CN101044230B - 功能流体用腐蚀保护剂、水溶性浓缩物及其用途 - Google Patents

功能流体用腐蚀保护剂、水溶性浓缩物及其用途 Download PDF

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CN101044230B
CN101044230B CN2005800358063A CN200580035806A CN101044230B CN 101044230 B CN101044230 B CN 101044230B CN 2005800358063 A CN2005800358063 A CN 2005800358063A CN 200580035806 A CN200580035806 A CN 200580035806A CN 101044230 B CN101044230 B CN 101044230B
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赫尔穆特·特伊尼森
S·特伊尼森
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Abstract

本发明公开了功能流体用腐蚀保护剂,其包含5-80重量%的基于具有10-20个碳原子的饱和或不饱和脂肪酸的至少一种脂肪酸烷醇酰胺、5-80重量%的具有2-14个碳原子的至少一种醇、和5-80重量%的具有10-12个碳原子的至少一种芳族单羧酸或脂族二羧酸,其中这些组分的总和为100重量%,和所述重量%相对于所述腐蚀保护剂的重量;水基功能流体用的含有所述腐蚀保护剂的水溶性浓缩物;以及其用于制备金属成形和金属切削用的冷却/润滑剂、研磨剂、液压油和润滑剂的用途。

Description

功能流体用腐蚀保护剂、水溶性浓缩物及其用途
本发明包括功能流体用腐蚀保护剂、用于含水功能流体的包含该腐蚀保护剂的水溶性浓缩物、以及其用途。
含水功能流体由于其低可燃性和低环境风险而受到增大的关注。这些功能流体是用作金属成形和金属切削用冷却/润滑剂、研磨剂、润滑剂的流体,以及特别地用作压力流体,即液压油(Hydraulikflüssigkeiten)。这些含水功能流体也称为HFA流体或HFA液压油。该HFA液压油特别地用于矿业中的液压工作面支护***。它们通过混合1-20重量%的包含必要有效成分之一的含水浓缩物和辅助的99-80重量%的水而现场制成。所述浓缩物可包含作为润滑剂的合成制品或基于矿物油的制品。取决于所述水溶性浓缩物的组成,HFA液压油为包括微乳液在内的与矿物油或合成油的乳液(HFAE)或者溶液(HFAS)。该HFA液压油具有水的粘度,并可用于+5℃至+55℃的温度范围内。
当该类型含水功能流体或HFA液压油不能提供充分的防腐作用时,这会导致与所述功能流体相接触的表面即液压***的腐蚀。特别地,该腐蚀可引起剥蚀、空穴、凹坑形成,以及甚至引起结垢腐蚀产物的沉淀。由于当将HFA液压油用于大型液压***如矿业中的工作面支护时,必须不惜任何代价来避免该类腐蚀,因而这些含水功能流体包含腐蚀保护剂及其它添加剂,如动物油、植物油、矿物油和/或合成油、脂肪、或者油组分或脂肪组分作为润滑剂、脂肪醇、杀生物剂、杀菌剂、络合剂、重金属抑制剂、非离子或阴离子乳化剂、分散剂和消泡剂。
从EP 1175489 A1中,我们得知用于制备包含油相、水相、杀细菌剂或杀真菌剂和高压组分的含水切削液的方法。这些切削液可包含有机酸如癸二酸。
从DE 19833894 A1中,我们得知包含天然或合成矿物油、乳化剂、溶剂、防腐剂、金属抑制剂及其它典型添加剂和具有小于7.7的pH以确保皮肤耐受性的水溶性冷却-润滑浓缩物。作为腐蚀保护剂,该浓缩物可包含硼酸与伯或叔烷醇胺、乙氧基化或丙氧基化脂肪酸或脂肪酸烷醇酰胺、磷酸酯、***或噻二唑中的单独一种或相互组合的反应产物。尽管该文献提及可使用具有pH值接近中性的该浓缩物制备含水冷却/润滑剂,以及提及没有导致用所述冷却/润滑剂的水溶液处理的金属部件的腐蚀,但是由其制成的这些浓缩物和所述功能流体并不具有令人满意的腐蚀保护效果。特别地,当这些含水冷却/润滑剂与金属表面长时间接触时它们会导致被暴露的金属表面的腐蚀,如在液压***中的情况,即通过不希望的结垢沉淀和剥蚀。
因此本发明的目的是提供功能流体用腐蚀保护剂,其中在不降低该流体的根据其他要求的性能的情况下所述HFA流体(即用于液压***的HFA液压油)的腐蚀保护性能得以改进,因此其可以用于大体积的极其昂贵的液压***中,如用于矿业中。
令人惊讶地,已经发现通过本身分别已知的至少三种不同腐蚀保护添加剂的组合,将所述HFA液压油的腐蚀保护性能提高至出乎意料的高水平,因此不但可以防止剥蚀、空穴和凹坑形成,而且可以完全避免结垢腐蚀产物的沉淀,这可以在根据DSK Norm N 762830的缝隙腐蚀测试中使用典型HFA流体而观察到,如下文所述。
因此本发明的目的是根据主权利要求的腐蚀保护剂。从属权利要求涉及本发明该目的的优选实施方式、包含该腐蚀保护剂的水溶性浓缩物和其用于制备金属成形和切削用的含水的冷却/润滑剂、研磨剂、液压油或润滑剂的用途。
因此本发明的一个实施方式是功能流体用腐蚀保护剂,其包含5-80重量%的基于具有10-20个碳原子的饱和或不饱和脂肪酸的至少一种脂肪酸烷醇酰胺、5-80重量%的具有2-14个碳原子的至少一种醇和5-80重量%的具有10-12个碳原子的至少一种芳族单羧酸或脂族二羧酸,其中这些组分的总和为100重量%,以及所述重量百分数相对于所述腐蚀保护剂的重量。
在下面实施例和对比实施例中解释的比较实验已显示只有当所述腐蚀保护剂包含所述三种必需组分,和所述芳族单羧酸或脂族二羧酸总共具有包括羧基在内的10-12个碳原子时,才能完全避免不希望的腐蚀。例如,当存在具有10个碳原子的脂族单羧酸如新癸酸时,则不能避免固体沉淀物和线状腐蚀的出现。从本领域技术人员的角度考虑,该结果无疑是令人惊讶和出乎意料的。
优选地,根据本发明的所述腐蚀保护剂包含25-60重量%的所述至少一种脂肪酸烷醇酰胺、15-25重量%的所述至少一种醇、和20-50重量%的上文定义类型的至少一种芳族单羧酸或脂族二羧酸。
在根据本发明的所述腐蚀保护剂中的所述脂肪酸烷醇酰胺优选基于具有12-18个碳原子的饱和或不饱和脂肪酸,和具有2-6个碳原子的烷醇胺,即单乙醇胺、二乙醇胺、三乙醇胺、单丙醇胺、单异丙醇胺、2-氨基-2-甲基-1-丙醇、2-氨基-2-乙基-1,3-丙二醇和/或二甘醇胺,所述二甘醇胺也称为2-氨基乙氧基乙醇或乙二醇-2-氨基乙基醚。
根据本发明的特别优选的脂肪酸烷醇酰胺是椰油酸烷醇酰胺和妥尔油脂肪酸单烷醇酰胺,如椰油酸单乙醇酰胺、椰油酸单丙醇酰胺,和尤其是来自椰油酸、椰子油、妥尔油脂肪酸和/或妥尔油和二甘醇胺的反应产物。
根据本发明的所述腐蚀保护剂包含第二必需组分脂族、芳族或脂族-芳族单醇或二醇,优选具有8-10个碳原子,和特别优选异丙醇、正丁醇、丁基二甘醇、己二醇、丁基三甘醇、苄醇和/或苯氧乙醇。
用作根据本发明的所述腐蚀保护剂的第三重要组分的所述芳族单羧酸或脂族二羧酸优选选自癸二酸、十一烷二酸、十二烷二酸和对叔丁基苯甲酸。已证明这些酸的混合物是特别有效的,特别是十一烷二酸和十二烷二酸的混合物,其以3∶1-1∶3的重量比,和特别地以1∶1的重量比。
本发明的另一个目的是用于含水功能流体、特别用于HFA液压油的水溶性浓缩物,其包含动物油、植物油、矿物油和/或合成油、脂肪、或者油组分或脂肪组分作为润滑剂、脂肪醇、杀生物剂、杀菌剂、络合剂、重金属抑制剂、非离子或阴离子乳化剂、分散剂、消泡剂、腐蚀保护剂、和水、和作为其余部分的典型添加剂、以及作为根据本发明的重要组分的为2-20重量%、优选为5-15重量%的如上文定义的所述腐蚀保护剂,其中重量百分比相对于所述水溶性浓缩物的重量。在一个优选方案中,本发明涉及一种用于含水功能流体的水溶性浓缩物,其包含动物油、植物油、矿物油和/或合成油、脂肪、油组分或脂肪组分作为润滑剂、脂肪醇、杀生物剂、杀菌剂、络合剂、重金属抑制剂、非离子或阴离子乳化剂、分散剂、消泡剂、腐蚀保护剂、溶剂、防腐剂、和水、和作为其余部分的典型添加剂,特征在于其包含作为腐蚀保护剂的2-20重量%、优选5-15重量%的如权利要求1-10任一项中的所述腐蚀保护剂,和所述重量%相对于所述浓缩物的重量。
根据一个优选实施方式,所述水溶性浓缩物包含1-12重量%、优选2-8重量%的基于具有10-20个碳原子的饱和或不饱和脂肪酸的至少一种脂肪酸烷醇酰胺、1-8重量%、优选1.5-5重量%的具有2-14个碳原子的至少一种醇、和1-8重量%、优选1-5重量%的具有10-12个碳原子的芳族单羧酸或脂族二羧酸。
所述水溶性浓缩物有利地包含基于具有12-18个碳原子的饱和或不饱和脂肪酸和具有2-6个碳原子的烷醇胺的脂肪酸烷醇酰胺,其中特别优选单乙醇胺、二乙醇胺、三乙醇胺、单丙醇胺、单异丙醇胺、2-氨基-2-甲基-1-丙醇、2-氨基-2-乙基-1,3-丙二醇和二甘醇胺作为所述烷醇胺。更优选地,所述浓缩物包含作为所述脂肪酸烷醇酰胺的椰油酸单烷醇酰胺和/或妥尔油酸妥尔油脂肪酸单烷醇胺,特别是椰油酸单乙醇酰胺和/或妥尔油酸妥尔油脂肪酸单丙醇酰胺。根据另一个优选实施方式,将椰油酸、椰子油、妥尔油酸妥尔油脂肪酸和/或妥尔油和二甘醇胺的反应产物用作所述脂肪酸烷醇酰胺浓缩物有利地包含具有3-10个碳原子的脂族、芳族或脂族-芳族单醇或二醇作为所述醇,更优选为异丙醇、正丁醇、丁基二甘醇、己二醇、丁基三甘醇、苄醇和苯氧乙醇,其中这些醇可以单独或以任何所希望的混合物形式使用。
所述水溶性浓缩物优选包含作为所述芳族单羧酸或脂族二羧酸的癸二酸、十一烷二酸、十二烷二酸或对叔丁基苯甲酸,其中这些酸可单独或以混合物的形式使用。特别优选十一烷二酸和十二烷二酸以重量比3∶1-1∶3、特别地1∶1的混合物。已发现这些混合物在腐蚀保护效果方面是特别有利的。
根据另一个优选实施方式,根据本发明的所述水溶性浓缩物可具有0.5-3重量%的杀生物化合物,其选***生物季铵化合物、胍衍生物、O-或N-缩甲醛、O-或N-乙缩醛、异噻唑啉类、异噻唑啉酮类、脂族胺或二胺、3-碘-2-丙炔基-丁基氨基甲酸酯(3-Iod-2-propinyl-butylcarbamat)、双(3-氨基丙基)-十二烷基胺及其混合物。作为杀真菌剂或杀细菌剂,所述浓缩物可包含0.5-3重量%的杀菌的吡啶衍生物,优选羟基吡啶氧化物或羟基吡啶氧化物衍生物如2-吡啶硫醇-1-氧化物钠盐。
根据另一个优选实施方式,根据本发明的所述水溶性浓缩物可包含0.5-3重量%的杀生物化合物,其选***生物季铵化合物、胍衍生物、O-或N-缩甲醛、O-或N-乙缩醛、异噻唑啉类、异噻唑啉酮类、脂族胺或二胺、3-碘-2-丙炔基-丁基氨基甲酸酯、双(3-氨基丙基)-十二烷基胺及其混合物。作为杀真菌剂或杀细菌剂,所述浓缩物可包含0.5-3重量%的杀菌的吡啶衍生物,优选羟基吡啶氧化物或羟基吡啶氧化物衍生物如2-吡啶硫醇-1-氧化物钠盐。
作为络合剂,根据本发明的所述浓缩物可包含0.5-5重量%的乙二胺四乙酸或其碱金属或铵盐、柠檬酸钠、葡糖酸钠、N,N′-双水杨内酯类、和/或它们的衍生物。
根据另一个有利实施方式,根据本发明的所述水溶性浓缩物包含1-8重量%、优选2-5重量%的附加腐蚀保护剂,其选自磷酸酯如乙基己基磷酸、膦酸衍生物、二胺氧乙醇(Diaminoxethylat)、三胺氧乙醇(Triaminoxethylat)、烷基咪唑啉、聚胺萘二甲酸胺类、合成或天然磺酸盐如石油磺酸盐、对叔丁基苯甲酸、三羧酸类、新癸酸类、5或6-羧基-4-己基-2-己烯-1-辛酸、饱和或不饱和脂肪酸、乙氧基化或丙氧基化脂肪酸和脂肪酸烷醇酰胺、噻二唑化合物及它们的混合物。
此外,根据本发明的所述水溶性浓缩物可包含作为附加腐蚀保护剂的3-35重量%的来自硼酸与伯或叔烷醇胺的反应产物。
根据本发明的所述浓缩物可进一步包含0.05-1.5重量%的苯并***和/或甲苯甲酰***和/或其衍生物作为重金属抑制剂。
根据本发明,所述水溶性浓缩物包含3-70重量%的天然或合成矿物油作为动物、植物、矿物和/或合成润滑剂;2-40重量%的酯油,其为本领域技术人员公知的典型合成酯油;1-6重量%的磷酸化和/或乙氧基化的醇和/或2-35重量%的聚二醇和/或聚乙烯吡咯烷酮,条件是该润滑剂占所述水溶性浓缩物的10-70重量%。
作为消泡剂,所述浓缩物可包含0.05-1重量%的硅氧烷化合物,同时优选1-5重量%的油酰基肌氨酸(Oleoylsarcosid)作为乳化剂。所述浓缩物可包含0.2-5重量%的丙烯酸聚合物作为分散剂,特别是聚(甲基)丙烯酸的盐。
根据一个优选实施方式,相当于得到的所述功能流体而言,在用水稀释到1-20重量%的浓度后,所述水溶性浓缩物具有8.4-9.8、优选9.0-9.5的pH值。
根据另一个实施方式,本发明涉及通过混合1-20重量、优选2-5重量%的如上所述水溶性浓缩物与99-80重量%、优选99-95重量%的水,如上所述的水溶性浓缩物用于制备金属成形和金属切削用的水基的冷却/润滑剂、研磨剂、液压油或润滑剂的用途。在根据本发明的用途的意义上,认为非切削金属成形是深冲压、冷成形或轧制,而切削金属制造包括金属的弯曲、磨碎、钻孔和研磨。
已经惊讶地确定根据本发明的所述水溶性浓缩物即使当与硬度为9°dH~42°dH的水在2%浓度水平上混合时,也可产生绝对稳定(甚至在50℃温度下600小时后)的乳液形式的HFA液压油。
通过简单混合所述组分而制备根据本发明的所述腐蚀保护剂。通过将在水中可溶或可分散的所述组分首先加入到水中,然后将油溶性成分溶解或分散在所述油组分中,然后将所述含水混合物缓慢加入到所述矿物油混合物中而制备本发明的所述水溶性浓缩物。
以下实施例用来进一步阐明本发明。
在实施例和对比实施例中,使用根据DSK norm N 762830的缝隙腐蚀测试,测定由根据本发明的所述腐蚀保护剂而得到的腐蚀保护效果。在Glückauf138(2002)No.5,208-212页中公开了使用所述缝隙腐蚀测试的腐蚀测试方法。所述方法包括将在纯静态条件下于95%湿度和35℃的测试温度将待测试的所述压力流体或液压油保持在规定冲压装置(活塞-汽缸)中达21天。在所述汽缸的内表面和所述活塞上的青铜部分之间形成缝隙区域。将典型密封环放于所述青铜部分上。在与处于测试中的所述流体接触21天后,拆卸所述冲压装置并检查所述汽缸的内表面上的缝隙区域的腐蚀状况。该缝隙腐蚀测试显示如果不存在足够的腐蚀保护作用,除了剥蚀和凹坑形成外,在所述汽缸表面上的缝隙区域中还沉积了鳞片状颜色相当不同的腐蚀产物。如果这些沉积物位于在所述汽缸表面上的密封环的缝隙区域中,则通常还在所述密封环表面和所述青铜表面上发现这些沉积物。小颗粒尤其聚集在密封唇上,这些小颗粒是导致围绕所述汽缸表面周边的线状腐蚀的原因。关于术语“缝隙腐蚀”的定义,参考标准DIN EN ISO8044-3.17。
实施例1-5和对比实施例A-E
首先使用列于下表1-3中的组分来制备水溶性浓缩物,然后以2重量份浓缩物与98重量份水的比例进行混合以制备HFA液压油,然后使用如上所述的缝隙腐蚀测试对其进行测试。
为了制备所述水溶性浓缩物,首先提供水,向其中加入氢氧化钾并通过搅拌使其溶解。加入在每种情况中使用的酸如癸二酸、十二烷二酸、十一烷二酸,或在对比实施例E中使用的新癸酸,并在50℃下进行搅拌直至该混合物的pH值为7。然后加入柠檬酸钠和单乙醇胺,并在搅拌下将所述混合物冷却到25℃。
在分开的容器中,加热作为润滑剂的一部分脂族烃(50%),然后在搅拌下加入脂肪酸烷醇酰胺、石油磺酸钠(Natriumpetrolsulfonat),并然后加入余下的脂族烃,随后加入其余成分。然后彻底混合和将从第一阶段得到的含水混合物在搅拌下加入到所述脂族烃混合物中。所得产物是淡褐色、澄清、略有粘性的浓缩物,然后将其与水进行混合以制备包含2重量%所述浓缩物和98重量%水的所述含水功能流体(HFA液压油)。将该HFA液压油置于用于所述缝隙腐蚀测试的冲压装置的缝隙区域中并在95%的湿度和35℃的温度下静置保存21天。在打开所述冲压装置并移出其中包含的所述HFA流体后,检查测试固定物的在外管底部上、在所述缝隙区域中和在所述青铜活塞区域中的淤积,和检查在内管和外管中进行清洁前的沉积物,和检查在所述内管和外管中进行清洁后的锈蚀,和检查在所述汽缸内表面上和在所述汽缸的缝隙区域中以及在所述青铜活塞表面上的固体沉积物。
如下表1-3中所显示,使用根据本发明的所述HFA液压油时不存在腐蚀效应,而对比实施例A和B中的产物不能通过根据DSN norm N 762830的腐蚀测试,因为在清洁前可在汽缸上发现沉积物、以及在所述汽缸的缝隙区域中发现固体沉积物和围绕所述汽缸的缝隙区域周边发现线状腐蚀。
 
表1 实施例1 对比A 实施例2 对比B
组分 重量% 重量% 重量% 重量%
28.0 31.6 28.0 32.0
甲苯甲酰***/苯并*** 0.5 0.5 0.5 0.5
脂肪醇 聚乙二醇醚 3.6 3.6 3.6 3.6
油酰基肌氨酸 1.8 1.8 1.8 1.8
六氢三嗪 1.2 1.2 1.2 1.2
脂族烃,沸点范围<200℃(BNS4) 42.8 42.8 42.8 42.8
合成石油磺酸钠 1.8 1.8 1.8 1.8
氢氧化钾 1.3 1.3 1.3
柠檬酸钠 0.9 0.9 0.9 0.9
三乙醇胺,纯
油基醚羧酸5EO 1.8 1.8 1.8 1.8
5-,6-羧基-4-己基-2-环己烯-1-辛酸
聚硅氧烷消泡剂 0.25 0.25 0.25 0.25
单乙醇胺 2.6 2.6 2.6 2.6
妥尔油脂肪酸
[0041] 
2-乙基己基磷酸
3-碘-2-丙炔基-丁基氨基甲酸酯 0.35 0.35 0.35 0.35
双(3-氨基丙基)-十二烷基胺 0.5 0.5 0.5 0.5
椰油酸烷醇酰胺 3.0 3.0
妥尔油脂肪酸烷醇酰胺 6.3 6.3 3.3 3.3
正丁醇 0.9 0.9 0.9
苄醇 2.7 2.7 2.7
丁基二甘醇
癸二酸
十二烷二酸 1.35 1.35 1.35
十一烷二酸 1.35 1.35 1.35
新癸酸(C<sub>10</sub>单羧酸)
总和 100.00 100.00 100.00 100.00
稀释后的pH值 9.3 8.8 9.2 9.4
根据DSK N 762 830的缝隙腐蚀测试 无腐蚀 在汽缸中的沉积物,固体沉积物,线状腐蚀 无腐蚀 在汽缸中的沉积物,固体沉积物,线状腐蚀
[0042] 
表2 实施例3 对比C 实施例4 对比D
组分 重量% 重量% 重量% 重量%
25.7 30.1 59.0 62.5
甲苯甲酰***/苯并*** 0.2 0.2 0.2 0.2
脂肪醇 聚乙二醇醚 3.6 3.6 3.0 3.0
油酰基肌氨酸 1.8 1.8 1.0 1.0
六氢三嗪 0.5 0.5 1.0 1.0
脂族烃,沸点范围<200℃(BNS4) 42.8 42.8 13.0 13.0
合成石油磺酸钠 1.8 1.8 1.0 1.0
氢氧化钾 1.0 1.0 1.0 1.0
柠檬酸钠 0.9 0.9 1.0 1.0
三乙醇胺,纯
油基醚羧酸5EO 1.8 1.8 2.0 2.0
5-,6-羧基-4-己基-2-环己烯-1-辛酸 0.75 0.75
聚硅氧烷消泡剂 0.25 0.25 0.5 0.5
单乙醇胺 4.3 4.3 3.8 3.8
妥尔油脂肪酸 0.8 0.8
2-乙基己基磷酸 2.0 2.0 3.0 3.0
3-碘-2-丙炔基丁基氨基甲酸酯
双(3-氨基丙基)-十二烷基胺 0.5 0.5
椰油酸烷醇酰胺 5.0 5.0 5.0 5.0
妥尔油脂肪酸烷醇酰胺
正丁醇 0.9 1.0
苄醇 2.5 2.5
丁基二甘醇 1.0
癸二酸 1.0 1.0
十二烷二酸 1.0 1.0
[0043] 
十一烷二酸 1.0 1.0 1.0 1.0
新癸酸(C<sub>10</sub>单羧酸)
总和 100.00 100.00 100.0 100.0
稀释后的pH值 9.40 9.40 9.2 8.6
根据DSK N 762 830的缝隙腐蚀测试 无腐蚀 在汽缸中的沉积物,固体沉积物,线状腐蚀 无腐蚀 在汽缸中的沉积物,固体沉积物,线状腐蚀
 
表3 实施例5 对比E
组分 重量% 重量%
61.5 61.5
甲苯甲酰***/苯并*** 0.2 0.2
脂肪醇 聚乙二醇醚 3.0 3.0
油酰基肌氨酸 1.0 1.0
六氢三嗪 1.0 1.0
脂族烃,沸点范围<200℃(BNS4) 13.0 13.0
合成石油磺酸钠 1.0 1.0
氢氧化钾 1.0 1.0
柠檬酸钠 1.0 1.0
三乙醇胺,纯 2.0 2.0
油基醚羧酸5EO 2.0 2.0
5-,6-羧基-4-己基-2-环己烯-1-辛酸
聚硅氧烷消泡剂 0.5 0.5
[0045] 
单乙醇胺 0.3 0.3
妥尔油脂肪酸
2-乙基己基磷酸
3-碘-2-丙炔基丁基氨基甲酸酯
双(3-氨基丙基)-十二烷基胺
椰油酸烷醇酰胺 5.0 5.0
妥尔油脂肪酸烷醇酰胺
正丁醇 1.0 1.0
苄醇 1.5 1.5
丁基二甘醇 3.0 3.0
癸二酸
十二烷二酸 1.0
十一烷二酸 1.0
新癸酸(C<sub>10</sub>单羧酸) 2.0
总和 100.00 100.00
稀释后的pH值 8.9 9.0
根据DSK N 762 830的缝隙腐蚀测试 无腐蚀 在汽缸中的沉积物,固体沉积物,线状腐蚀
所述对比实施例E特别显示包含新癸酸即C10-单羧酸的含水液压油引起了明显的腐蚀效应,并因此不适合用作HFA液压油,而根据本发明的所述腐蚀保护剂和包含它的根据本发明的不同于本领域现有技术的特定脂族二羧酸的所述HFA液压油显示出无腐蚀效应,和直接适用于例如用于矿业的液压工作面支护***中。
根据本发明的所述规定脂肪酸烷醇酰胺、所述规定醇和所述规定芳族单羧酸或规定脂族二羧酸的组合在腐蚀保护性能上的跨越性改善结果是令人惊讶的,并且决不能预测到该结果。

Claims (41)

1.功能流体用腐蚀保护剂,其包含5-80重量%的基于具有10-20个碳原子的饱和或不饱和脂肪酸的至少一种脂肪酸烷醇酰胺、5-80重量%的具有2-14个碳原子的至少一种醇、和5-80重量%的具有10-12个碳原子的至少一种芳族单羧酸或脂族二羧酸,其中这些组分的总和为100重量%,和所述重量%相对于所述腐蚀保护剂的重量。
2.如权利要求1中的腐蚀保护剂,特征在于其包含25-60重量%的至少一种脂肪酸烷醇酰胺、15-25重量%的至少一种醇和20-50重量%的至少一种芳族单羧酸或脂族二羧酸,和这些组分的总和为100重量%。
3.如权利要求1或2中的腐蚀保护剂,特征在于其包含基于具有12-18个碳原子的饱和或不饱和脂肪酸和具有2-6个碳原子的烷醇胺的脂肪酸烷醇酰胺。
4.如权利要求3中的腐蚀保护剂,特征在于其包含基于具有12-18个碳原子的饱和或不饱和脂肪酸和单乙醇胺、二乙醇胺、三乙醇胺、单丙醇胺、单异丙醇胺、2-氨基-2-甲基-1-丙醇、2-氨基-2-乙基-1,3-丙二醇和/或二甘醇胺的脂肪酸烷醇酰胺。
5.如权利要求4中的腐蚀保护剂,特征在于其包含椰油酸单烷醇酰胺和/或妥尔油脂肪酸单烷醇酰胺作为所述脂肪酸烷醇酰胺。
6.如权利要求5中的腐蚀保护剂,特征在于其包含椰油酸、椰子油、妥尔油脂肪酸和/或妥尔油与二甘醇胺的反应产物作为所述脂肪酸烷醇酰胺。
7.如权利要求5中的腐蚀保护剂,特征在于其包含椰油酸单乙醇酰胺、椰油酸单丙醇酰胺、妥尔油脂肪酸单乙醇酰胺和/或妥尔油脂肪酸单丙醇酰胺作为所述脂肪酸烷醇酰胺。
8.如权利要求1或2中的腐蚀保护剂,特征在于其包含具有3-10个碳原子的脂族、芳族或脂族-芳族单醇或二醇作为所述醇。
9.如权利要求8中的腐蚀保护剂,特征在于其包含异丙醇、正丁醇、丁基二甘醇、己二醇、丁基三甘醇、苄醇和/或苯氧乙醇作为所述醇。
10.如权利要求1或2中的腐蚀保护剂,特征在于其包含选自癸二酸、十一烷二酸、十二烷二酸和对叔丁基苯甲酸的芳族单羧酸或脂族二羧酸。
11.用于含水功能流体的水溶性浓缩物,其包含动物油、植物油、矿物油和/或合成油、脂肪、油组分或脂肪组分作为润滑剂、脂肪醇、杀生物剂、杀菌剂、络合剂、重金属抑制剂、非离子或阴离子乳化剂、分散剂、消泡剂、腐蚀保护剂、溶剂、防腐剂、和水,特征在于其包含作为腐蚀保护剂的2-20重量%的如权利要求1-10任一项中的所述腐蚀保护剂,和所述重量%相对于所述浓缩物的重量。
12.如权利要求11中的浓缩物,特征在于其包含作为腐蚀保护剂的5-15重量%的如权利要求1-10任一项中的所述腐蚀保护剂,和所述重量%相对于所述浓缩物的重量。
13.如权利要求11或12中的浓缩物,特征在于其包含1-12重量%的基于具有10-20个碳原子的饱和或不饱和脂肪酸的至少一种脂肪酸烷醇酰胺、1-8重量%的具有2-14个碳原子的至少一种醇、和1-8重量%的具有10-12个碳原子的至少一种芳族单羧酸或脂族二羧酸。
14.如权利要求13中的浓缩物,特征在于其包含2-8重量%的至少一种脂肪酸烷醇酰胺、1.5-5重量%的至少一种醇、和1-5重量%的至少一种芳族单羧酸或脂族二羧酸。
15.如权利要求11或12中的浓缩物,特征在于其包含基于具有12-18个碳原子的饱和或不饱和脂肪酸和具有2-6个碳原子的烷醇胺的脂肪酸烷醇酰胺。
16.如权利要求15中的浓缩物,特征在于其包含基于具有12-18个碳原子的饱和或不饱和脂肪酸和单乙醇胺、二乙醇胺、三乙醇胺、单丙醇胺、单异丙醇胺、2-氨基-2-甲基-1-丙醇、2-氨基-2-乙基-1,3-丙二醇和/或二甘醇胺的脂肪酸烷醇酰胺。
17.如权利要求15中的浓缩物,特征在于其包含椰油酸单烷醇酰胺和/或妥尔油脂肪酸单烷醇酰胺作为所述脂肪酸烷醇酰胺。
18.如权利要求17中的浓缩物,特征在于其包含椰油酸、椰子油、妥尔油脂肪酸和/或妥尔油与二甘醇胺的反应产物作为所述脂肪酸烷醇酰胺。
19.如权利要求17中的浓缩物,特征在于其包含椰油酸单乙醇酰胺、椰油酸单丙醇酰胺、妥尔油脂肪酸单乙醇酰胺和/或妥尔油脂肪酸单丙醇酰胺作为所述脂肪酸烷醇酰胺。
20.如权利要求11或12中的浓缩物,特征在于其包含具有3-10个碳原子的脂族、芳族或脂族-芳族单醇或二醇作为所述醇。
21.如权利要求20中的浓缩物,特征在于其包含异丙醇、正丁醇、丁基二甘醇、己二醇、丁基三甘醇、苄醇和/或苯氧乙醇作为所述醇。
22.如权利要求11或12中的浓缩物,特征在于其包含选自癸二酸、十一烷二酸、十二烷二酸和对叔丁基苯甲酸的芳族单羧酸或脂族二羧酸。
23.如权利要求11或12中的浓缩物,特征在于其包含0.5-3重量%的杀生物化合物,其选***生物季铵化合物、胍衍生物、O或N-缩甲醛、O或N-乙缩醛、异噻唑啉类、异噻唑啉酮类、脂族胺或二胺、3-碘-2-丙炔基-丁基氨基甲酸酯、双(3-氨基丙基)-十二烷基胺及其混合物。
24.如权利要求11或12中的浓缩物,特征在于其包含0.5-3重量%的杀菌的吡啶衍生物作为杀真菌剂或杀细菌剂。
25.如权利要求24中的浓缩物,特征在于所述杀菌的吡啶衍生物为羟基吡啶氧化物或羟基吡啶氧化物衍生物。
26.如权利要求24中的浓缩物,特征在于所述杀菌的吡啶衍生物为2-吡啶硫醇-1-氧化物钠盐。
27.如权利要求11或12中的浓缩物,特征在于其包含0.5-5重量%的乙二胺四乙酸或其碱金属或铵盐、柠檬酸钠、葡糖酸钠、N,N′-双水杨内酯类和/或它们的衍生物作为络合剂。
28.如权利要求11或12中的浓缩物,特征在于其包含1-8重量%的附加腐蚀保护剂,其选自磷酸酯、膦酸衍生物、二胺氧乙醇、三胺氧乙醇、烷基咪唑啉、聚胺萘二甲酸胺类、合成或天然磺酸盐、对叔丁基苯甲酸、三羧酸类、新癸酸类、5或6-羧基-4-己基-2-己烯-1-辛酸、饱和或不饱和脂肪酸、乙氧基化或丙氧基化脂肪酸和脂肪酸烷醇酰胺、噻二唑化合物及它们的混合物。
29.如权利要求28中的浓缩物,特征在于其包含2-5重量%的附加腐蚀保护剂。
30.如权利要求28中的浓缩物,特征在于所述磷酸酯为乙基己基磷酸。
31.如权利要求28中的浓缩物,特征在于所述合成或天然磺酸盐为石油磺酸盐。
32.如权利要求11或12中的浓缩物,特征在于其包含3-25重量%的来自硼酸与伯或叔烷醇胺的反应产物作为附加腐蚀保护剂。
33.如权利要求11或12中的浓缩物,特征在于其包含0.05-1.5重量%的苯并***和/或甲苯甲酰***和/或其衍生物作为重金属抑制剂。
34.如权利要求11或12中的浓缩物,特征在于其包含3-70重量%的天然或合成矿物油;2-40重量%的酯油;1-6重量%的磷酸化和/或乙氧基化的醇和/或2-35重量%的聚二醇和/或聚乙烯吡咯烷酮作为动物、植物、矿物和/或合成润滑剂,条件是该润滑剂占所述浓缩物的10-70重量%。
35.如权利要求11或12中的浓缩物,特征在于其包含0.05-1重量%的硅氧烷化合物作为消泡剂。
36.如权利要求11或12中的浓缩物,特征在于其包含1-5重量%的油酰基肌氨酸和/或乙氧基化油基醚羧酸作为乳化剂。
37.如权利要求11或12中的浓缩物,特征在于其包含0.2-5重量%的丙烯酸聚合物作为分散剂。
38.如权利要求37中的浓缩物,特征在于所述分散剂是聚(甲基)丙烯酸的盐。
39.如权利要求11或12中的浓缩物,特征在于在用水稀释到相对于所得功能流体的1-20重量%的浓度后,其具有8.4-9.8的pH值。
40.如权利要求39中的浓缩物,特征在于在用水稀释到相对于所得功能流体的1-20重量%的浓度后,其具有9.0-9.5的pH值。
41.如权利要求11-40至少一项中的所述水溶性浓缩物通过混合1-20重量%的该浓缩物与99-80重量%的水而用于制备金属成形和金属切削用的水基的冷却-润滑剂、研磨剂、液压油和润滑剂的用途。
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