CN116410805A - 一种润滑油添加剂及润滑油 - Google Patents
一种润滑油添加剂及润滑油 Download PDFInfo
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- CN116410805A CN116410805A CN202111663080.5A CN202111663080A CN116410805A CN 116410805 A CN116410805 A CN 116410805A CN 202111663080 A CN202111663080 A CN 202111663080A CN 116410805 A CN116410805 A CN 116410805A
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- lubricating oil
- oil additive
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- ionic liquid
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 102
- 239000000654 additive Substances 0.000 title claims abstract description 79
- 230000000996 additive effect Effects 0.000 title claims abstract description 79
- 239000002199 base oil Substances 0.000 claims abstract description 39
- 239000002608 ionic liquid Substances 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000003599 detergent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- -1 amyl diphenylamine Chemical group 0.000 claims description 29
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 23
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 6
- 239000006078 metal deactivator Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 150000004867 thiadiazoles Chemical class 0.000 claims description 5
- YSIQDTZQRDDQNF-UHFFFAOYSA-L barium(2+);2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Ba+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 YSIQDTZQRDDQNF-UHFFFAOYSA-L 0.000 claims description 4
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical class C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 3
- XBBHFQNIEJGGIG-UHFFFAOYSA-N dibutyllead Chemical compound CCCC[Pb]CCCC XBBHFQNIEJGGIG-UHFFFAOYSA-N 0.000 claims description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 claims description 2
- RNQNKOBSVNOJRI-UHFFFAOYSA-N heptan-4-imine Chemical compound CCCC(=N)CCC RNQNKOBSVNOJRI-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 10
- 239000013556 antirust agent Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 7
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical class CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000008054 sulfonate salts Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003873 salicylate salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- C10M157/00—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential
- C10M157/10—Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a compound containing atoms of elements not provided for in groups C10M157/02 - C10M157/08
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2227/061—Esters derived from boron
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Abstract
本发明提供一种润滑油添加剂及润滑油。本发明的润滑油添加剂,按照质量百分含量包括:清净剂1.5‑3%;分散剂50‑80%;抗磨剂3.5‑5%;离子液体2%‑10%;抗氧剂5%‑6%;防锈剂1%‑2%;金属钝化剂0.1%‑0.6%;其余为基础油;其中,所述离子液体包括式1的结构:其中,n选自4‑9中的正整数。本发明的润滑油添加剂能够兼具较为优良的抗磨性、防腐蚀性、流动性、稳定性和环境友好性。
Description
技术领域
本发明涉及润滑油技术领域,特别涉及一种润滑油添加剂及润滑油。
背景技术
目前,全球新能源汽车的发展主要以纯电动汽车和混合动力汽车为主。电动汽车减速箱油除了要具备传统自动变速箱油的润滑、冷却、动力传递等功能外,还需要具备高转速电机下油品的齿轮和轴承保护性能、电化学性能、铜腐蚀性能以及材料兼容性。润滑油添加剂的性能直接影响减速箱油的性能。
因此,急需制备一种兼具较为优良的抗磨性、防腐蚀性、流动性、稳定性和环境友好性的润滑油添加剂。
发明内容
本发明提供一种润滑油添加剂,该润滑油添加剂能够兼具较为优良的抗磨性、防腐蚀性、流动性、稳定性和环境友好性。
本发明提供一种润滑油,该润滑油由于包括上述的润滑油添加剂,所以不仅兼具较为优异的抗磨性、流动性、防腐蚀和稳定性,而且具有较为优异的环保性。
本发明提供一种润滑油添加剂,按照质量百分含量包括:
其余为基础油;
其中,所述离子液体包括以下结构:
其中,n选自4-9中的正整数。
如上所述的润滑油添加剂,其中,按照质量百分含量包括:
其余为基础油。
如上所述的润滑油添加剂,其中,所述清净剂包括磺酸盐和/或酚盐。
如上所述的润滑油添加剂,其中,所述分散剂包括单丁二酰亚胺和/或硼化丁二酰亚胺。
如上所述的润滑油添加剂,其中,所述抗磨剂选自丁基三苯基硫代磷酸酯、二丁基二硫代氨基甲酸铅和二烷基二硫代磷酸酯中的至少一种。
如上所述的润滑油添加剂,其中,所述抗氧剂包括辛基/戊基二苯胺和/或辛基取代二苯胺。
如上所述的润滑油添加剂,其中,所述防锈剂选自二壬基萘磺酸钡、十二烯基丁二酸和N,N’-双(苯丙并三氮唑亚甲基)月桂胺中的至少一种。
如上所述的润滑油添加剂,其中,所述金属钝化剂包括甲苯并三唑衍生物和/或噻二唑衍生物。
如上所述的润滑油添加剂,其中,所述基础油为II类基础油。
本发明还提供一种润滑油,其中,包括如上所述的润滑油添加剂。
本发明提供一种润滑油添加剂,该润滑油添加剂包括特定含量的离子液体、清净剂、分散剂、抗磨剂、抗氧剂、防锈剂、金属钝化剂和基础油,离子液体包括咪唑阳离子以及羧酸阴离子。由于组成润滑油添加剂的离子液体包括咪唑阳离子以及羧酸阴离子,所以该润滑油添加剂具有较为优异的抗磨性、防腐蚀性和稳定性;并且该离子液体还具有溶解性能优良的优点,能够与其它组分进行较为优良的配伍,进一步提高润滑油添加剂的抗磨性、流动性、防腐蚀性和稳定性。值得一提的是,该离子液体中并不含有硫元素和磷元素,使用该离子液体能够尽可能降低润滑油添加剂中的硫元素和磷元素,所以能够提高润滑油添加剂的环保性能。
本发明的润滑油,由于包括上述的润滑油添加剂,所以不仅具有较为优异的抗磨性、流动性、防腐蚀性和稳定性,而且环保性好,具有较为广泛的应用前景。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
本发明的第一方面提供一种润滑油添加剂,按照质量百分含量包括:
其余为基础油;
其中,离子液体包括包括以下结构:
其中,n选自4-9中的正整数。
本发明不限定离子液体的具体来源,可以采用本领域常用的制备方法制备离子液体,也可以通过商业购买得到离子液体。
进一步地,当离子液体的结构式为
本发明对清净剂、分散剂、抗磨剂、抗氧剂、防锈剂、金属钝化剂和基础油不做特别限定,可以选自本领域常用的清净剂、分散剂、抗磨剂、抗氧剂、防锈剂、金属钝化剂和基础油。
本发明中,离子液体包括咪唑阳离子以及羧酸阴离子,使用该离子液体制备润滑油添加剂,能够提高润滑油添加剂的抗磨性和稳定性,并且该离子液体能够钝化金属活性,提高润滑油添加剂的防腐蚀性能;该离子液体还具有溶解性能优良的优点,是良好的溶剂,能够与其它组分进行较为优良的配伍,进一步提高润滑油添加剂的流动性、抗磨性、稳定性以及防腐蚀性能。
本发明的离子液体中不含有硫元素和磷元素,是一种绿色环保的溶剂,使用该离子液体能够尽可能降低润滑油添加剂中的硫元素和磷元素,所以本发明的润滑油添加剂还具有优异的环保性能。
进一步地,当润滑油添加剂按照质量百分含量包括:
其余为基础油时,该润滑油添加剂具有更为优异的抗磨性、防腐蚀性和稳定性。
本发明中,可以对清净剂、分散剂、抗磨剂、抗氧剂、防锈剂、金属钝化剂和基础油的原料进行进一步的选择,以期进一步提高各原料的配伍性,改善润滑油添加剂的流动性、抗磨性、防腐蚀性、稳定性和环保性能。
在本发明的一些实施方式中,清净剂包括磺酸盐和/或酚盐。磺酸盐可以为高碱值磺酸盐,酚盐可以为高碱值酚盐。
在本发明的一些实施方式中,分散剂包括单丁二酰亚胺和/或硼化丁二酰亚胺。
在本发明的一些实施方式中,抗磨剂可以为极压抗磨剂,极压抗磨剂可以选自丁基三苯基硫代磷酸酯、二丁基二硫代氨基甲酸铅和二烷基二硫代磷酸酯中的至少一种。
在本发明的一些实施方式中,抗氧剂包括辛基/戊基二苯胺和/或辛基取代二苯胺。
本发明中,辛基/戊基二苯胺为辛基取代二苯胺和戊基取代二苯胺的混合物,本发明不限定辛基取代二苯胺和戊基取代二苯胺的质量比。辛基取代二苯胺指的辛基取代苯环上的氢原子形成的化合物,戊基取代二苯胺指的是戊基取代苯环上的氢原子形成的化合物。
在本发明的一些实施方式中,防锈剂选自二壬基萘磺酸钡、十二烯基丁二酸和N,N’-双(苯丙并三氮唑亚甲基)月桂胺中的至少一种。
本发明中,使用上述的防锈剂,能够使润滑油添加剂更好的在金属表面形成吸附膜,抑制金属与水和氧的接触,减少金属的锈蚀,更进一步的改善润滑油添加剂的防锈性能。
在本发明的一些实施方式中,金属钝化剂包括甲苯并三唑衍生物和/或噻二唑衍生物。当金属钝化剂包括上述物质时,所获得的润滑油添加剂能够更好的在金属表面形成化学保护膜,阻止金属变为离子,进而能够防止金属离子催化氧化油品,延长润滑油添加剂的使用寿命,而且所形成的化学保护膜还能够防止硫和有机酸腐蚀金属,提高润滑油添加剂的防腐蚀能力。
在本发明的一些实施方式中,基础油为II类基础油。
本发明一些实施方式中的润滑油添加剂可以通过将各原料按照上述的组成混合均匀得到。本发明对各原料的添加顺序、搅拌速率、混合温度不做特别限定。
本发明的润滑油添加剂,不仅兼具较为优良的流动性、抗磨性、防腐蚀性、稳定性和环保性能,而且制备工艺简单,易于操作,应用范围广。
本发明的第二方面提供一种润滑油,包括上述的润滑油添加剂。
本发明中,将一定含量的润滑油添加剂与基础油进行混合,能够得到润滑油。本发明对基础油不做特别限定,可以为本领域常用的基础油,例如,基础油可以为I类基础油、Ⅱ类基础油和III类基础油中的至少一种。在具体的实施方式中,基础油为Ⅱ类基础油和III类基础油的混合物。
由于润滑油包括上述的润滑油添加剂,所以该润滑油兼具较为优异的抗抗磨性、防腐蚀性、稳定性和环保性能,在用于电动车减速箱系统中时,能够防止金属腐蚀,对齿轮和轴承具有优异的保护作用。并且该润还有具有优异的低温流动性,能够满足水冷电机结构下的减速箱系统的润滑要求,具有广泛的应用前景。
以下,结合具体的实施例进一步说明本发明的技术方案。
各实施例中的离子液体的结构式为
其中,n选自4-9中的正整数,通过商业购买得到;
各实施例和对比例中的磺酸盐为磺酸钙,型号为HiTEC611;
各实施例和对比例中的甲苯并三唑衍生物为IR39;
各实施例和对比例中的II类基础油为HVIH3,购买自韩国SK;
各实施例和对比例中的噻二唑衍生物为T561;
各实施例和对比例中的水杨酸盐为C9375;
各实施例和对比例中的III类基础油为VHVI6,购买自韩国SK;
各实施例和对比例中的辛基/戊基二苯胺为L57;
各实施例和对比例中的二丁基二硫代氨基甲酸铅为T353。
实施例1
本实施例的润滑油添加剂的组成见表1:
表1
名称 | 质量百分含量/% |
磺酸盐 | 2.0 |
单丁二酰亚胺 | 70 |
二丁基二硫代氨基甲酸铅 | 4.5 |
离子液体(n=4) | 3.0 |
十二烯基丁二酸 | 1.0 |
辛基/戊基二苯胺 | 5.0 |
甲苯并三唑衍生物 | 0.2 |
II类基础油 | 14.3 |
实施例2
本实施例的润滑油添加剂的组成见表2:
表2
名称 | 质量百分含量/% |
磺酸盐 | 2.3 |
硼化丁二酰亚胺 | 79.2 |
二烷基二硫代磷酸酯 | 3.5 |
离子液体(n=6) | 2.5 |
二壬基萘磺酸钡 | 1.8 |
辛基/戊基二苯胺 | 5.7 |
噻二唑衍生物 | 0.6 |
II类基础油 | 4.4 |
实施例3
本实施例的润滑油添加剂的组成见表3:
表3
名称 | 质量百分含量/% |
水杨酸盐 | 3.0 |
硼化丁二酰亚胺 | 67.5 |
丁基三苯基硫代磷酸酯 | 5.0 |
离子液体(n=7) | 10 |
N,N’-双(苯丙并三氮唑亚甲基)月桂胺 | 1.5 |
辛基取代二苯胺 | 6.0 |
甲苯并三唑衍生物 | 0.5 |
II类基础油 | 6.5 |
实施例4
本实施例的润滑油添加剂的组成见表4:
表4
名称 | 质量百分含量/% |
水杨酸盐 | 1.5 |
硼化丁二酰亚胺 | 65.4 |
丁基三苯基硫代磷酸酯 | 4.5 |
离子液体(n=9) | 9 |
N,N’-双(苯丙并三氮唑亚甲基)月桂胺 | 1.2 |
辛基取代二苯胺 | 5.5 |
甲苯并三唑衍生物 | 0.3 |
II类基础油 | 12.6 |
实施例5
本实施例的润滑油添加剂的组成见表5:
表5
实施例6
本实施例中的润滑油通过分别将实施例1中的润滑油添加剂与III类基础油以及II类基础油混合得到;
其中,基于润滑油的总质量,润滑油添加剂的质量百分含量为6.55%,II类基础油的质量百分含量为45%,III类基础油的质量百分含量为42.95%,黏度指数改进剂V1010的质量百分含量为5.5%。
实施例7
本实施例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为实施例2中的润滑油添加剂。
实施例8
本实施例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为实施例3中的润滑油添加剂。
实施例9
本实施例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为实施例4中的润滑油添加剂。
实施例10
本实施例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为实施例5中的润滑油添加剂。
对比例1
本实施例的润滑油添加剂的组成见表6:
表6
名称 | 质量百分含量/% |
磺酸盐 | 2.0 |
单丁二酰亚胺 | 70 |
二丁基二硫代氨基甲酸铅 | 4.5 |
十二烯基丁二酸 | 1.0 |
辛基/戊基二苯胺 | 5.0 |
甲苯并三唑衍生物 | 0.2 |
II类基础油 | 17.3 |
对比例2
本实施例的润滑油添加剂的组成见表7:
表7
名称 | 质量百分含量/% |
磺酸盐 | 1.0 |
单丁二酰亚胺 | 49 |
二丁基二硫代氨基甲酸铅 | 3.0 |
离子液体(n=4) | 20 |
十二烯基丁二酸 | 2.1 |
辛基/戊基二苯胺 | 4.8 |
甲苯并三唑衍生物 | 0.8 |
II类基础油 | 19.3 |
对比例3
本对比例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为对比例1中的润滑油添加剂。
对比例4
本对比例中的润滑油与实施例6中的基本相同,唯一不同的是润滑油添加剂为对比例2中的润滑油添加剂。
性能表征
1、对实施例6-10和对比例3-4中的润滑油进行性能测试,测试结果见表8。
表8
从表8可以看出,本发明实施例的润滑油具有优异的抗磨性、流动性、防腐蚀性和稳定性,具有较为广泛的应用前景。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
3.根据权利要求1或2所述的润滑油添加剂,其特征在于,所述清净剂包括磺酸盐和/或酚盐。
4.根据权利要求1-3任一项所述的润滑油添加剂,其特征在于,所述分散剂包括单丁二酰亚胺和/或硼化丁二酰亚胺。
5.根据权利要求1-4任一项所述的润滑油添加剂,其特征在于,所述抗磨剂选自丁基三苯基硫代磷酸酯、二丁基二硫代氨基甲酸铅和二烷基二硫代磷酸酯中的至少一种。
6.根据权利要求1-5任一项所述的润滑油添加剂,其特征在于,所述抗氧剂包括辛基/戊基二苯胺和/或辛基取代二苯胺。
7.根据权利要求1-6任一项所述的润滑油添加剂,其特征在于,所述防锈剂选自二壬基萘磺酸钡、十二烯基丁二酸和N,N’-双(苯丙并三氮唑亚甲基)月桂胺中的至少一种。
8.根据权利要求1-7任一项所述的润滑油添加剂,其特征在于,所述金属钝化剂包括甲苯并三唑衍生物和/或噻二唑衍生物。
9.根据权利要求1-8任一项所述的润滑油添加剂,其特征在于,所述基础油为II类基础油。
10.一种润滑油,其特征在于,包括权利要求1-9任一项所述的润滑油添加剂。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1335379A (zh) * | 2000-07-25 | 2002-02-13 | 中国石油天然气股份有限公司兰州炼化分公司 | 抗磨液压润滑油添加剂组合物 |
CN101542647A (zh) * | 2006-09-22 | 2009-09-23 | 巴斯夫欧洲公司 | 磁流变配制剂 |
CN101675023A (zh) * | 2007-05-05 | 2010-03-17 | 巴斯夫欧洲公司 | 包含聚醚羧酸根作为阴离子的离子液体,其制备方法及其用途 |
CN104232244A (zh) * | 2013-06-07 | 2014-12-24 | 中国石油化工股份有限公司 | 一种咪唑类离子液体在润滑油添加剂中的应用 |
CN106467826A (zh) * | 2015-08-18 | 2017-03-01 | 华信凯伟科技(天津)有限公司 | 一种抗磨润滑油添加剂 |
US20170096614A1 (en) * | 2014-03-18 | 2017-04-06 | Council Of Scientific & Industrial Research | Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof |
CN110845417A (zh) * | 2019-11-27 | 2020-02-28 | 中国科学院兰州化学物理研究所 | 一种氨基酸离子液体水基添加剂及其制备方法和应用 |
CN111286386A (zh) * | 2020-02-24 | 2020-06-16 | 玛可索(苏州)石化有限公司 | 一种润滑油添加剂组合物 |
-
2021
- 2021-12-30 CN CN202111663080.5A patent/CN116410805A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1335379A (zh) * | 2000-07-25 | 2002-02-13 | 中国石油天然气股份有限公司兰州炼化分公司 | 抗磨液压润滑油添加剂组合物 |
CN101542647A (zh) * | 2006-09-22 | 2009-09-23 | 巴斯夫欧洲公司 | 磁流变配制剂 |
CN101675023A (zh) * | 2007-05-05 | 2010-03-17 | 巴斯夫欧洲公司 | 包含聚醚羧酸根作为阴离子的离子液体,其制备方法及其用途 |
CN104232244A (zh) * | 2013-06-07 | 2014-12-24 | 中国石油化工股份有限公司 | 一种咪唑类离子液体在润滑油添加剂中的应用 |
US20170096614A1 (en) * | 2014-03-18 | 2017-04-06 | Council Of Scientific & Industrial Research | Halogen free ionic liquids as lubricant or lubricant additives and a process for the preparation thereof |
CN106467826A (zh) * | 2015-08-18 | 2017-03-01 | 华信凯伟科技(天津)有限公司 | 一种抗磨润滑油添加剂 |
CN110845417A (zh) * | 2019-11-27 | 2020-02-28 | 中国科学院兰州化学物理研究所 | 一种氨基酸离子液体水基添加剂及其制备方法和应用 |
CN111286386A (zh) * | 2020-02-24 | 2020-06-16 | 玛可索(苏州)石化有限公司 | 一种润滑油添加剂组合物 |
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