加工液、涡轮和变压器用油的用途。
CN201480026303.9A 2013-05-07 2014-05-06 通过特定碳二亚胺制备稳定的油配制品的方法 Pending CN105209585A (zh)

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