CN115433622A - 减少发动机油泥的润滑油组合物 - Google Patents
减少发动机油泥的润滑油组合物 Download PDFInfo
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- CN115433622A CN115433622A CN202210629752.9A CN202210629752A CN115433622A CN 115433622 A CN115433622 A CN 115433622A CN 202210629752 A CN202210629752 A CN 202210629752A CN 115433622 A CN115433622 A CN 115433622A
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- Prior art keywords
- lubricating oil
- oil composition
- nitrogen
- dispersant
- hydrocarbyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 226
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 147
- 239000010802 sludge Substances 0.000 title claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 204
- 239000002270 dispersing agent Substances 0.000 claims abstract description 146
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 106
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 74
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 55
- 239000002199 base oil Substances 0.000 claims abstract description 32
- 230000001050 lubricating effect Effects 0.000 claims abstract description 12
- -1 phosphate ester Chemical class 0.000 claims description 150
- 150000001875 compounds Chemical class 0.000 claims description 75
- 239000003599 detergent Substances 0.000 claims description 64
- 229910052751 metal Inorganic materials 0.000 claims description 62
- 239000002184 metal Substances 0.000 claims description 62
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 59
- 229910052698 phosphorus Inorganic materials 0.000 claims description 51
- 239000011574 phosphorus Substances 0.000 claims description 51
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 47
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 229920000768 polyamine Polymers 0.000 claims description 40
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
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- 239000011701 zinc Substances 0.000 claims description 28
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- 229910052796 boron Inorganic materials 0.000 claims description 17
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- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 13
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- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 13
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
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- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 claims description 8
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000011133 lead Substances 0.000 claims description 6
- 150000003873 salicylate salts Chemical class 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 5
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 5
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- 239000011135 tin Substances 0.000 claims description 5
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- 239000004698 Polyethylene Substances 0.000 claims description 4
- 125000006574 non-aromatic ring group Chemical group 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 150000003871 sulfonates Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims 1
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- 238000000034 method Methods 0.000 description 67
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- 229910052791 calcium Inorganic materials 0.000 description 39
- 239000011575 calcium Substances 0.000 description 39
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 33
- 229920002367 Polyisobutene Polymers 0.000 description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 29
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
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- ITRFOBBKTCNNFN-UHFFFAOYSA-N tris(sulfanyl)-sulfanylidene-$l^{5}-phosphane Chemical compound SP(S)(S)=S ITRFOBBKTCNNFN-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- NVSDADJBGGUCLP-UHFFFAOYSA-N trisulfur Chemical class S=S=S NVSDADJBGGUCLP-UHFFFAOYSA-N 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- DZRKYXRDCSRVLF-UHFFFAOYSA-L zinc;bis(2-dodecylphenoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCCCCCCCCC1=CC=CC=C1OP([S-])(=S)OC1=CC=CC=C1CCCCCCCCCCCC.CCCCCCCCCCCCC1=CC=CC=C1OP([S-])(=S)OC1=CC=CC=C1CCCCCCCCCCCC DZRKYXRDCSRVLF-UHFFFAOYSA-L 0.000 description 1
- OECQDNKCDGGPFY-UHFFFAOYSA-L zinc;bis(2-ethylhexoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCC(CC)COP([S-])(=S)OCC(CC)CCCC.CCCCC(CC)COP([S-])(=S)OCC(CC)CCCC OECQDNKCDGGPFY-UHFFFAOYSA-L 0.000 description 1
- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 1
- JTRDOXTXNZMWMG-UHFFFAOYSA-L zinc;bis(8-methylnonoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCCCOP([S-])(=S)OCCCCCCCC(C)C.CC(C)CCCCCCCOP([S-])(=S)OCCCCCCCC(C)C JTRDOXTXNZMWMG-UHFFFAOYSA-L 0.000 description 1
- CVDZJQFKUVADND-UHFFFAOYSA-L zinc;di(propan-2-yloxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)OP([S-])(=S)OC(C)C.CC(C)OP([S-])(=S)OC(C)C CVDZJQFKUVADND-UHFFFAOYSA-L 0.000 description 1
- MECFLMNXIXDIOF-UHFFFAOYSA-L zinc;dibutoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCOP([S-])(=S)OCCCC.CCCCOP([S-])(=S)OCCCC MECFLMNXIXDIOF-UHFFFAOYSA-L 0.000 description 1
- IWSCWDSOLLPNTC-UHFFFAOYSA-L zinc;dipentoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CCCCCOP([S-])(=S)OCCCCC.CCCCCOP([S-])(=S)OCCCCC IWSCWDSOLLPNTC-UHFFFAOYSA-L 0.000 description 1
- USEBTXRETYRZKO-UHFFFAOYSA-L zinc;n,n-dioctylcarbamodithioate Chemical compound [Zn+2].CCCCCCCCN(C([S-])=S)CCCCCCCC.CCCCCCCCN(C([S-])=S)CCCCCCCC USEBTXRETYRZKO-UHFFFAOYSA-L 0.000 description 1
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Abstract
本公开内容描述了润滑油组合物。通过选择控制润滑油组合物中的总氮以及氮源类物质润滑油添加剂,有效地将发动机平均油泥值降至最低。一般而言,这里的润滑油组合物至少包括一种具有润滑粘度的基础油、一种分散剂体系,以及至少一种抗氧剂。
Description
技术领域
本公开内容主要涉及润滑油组合物及其添加剂,这些组合物可有效减少发动机油泥
背景
作为机油(通常也称作发动机油或曲轴箱油)而用于汽油或柴油汽车发动机的润滑油,通常包括一种基础油或一种具有润滑黏度的基础油与一种或多种添加剂形成的混合物,从而满足预期使用的特定性能要求。现代行业标准对这些油的组成和性能提出了越来越严格的要求,这几乎没有给润滑油的配方留下灵活性空间。润滑油制造商希望满足各种行业标准,但他们面临的挑战是,如何以具有成本效益的方式同时满足所有性能和行业标准。
随着制造商继续争取提高效率和燃油经济性,人们对发动机、润滑油及其部件的要求也不断提高。今天的润滑油通常需要经过更加严格的试验和认证。人们最近关注的一个领域是,评估长期运行期间,润滑油在发动机气缸盖、油槽、阀盖和/或正时齿轮盖中形成油泥时发挥的作用。更新、更严格的发动机试验,比如M271EVO燃油发动机试验(CECL-107-19),对润滑油提出了更高的要求。润滑油不仅要最大程度减少油泥的形成,而且要将油泥充分悬浮在溶液中,从而将液体黏度增加量和相关油压增加量降到最低水平。
摘要和术语
根据某个实施方案,本文描述了依据CEC 107-19可以有效减少发动机油泥的润滑油组合物。一方面,润滑油组合物包括一种具有润滑黏度的基础油和分散剂体系与抗氧化剂体系提供的氮。在某些方面,分散剂体系至少包括一种被烃基取代的琥珀酰亚胺分散剂,它可由一种被烃基取代的酰化剂与一种氮源发生反应得到。抗氧化剂体系至少包括一种绿支安抗氧化剂。另一方面,在润滑油组合物中。分散剂体系提供的氮与润滑油组合物中总氮的重量比约为0.6:1至0.85:1。分散剂体系提供的氮中,至少75%是一次氮源或二次氮源,它们并不是反应后产生的。
从其他方法或具体情况来看,上一段所述的润滑油组合物可能以任何方式与可选功能或可选实施方案结合。这些可选功能或可选实施方案包括以下一种或多种:抗氧化剂体系中至少一种绿支安抗氧化剂提供的氮与润滑油组合物中总氮的重量比,即大约0.15:1至0.4:1;和/或分散剂体系提供的氮与至少一种绿支安抗氧化剂提供的氮的重量比,即大约1.8:1至5.3:1;和/或依据CEC L-107-19,进一步包括约7至10平均指标值发动机油泥;和/或包括某种磷源,它包括一种或多种含磷化合物,这些含磷化合物是从一种硫代磷酸盐、二硫代磷酸盐、金属磷酸盐、金属硫代磷酸盐、金属二硫代磷酸盐、磷酸盐、亚磷酸盐、磷酸酯及其盐和混合物中独立筛选出来的;和/或包括一种洗涤剂体系,它至少包括一种含金属洗涤剂,可为成分提供含量高达3500ppm的金属,并且合并总碱值为0至大约500;和/或分散剂体系中被烃基取代的琥珀酰亚胺分散剂具有公式一所示结构:
其中R1为烃基官能团,其数均分子量为大约350至大约5,000;R2、R3和R4为独立的二价C1-C6亚胺;R5和R6为独立存在的氢气、C1-C6烷基,或者与氮结合,形成一个5元或6元环,该环可以与任意一个或多个芳香环或非芳香环结合;n为整数,取值为0至8;y和z均为整数,并且y+z=1;;和/或R5和R6与氮结合,形成公式二中的一个自由基
和/或其中酰化剂为顺丁烯二酸酐;氮源为从多乙烯多胺的混合物中筛选出的聚亚烷基多胺(平均含有5个氮原子)、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺或其组合;烃基取代物的数均分子量为大约1000至大约2,500;和/或其中分散剂体系至少包含两种烃基取代的琥珀酰亚胺分散剂,并且采用硼源和/或顺丁烯二酸酐只对一种被烃基取代的琥珀酰亚胺分散剂进行反应后处理;和/或其中分散剂体系包含的未经反应后处理的分散剂约为经过后处理的分散剂数量的2至4倍;和/或其中分散剂体系为润滑油组合物提供的总硼量不超过约300ppm;和/或其中存在的磷源可为润滑油组合物提供大约900ppm的磷;和/或其中一种或多种含磷化合物是从一种金属磷酸盐、一种金属硫代磷酸盐、一种金属二硫代磷酸盐或其组合中独立筛选出来的;和/或其中一种或多种含磷化合物是一种金属二硫代磷酸盐,它的烷基内含有12至32个碳原子,每个烷基平均含有3至8个碳原子;和/或其中一种或多种含磷化合物包括第一种金属二硫代磷酸盐,其中烷基来自仲醇;第二种金属硫代磷酸盐,其烷基来自伯醇;和/或其中一种或多种含磷化合物的金属是从官能团中独立筛选出来的,该官能团含有铝、铅、锡、钼、锰、镍、铜、钛、钨、锆或锌;和/或其中至少一种为润滑油组合物提供氮的抗氧化剂是一种绿支安抗氧化剂,它是从一种芳香胺、一种烷基化二苯胺、一种苯基-α-萘胺、一种烷基化苯基-α-萘胺、一种受阻非芳香胺或其组合中筛选出来的;和/或其中润滑油组合物包括第二种抗氧化剂,它是从一种酚类抗氧化剂、一种硫化烯烃、一种绿支安抗氧化剂或其组合中筛选出来的;和/或其中洗涤剂体系包括一种或多种含金属石碳酸盐、含硫石碳酸盐、磺酸盐、calixarates、salixarates、水杨酸盐、羧酸、磷酸、单和/或二硫代磷酸、烷基酚、硫耦合烷基酚化合物、亚甲基桥苯酚或其组合。
然而,在其他实施方案或方法中,目前公开的信息提供了根据CEC L-107-19,使用某种润滑油组合物减少发动机油泥的方法,和/或对发动机进行润滑以减少发动机油泥的方法。特别是,使用前两段中润滑油组合物的任何一种实施方案,根据CEC L-107-19,实现了发动机平均油泥为大约7至10merits的目标。
提供以下术语定义,以便阐明本文使用的特定术语的含义。
术语“油成分”、“润滑油组合物”、“润滑组合物”、“润滑油”、“润滑油组合物”、“润滑组分”、“充分配制的润滑油组合物”、“润滑油”、“曲轴箱油”、“曲轴箱润滑油”、“发动机油”、“发动机润滑油”、“机油”和“电动机润滑油”为同义的、可以完全互换的术语,指的是成品润滑油,它的主要成分是一种基础油,另外还包括少量添加剂成分。
在本文中,术语“添加剂包”、“添加剂浓缩物”、“添加剂成分”、“发动机油添加剂包”、“发动机油添加剂浓缩物”、“曲轴箱添加剂包”、“曲轴箱添加剂浓缩物”、“机油添加剂包”、“机油浓缩物”为同义的、可以完全互换的术语,指的是润滑油组合物,不包括基础油混合物的主要成分。添加剂包可能含有或不含有黏度指数改善剂或倾点降低剂。
术语“高碱性”与金属盐有关,比如金属磺酸盐、羧酸盐、水杨酸盐和/或石碳酸盐,其中金属含量大于化学计量含量。这些盐的转化率超过100%(即,它们可能组成将酸转化为其“正”盐、“中性”盐所需金属理论用量的100%以上)。词语“金属比率”通常缩写为MR,根据已知化学反应性和化学计量学,用它来表示高碱性盐中金属的总化学当量与中性盐中金属的化学当量之比。在正盐或中性盐中,金属比率为1;在高碱性盐中,MR大于1。它们通常指的是高碱性、超碱性或超强碱性盐,可能是有机硫酸盐、羧酸盐、水杨酸盐、磺酸盐和/或石碳酸盐。
术语“碱土金属”涉及钙、钡、镁和锶;术语“碱金属”指的是锂、钠、钾、铷和铯。
在本文中,术语“烃基”或“烃基取代基”或“烃基官能团”使用的是其普通含义,对于熟悉这个领域的人来说,这个含义是众所周知的。具体而言,它指的是这样一种官能团——它有一个碳原子与分子的剩余部分直接连接,并且主要具有烃的性质。每个烃基官能团都是从烃取代基和被取代的烃取代基中独立筛选出来的,后者含有一个或多个卤素取代基、羟基、烷氧基、巯基、硝基、亚硝基、氨基、吡啶基、呋喃基、咪唑基、氧和氮。其中,在烃基中,每十个碳原子所构成的非烃类取代基不超过两种。
在本文中,术语“亚烃基取代基”或“亚烃基官能团”使用的是其普通含义,对于熟悉这个领域的人来说,这个含义是众所周知的。具体而言,它指的是这样一种官能团——它通过一个碳原子,与分子剩余部分的两个位置直接连接,并且主要具有烃的性质。每个亚烃基官能团都是从二价烃取代基和取代的二价烃取代基中独立筛选出来的,后者含有卤素取代基、烷基、芳香基、烷基芳香基、羧基、烷氧基、巯基、硝基、亚硝基、氨基、吡啶基、呋喃基、咪唑基、氧和氮。其中,在亚烃基中,每十个碳原子所构成的非烃类取代基不超过两种。
在本文中,除非另有说明,否则术语“重量百分比”指的是列举的成分与整个成分的重量之比。
本文中的术语“可溶”、“油溶”或“可分散”可能但不一定表示化合物或添加剂是可溶的、可溶解的、可混合的或能够以任意比例悬浮在油中。但是,上述术语表示,例如,它们在油中可溶、可悬浮、可溶解或可稳定分散,其程度足以使它们在含油环境中产生预期效果。另外,如有需要,也允许与含量更高的某种添加剂混合。
在本文中,术语“TBN”表示采用ASTM D2896规定的方法测得的总碱值,单位为mgKOH/g。
在本文中,术语“烷基”指的是直链、支链、环状和/或取代的饱和链部分,碳原子数量大约为1至100。在本文中,术语“烯基”指的是直链、支链、环状和/或取代的不饱和链部分,碳原子数量大约为3至10。在本文中,术语“芳香基”指的是单环和多环芳香族化合物,可能含有烷基、烯基、烷基芳香基、氨基、羧基、烷氧基、卤素取代基和/或杂原子(包括但不限于氮、氧和硫)。
在本文中,“反应后”或“处理后”指的是与硼、磷和/或顺丁烯二酸酐进一步反应或使用其进一步处理的某种化合物;可能指的是分散剂,伯胺和/或仲胺与上述化合物在分散剂中进一步反应,并将上述胺中至少一部分转化为叔胺。US 5,241,003对上述后续反应或处理进行了进一步描述,并通过引用纳入本文。相反地,不是“反应后”或“处理后”的成分没有经过上述进一步加工、反应和/或处理。在存在分散剂的情况下,这些成分包括一定量的伯胺和/或仲胺。
对于本文中任何实施方案的分子量,可以使用Waters提供的胶凝渗透色谱(GPC)仪器或类似仪器测定,并使用Waters Empower Software或类似软件处理数据。GPC仪器可配备一个Waters分离模块或Waters折光率检测器(或类似可选设备)。GPC工作条件包括一个保护柱、4个Agilent PLgel柱(长度为300×7.5mm;粒径为5μ,孔径范围为),柱温约为40℃。可以使用不稳定的HPLC级四氢呋喃(THF)作为溶剂,流量为1.0mL/min。可以采用市售聚苯乙烯(PS)标准物质校准GPC仪器,其窄分子量分布范围为500-380,000g/mol。针对质量小于500g/mol的样本,可推断出校准曲线。可将样品和PS标准物质溶解在THF中,制备浓度为0.1至0.5wt%,使用时无需过滤。GPC测量结果如US 5,266,223所述,并通过引用纳入本文。另外,GPC方法提供了分子量分布信息;例如,参见W.W.Yau,J.J.Kirkland和D.D.Bly,“现代尺寸排阻液相色谱法”,约翰·威利出版公司,1979年,纽约。同样,通过引用纳入本文。
关于公布信息的更多细节和优势,将在后续说明中加以部分阐述,和/或通过公布的信息实践获得。通过所附声明中特别指出的元素和组合,可以获得公布信息的细节和优势。需要理解的一点是,上述一般说明和以下详细说明仅作为范例起到解释作用,根据声明,并不受公布信息的限制。
图纸插图简要说明
图1是发动机油泥平均值(AES)图表,它与分散剂氮和润滑油氮总量的重量比有关;
图2是AES图表,它与抗氧化剂氮和润滑油氮总量的重量比有关;
图3是AES图表,它与反应后氮在分散剂体系中的重量比有关;以及
图4是AES图表,它与分散剂氮和抗氧化剂氮的重量比有关。
详细说明
发动机或曲轴箱润滑油通常用于配备火花点火或压缩点火发动机的汽车,以减小摩擦并带来其他好处。这类发动机可用于汽车、卡车、摩托车和/或火车(这里仅举几个例子)。可以采用的燃料包括但不限于以下类型:汽油、柴油、乙醇、生物燃料、压缩天然气等。这类发动机包括混合电动发动机——包括一台内燃机和一个电力或电池电源和/或先进混合发动机或内燃机——包括发动机自动停止功能(汽车静止时)。本文中的润滑油组合物可有效减少此类发动机中的油泥形成和/或提高润滑油中的油泥悬浮比例,从而提高液体黏度和/或限制由于发动机油泥导致的压力上升。
目前公布的信息涉及采用一种方法或实施方案,描述了润滑油的独特成分。通过选择润滑油添加剂,控制润滑油组合物中的总氮和氮源,在M271EVO燃油发动机试验(CECL-107-19)中可以有效减少发动机油泥(AES)。在某些方面,本文所述润滑油组合物至少包括一种具有润滑黏度的基础油、一种分散剂体系以及至少一种抗氧化剂。它们与作为成分之一的氮之间有着独特的关系。分散剂体系提供一种氮源,至少包括一种烃基取代的琥珀酰亚胺分散剂,它可由一种烃基取代的酰化剂与氮源发生反应得到。至少包括一种抗氧化剂,它还提供了氮源,并可能含有非绿支安抗氧化剂,比如酚类抗氧化剂,用于特殊目的。如果采用其他方法,本文中的润滑油组合物还至少包括一种可选洗涤剂体系。该体系至少含有一种含金属的洗涤剂,可为成分提供含量高达3500ppm的金属(对于其他方法,金属含量约为2500ppm),并且总碱值约为0至150。润滑油组合物可能还含有一种可选磷源。这些磷源是一种或多种含磷化合物,它们是从一种硫代磷酸盐、一种二硫代磷酸盐、一种金属磷酸盐、一种金属硫代磷酸盐、一种金属二硫代磷酸盐、一种磷酸盐、一种亚磷酸盐、一种磷酸酯及其盐和混合物中独立筛选出来的。
由于含有这些物质,润滑油组合物可以控制液体中的氮量和氮源。例如,对于某种方法,在润滑油组合物中,分散剂体系提供的氮与润滑油组合物中总氮的重量比为大约0.6:1至大约0.8:1。对于其他方法,在润滑油组合物中,分散剂体系提供的氮至少有约75%作为一次氮源或二次氮源,它们并不是反应后产生的。然而,对于其他方法,在润滑油组合物中,由至少一种抗氧化剂提供的氮与润滑油组合物中总氮的重量比为大约0.15:1至大约0.36:1。而且/或在某些配方中,由分散剂体系提供的氮与由至少一种抗氧化剂提供的氮的重量比为大约1.8:1至大约5.2:1。令人意想不到的是,具有上述组成且满足这种氮量和氮源关系的液体,在严苛的M271EVO燃油发动机试验中可以显著控制油泥的形成。出乎意料的是,如图1至4所示,这些关于氮量和氮源的独特配方关系,在M271EVO试验中,对于控制油泥形成产生了最小和最大效果。在该试验中,当比率较低时,油泥平均性能较差。但是,出乎意料的是,在上述每种氮关系达到最大值时,油泥性能仍然较差。特别地,本文所述液体可以使发动机平均油泥(AES)等级达到7或以上(对于其他方法,等级为7至10)。根据CEC L-107-19,在完成M271燃油发动机试验后,取得了更好的结果,等级达到8或以上(或者等级为8至10)。
就组成而言,本文所述润滑油组合物首先包括一个提供氮源的分散剂体系。对于其他方法,在某些情况下还至少包括一个或两个被烃基取代的琥珀酰亚胺。它可由一种被烃基取代的酰化剂与氮源发生反应得到,比如下文讨论的各种聚亚烷基多胺。
对于某些方法,分散剂体系可能含有油溶性无灰分散剂,它们是从含有琥珀酰亚胺分散剂、琥珀酸酯和/或琥珀酸酯-酰胺的组合中筛选出来的。尽管分散剂可能是反应后产生的,含有能够与伯胺或仲胺官能团反应的各种分子,分散剂体系中大约至少75%或以上的氮暴露于伯胺或仲胺中,它们并不是反应后产生的。在这些方法中,本文所述的润滑油组合物中,分散剂的重量分数可能约为1至8。在其他方法中,重量分数为大约2.5至大约5.5(或这两个端点之间的任何其他范围)。
烃基-二羧酸或酸酐与氮源发生反应,比如聚亚烷基多胺,用于制备琥珀酰亚胺分散剂。琥珀酰亚胺分散剂及其制备方法如第7,897,696号美国专利和第4,234,435号美国专利所述,并通过引用纳入本文。烃基-二羧酸或酸酐的烃基部分可能来自聚烯烃基聚合物,比如(但不限于)丁烯聚合物、异丁烯聚合物。本文中合适的聚异丁烯包括由常规聚异丁烯或具有高反应活性的聚异丁烯形成的物质,它们的终端亚乙烯基含量至少约为60%,比如大约70%至大约90%及以上。合适的聚异丁烯可能包括那些采用BF3催化剂制备的聚异丁烯。
本文中分散剂的烃基取代物(比如聚异丁烯)数均分子量的变化范围可能比较大,比如从500至大约5000(对于其他方法,大约1000至3000)。采用聚苯乙烯(数均分子量为180至大约18,000)作为校准基准,通过凝胶渗透色谱法(GPC)可以测定其数均分子量。对于某种方法,分散剂体系包括两种分散剂:第一种分散剂所含聚异丁烯取代物的数均分子量大于1900,比如大约2000至大约5000;第二种分散剂所含聚异丁烯取代物的数均分子量小于大约1900,比如大约1000至大约1800。分散剂中的聚异丁烯部分最好具有分子量分布(MWD),也称为多分散性,该分子量分布由重均分子量(Mw)与数均分子量(Mn)的比率确定。最好使用Mw/Mn小于约2.2(最好小于约2.0)的聚合物。适当聚异丁烯取代基具有约1.5至约2.1或约1.6至约1.8的多分散性。
分散剂的二羧酸或酸酐可选自羧酸反应物,例如马来酸酐、马来酸、富马酸、苹果酸、酒石酸、衣康酸、衣康酸酐、柠檬酸、柠檬酸酐、甲基富马酸、乙基马来酸酐、二甲基马来酸酐、乙基马来酸、二甲基马来酸、己基马来酸等,包括相应的酸卤化物和C1-C4脂肪族酯。用于制备烃基二羧酸或酸酐的反应混合物中二羧酸或酸酐与烃基部分的摩尔比可能会变化很大。因此,摩尔比的变化范围为约5:1到约1:5,例如约3:1到约1:3。酸或酸酐与烃基部分的特别适当摩尔比为约1:1至约2.0:1。二羧酸或酸酐与烃基部分的另一种有用摩尔比约为1.3:1至1.8:1。
可使用任何一种聚亚烷基多胺来制备本文所述体系的分散添加剂。非限制性示例多胺可包括氨基胍碳酸氢盐(AGBC)、二乙烯三胺(DETA)、三乙烯四胺(TETA)、四乙烯五胺(TEPA)、五乙烯六胺(PEHA)和重多胺。重多胺可包含具有少量多胺低聚物(例如TEPA和PEHA)的聚烷基多胺混合物,但是,主要是具有七个或更多氮原子、每个分子两个或更多伯胺以及比传统多胺混合物更广泛支化的低聚物。通常,这些重多胺的每个分子平均有6.5个氮原子。美国专利(编号:6,548,458)公开了可用于制备烃基取代琥珀酰亚胺分散剂的附加非限制性多胺,通过引用,将该专利的公开内容全部纳入本文中。烃基二羧酸或酸酐与聚亚烷基多胺的摩尔比可以为约1:1至约3.0:1。
在一个实施方案中,分散剂可以是聚异丁烯琥珀酸酐(PIBSA)和多胺(例如四乙烯五胺等聚乙烯胺)或各种重多胺的反应产物。对于本文所述的分散剂,聚异丁烯取代琥珀酸酐与多胺摩尔比的范围为4:3至1:10。
在一些实例中,只要分散剂满足上述氮要求,可选择硼化、磷酸化本文中的分散剂或者使其与各种试剂(如马来酸酐)发生后反应。通常,这些分散剂为至少一种磷化合物、硼化合物和/或马来酸酐与上述至少一种无灰分散剂的反应产物。
用于形成本文中分散剂的适当硼化合物(如果使用)包括能够将含硼物引入无灰分散剂中的任何硼化合物或硼化合物混合物。可以使用能够完成此类反应的任何有机或无机硼化合物。因此,可以使用氧化硼、水合氧化硼、三氟化硼、三溴化硼、三氯化硼、HBF4硼酸,例如硼酸(例如烷基-B(OH)2或芳基-B(OH)2)、硼酸(即H3BO3)、四硼酸(即H2B5O7)、偏硼酸(即HBO2)、这些硼酸的铵盐以及这些硼酸的酯。将硼反应物引入反应混合物的便捷方法是使用三卤化硼与醚、有机酸、无机酸或碳氢化合物的络合物。此类络合物都是已知的,例如三氟化硼乙醚、三氟化硼苯酚、三氟化硼磷酸、三氯化硼氯乙酸、三溴化硼二氧六环和三氟化硼甲基乙醚。
用于形成分散剂的适当磷化合物(如果使用)包括能够将含磷物引入分散剂的磷化合物或磷化合物混合物。因此,可以使用能够完成此类反应的任何有机或无机磷化合物。所以,可以使用无机磷化合物,如无机磷酸和无机磷氧化物,包括其水合物。典型有机磷化合物包括磷酸的全酯和部分酯,例如磷酸、硫代磷酸、二硫代磷酸、三硫代磷酸和四硫代磷酸的单酯、二酯和三酯;磷酸、硫代磷酸、二硫代磷酸和三硫代磷酸的单酯、二酯和三酯;三烃基氧化膦;三烃基硫化膦;单烃基膦酸酯和二烃基膦酸酯(RPO(OR′)(OR″),其中R和R′为烃基,R″为氢原子或烃基)及其单硫、二硫和三硫类似物;单烃基膦酸酯和二烷基膦酸酯(RPO(OR′)(OR″),其中R和R′为烃基,R″为氢原子或烃基)及其单硫和二硫类似物;等等。因此,可使用以下化合物:亚磷酸(H3PO3,有时描述为H2(HPO3),有时称为正亚磷酸或膦酸)、磷酸(H3PO4,有时称为正磷酸)、低磷酸(H4P2O6)、偏磷酸(HPO3)、焦磷酸(H4P2O7)、次磷酸(H3PO2,有时称为次膦酸)、焦磷酸(H4P2O5,有时称为焦膦酸)、次膦酸(H3PO)、三聚磷酸(H5P3O10))、四聚磷酸(H5P4O13)、三偏磷酸(H3P3O9)、三氧化磷、四氧化磷、五氧化二磷等。有时,也可以使用部分或总硫类似物,例如四硫代磷酸(H3PS4)、一硫代磷酸(H3PO3S)、二硫代磷酸(H3PO2S2)、三硫代磷酸(H3POS3)、三硫化二磷、七硫化磷和五硫化磷(P2S5,有时称为P4S10)形成本发明的分散剂。也可以使用无机卤化磷化合物,例如PCl3、PBr3、POCl3、PSCl3等。
同样,可以使用有机磷化合物,如磷酸单酯、二酯和三酯(例如磷酸三烃基酯、磷酸二烷基酯、单烃基二酸磷酸酯及其混合物)、亚磷酸单酯、二酯和三酯(例如,亚磷酸三烃基酯、亚磷酸氢二烷基酯、烃基二酸亚磷酸酯及其混合物)、膦酸酯(“一次伯酸”、RP(O)(OR)2和“二次酸”)。R2P(O)(OR))、膦酸酯、膦酰卤化物(例如RP(O)Cl2和R2P(O)Cl)、卤代亚磷酸酯(例如,(RO)PCl2和(RO)2PCl)、卤代磷酸盐(例如,ROP(O)Cl2和(RO)2P(O)Cl、叔焦磷酸酯(例如,(RO)2P(O)—O—P(O)(OR)2)以及上述任何有机磷化合物的总硫或部分硫类似物等等,其中,每个烃基包含多达约100个碳原子,优选多达约50个碳原子,更优选择为多达约24个碳原子,最优选择为多达约12个碳原子。可以使用卤代卤化膦(例如,烃基四卤化磷、二烃基三卤化磷和三烃基二卤化磷)和卤代膦(单卤代膦和二卤代膦)。
如上所述,在一些实施方案中,本文所述润滑油组合物的分散剂体系可包括至少两种分散剂,一种来自具有约1900或以上(或约2000至约5000或约2000至约3000)相对较高数均分子量的聚异丁烯,另一种来自小于约1900(或约1000至约1900或约1000至约1800)相对较低数均分子量的聚异丁烯。在一些方法中,可以选择硼源(如硼酸和/或马来酸酐),对较低分子量取代基的分散剂进行后处理。在这种情况下,分散剂体系包含的非后处理分散剂大约是后处理分散剂的约2至4倍,并且/或者,在任何其他范围内,分散剂体系可以向润滑油组合物提供不超过约300ppm、不超过约250ppm、不超过约150ppm、不超过约120ppm的总硼以及某些情况下不超过约50至约200ppm的总硼。
在其他方法中,本文所述分散剂体系的烃基取代琥珀酰亚胺分散剂分别具有分子式1的结构:
其中,R1是具有约350至约5,000数均分子量(或上文所述分子量)的烃基取代基;R2、R3和R4分别为二价C1-C6部分;R5和R6分别为氢、C1-C6烷基,或者与相连接的氮一起形成5或6元环,可任意与一个或多个芳香环或非芳香环熔接;n是0到8之间的整数;y和z都是整数,其中:y+z=1。在一些方法中,分散剂是双琥珀酰亚胺,其中,R5和R6与其连接的氮一起形成分子式2的基团。
在一些方法中,酰化剂为马来酸酐,氮源为从平均具有5个氮原子的聚乙烯多胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺或其组合中选择的聚烷基多胺;所述烃基取代基的数均分子量约为1000~2,500。
如上所述,在M271EVO发动机试验中,分散剂体系的总氮和氮源有助于实现添加剂的污泥性能。在一个实施方案中,所述组合物中分散剂体系提供的总氮与润滑油组合物中总氮的重量比约为0.6:1至约0.8:1;在其他情况下,该重量比为约0.62:1至约0.81:1;在其他方法中,该重量比为约0.66:1至约0.78:1,这反映了在得到期望的平均发动机污泥试验结果(即AES约为7或更高或者约为8或更高)时的最小和最大影响(如图1所示)。同时,以一次或二次氮的形式暴露分散剂体系提供的至少约75%氮(至少约72%、至少约75%或甚至至少约80%氮),并且,并未为了得到所需发动机污泥性能而进行后反应(如图3所示)。
本文所述润滑油组合物还可包括提供磷源的可选抗磨体系,而且,在方法中,包括至少一种和(在某些情况下)至少两种含磷化合物,例如包括含磷化合物和/或无灰含磷化合物的金属。抗磨体系提供金属与含磷化合物的混合物,有效实现摩擦性能和/或污泥控制等功能。本文所述润滑油组合物可包括抗磨体系的约0.1wt%至约2.0wt%以及(在其他方法中)约0.5wt%至约1.5wt%(或其他范围),以便分别提供高达约900ppm的磷、高达约800ppm的磷或约50至约900ppm、约50至约800ppm的磷。
在这些方法中,抗磨体系包括两种或更多金属二烃基二硫代磷酸盐化合物的混合物,例如(但不限于)两种或更多二烃基二硫代磷酸锌化合物(ZDDP)。适当金属二硫代磷酸盐(例如ZDDP)可包括5至约10wt%的金属(在其他方法中,约6至约9wt%的金属,其中金属优选为锌)以及约8至约18wt%的硫(在其他方法中,约12至约18wt%的硫或约8至约15wt%的硫)。金属二硫代磷酸盐(例如ZDDP)还可包括约4wt%至约15wt%的磷以及约6wt%至约10wt%的磷(在一些方法中)。适当金属二烃基二硫代磷酸酯可以是任何一种二烃基二硫代磷酸酯金属盐,其中,金属可以是碱金属、碱土金属、铝、铅、锡、钼、锰、镍、铜、钛、锆、锌或其组合物。然而,该金属优选为锌。
当抗磨体系的含磷化合物为ZDDP时,ZDDP上的烷基可衍生自伯醇、仲醇和/或其混合物。例如,适于形成ZDDP烷基的伯醇包括但不限于乙基己醇、丁醇、正戊醇和/或C6和高级伯醇。适于形成ZDDP烷基的仲醇包括但不限于甲基异丁基甲醇、异丙醇或其混合物。在某些情况下,ZDDP的烷基可衍生自伯醇和仲醇的混合物,例如2-乙基己醇(伯)、异丁醇(伯)和异丙醇(仲)。例如,在一个实施方案中,抗磨体系中的一种ZDDP添加剂包括衍生自甲基异丁基甲醇(仲醇)的各种烷基。在其他实施方案中,抗磨体系的另一种ZDDP包括衍生自伯醇的各种烷基,例如2-乙基己醇等。在一种方法中,本文中的抗磨体系包括衍生自伯醇和仲醇的金属二烷基二硫代磷酸盐(优选二烷基二硫代磷酸锌)的混合物。在实施方案中,抗磨体系中结合的两种ZDDP添加剂的伯醇与仲醇的重量比至少为0.75:1至约3:1。
适当ZDDP的实例包括但不限于:O,O-二(C1-14-烷基)二硫代磷酸锌;
(混合O,O-二(仲丁基和异辛基))二硫代磷酸锌;O,O-二(支链和直链C3-8-烷基)二硫代磷酸锌;O,O-二(2-乙基己基)二硫代磷酸锌;O,O-二(混合异丁基和戊基)二硫代磷酸锌;混合O,O-二(1,3-二甲基丁基和异丙基)二硫代磷酸锌;O,O-二异辛基二硫代磷酸锌;O,O-二丁基二硫代磷酸锌;混合O,O-二(2-乙基己基、异丁基和异丙基)二硫代磷酸锌;O,O-二(十二烷基苯基)二硫代磷酸锌;O,O-二异癸基二硫代磷酸锌;O-(6-甲基庚基)-O-(1-甲基丙基)二硫代磷酸锌;O-(2-乙基己基)-O-(异丁基)二硫代磷酸锌;O,O-二异丙基二硫代磷酸锌;(混合己基和异丙基)二硫代磷酸锌;(O-(2-乙基己基)和O-异丙基混合)二硫代磷酸锌;O,O-二辛基二硫代磷酸锌;O,O-二戊基二硫代磷酸锌;O-(2-甲基丁基)-O-(2-甲基丙基)二硫代磷酸锌;以及O-(3-甲基丁基)-O-(2-甲基丙基)二硫代磷酸锌。
在其它方法中,本文所述抗磨体系中的每一种含磷化合物可各自具有分子式3的结构
其中,分子式1中的R单独包含1至18个碳原子,或2至12个碳原子,或约3至8个碳原子。抗磨体系可包含分子式1结构的两种化合物。在每种化合物中,R可为乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、戊基、正己基、异己基、正辛基、癸基、十二烷基、十八烷基、2-乙基己基、苯基、丁基苯基、环己基、甲基环戊基、丙烯基、丁烯基,以满足抗磨体系中上述伯醇与仲醇的选择比例。在一些实施方案中,上述分子式1中每个R基团中的碳原子数通常为约3个或更多、约4个或更多、约6个或更多、或约8个或更多。每个R基团的平均碳原子数为3到8个。R基团中的碳原子总数可为5至约72或者12至约32。在分子式1中,A是金属,例如铝、铅、锡、钼、锰、镍、铜、钛、锆、锌或其组合物。A最好为锌。
在其他方法中,抗磨体系的二烷基二硫代磷酸锌在抗磨体系中具有以下分子式4化学结构所示的磷化合物的硫-锌配位排列,而且,该结构可与上述分子式1互换使用。还应理解,分子式1和分子式2中所示的结构可呈现为单体、二聚体、三聚体或低聚物(例如四聚体)。
在一些实施方案中,抗磨体系的每种含磷化合物具有分子式3或4的结构,其中A为锌,抗磨体系内的化合物组合总量向润滑油组合物提供约70至约800ppm的磷(在其他方法中,约200至约800ppm)。如上所述,抗磨体系包括二烷基二硫代磷酸锌的混合物。抗磨体系最好可包括至少两种二烷基二硫代磷酸锌,其中,第一种二烷基二硫代磷酸锌仅衍生自伯醇,而第二种二烷基二硫代磷酸锌衍生自仲醇。
可根据已知方法,制备二烃基二硫代磷酸酯金属盐,首先,通常通过一种或多种醇或酚与P2S5反应,形成二烃基二硫代磷酸(DDPA),然后,将形成的DDPA与金属化合物(如氧化锌)中和。例如,可以通过伯醇和仲醇的混合物与P2S5发生反应,来制备DDPA。在这种情况下,DDPA包括来自伯醇和仲醇的烷基。也可以制备多个DDPA,其中,一个DDPA上的烷基完全衍生自仲醇,而另一个DDPA上的烷基完全衍生自伯醇。然后,将DDPA混合在一起,形成具有伯醇和仲醇烷基的DDPA混合物。
本文中的润滑油组合物还包括提供氮源的抗氧化剂体系,而且,在这些方法中,包括至少一种胺类抗氧化剂,在一些可选方法中,包括至少一种附加抗氧化剂。在这些方法中,针对总氮和/或分散剂氮来控制抗氧化剂体系中的氮量,以帮助实现污泥性能。在一些方法中,本文所述润滑油组合物中由至少一种抗氧化剂提供的氮与润滑油组合物中总氮的重量比约为0.15:1至约0.4:1,而且,在其他方法中,由分散剂体系提供的氮与由至少一种抗氧化剂提供的氮的重量比应控制在约1.8:1至约5.3:1的比率内。如图2和图4所示,根据M271EVO测试,此类关系还令人惊讶地显示了污泥控制的最小和最大影响。这些方法中,润滑油组合物可包括约0.3wt%至约4wt%的所述抗氧化剂,在其他方法中,可包括约0.5wt%至约3wt%的抗氧化剂(或采用其他范围)。
适当抗氧剂包括酚类抗氧剂、芳香胺类抗氧剂、含硫抗氧剂和有机亚磷酸酯等。例如,酚类抗氧剂包括2,6-二叔丁基苯酚、叔丁基苯酚、2,6-二叔丁基-4-甲基苯酚、4,4’-亚甲基双(2,6-二叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)和混合亚甲基桥联聚烷基苯酚的液体混合物以及4,4’-硫代双(2-甲基-6-叔丁基苯酚)、N,N’-二叔丁基苯二胺,4-二异丙胺基二苯胺、苯基α-萘胺、苯基α-萘胺和环烷基化二苯胺。实例包括空间位阻叔丁基化苯酚、双酚和肉桂酸衍生物及其组合物。
芳香胺抗氧剂包括但不限于二芳胺,其分子式如下:
其中,R'和R”分别表示具有6到30个碳原子的取代或未取代芳基。芳基的取代基包括脂肪族烃基,例如具有1到30个碳原子的烷基、羟基、卤素自由基、羧酸或酯基或硝基。芳基可以是取代或未取代苯基或萘基,特别是其中一个或两个芳基被至少一个具有4到30个碳原子(优选4到18个碳原子,最好选4到9个碳原子)的烷基取代。在这些方法中,取代了一个或两个芳基,例如单烷基化二苯胺、二烷基化二苯胺或单烷基化二苯胺和二烷基化二苯胺的混合物。
可使用二芳胺的实例包括但不限于:二苯胺;各种烷基化二苯胺、3-羟基二苯胺、N-苯基-1,2-苯二胺、N-苯基-1,4-苯二胺、单丁基二苯胺、二丁基二苯胺、单辛基二苯胺、二辛基二苯胺、单壬基二苯胺、二壬基二苯胺、单十四烷基二苯胺、二十四烷基二苯胺、苯基-α-萘胺、单辛基苯基-α-萘胺、苯基-β-萘胺、单庚基二苯胺、二庚基二苯胺、对位苯乙烯化二苯胺、混合丁基辛基二苯胺和混合辛基苯乙烯基二苯胺。
含硫抗氧剂可包括但不限于硫化烯烃,其特征在于生产中使用的烯烃类型和抗氧剂的最终硫含量。可优选高分子量烯烃(如果本文所述体系中使用的话),例如平均分子量为168至351g/mol的烯烃。可使用烯烃的实例包括α-烯烃、异构化α-烯烃、支链烯烃、环烯烃以及其组合物。
α-烯烃包括但不限于任何C4至C25α-烯烃。在硫化反应之前或硫化反应期间,可以对α-烯烃进行异构化处理。还可以使用含内部双键和/或分支α-烯烃的结构和/或构象异构体。例如,异丁烯是α-烯烃1-丁烯的支链烯烃对应物。烯烃硫化反应中可能使用的硫源包括:元素硫、一氯化硫、二氯化硫、硫化钠、多硫化钠以及共同添加的或硫化过程的不同阶段添加的这些硫的混合物。
由于具有不饱和性,不饱和油也可以硫化,并且作为抗氧化剂。可使用油或脂肪的实例包括玉米油、菜籽油、棉籽油、葡萄籽油、橄榄油、棕榈油、花生油、椰子油、菜籽油、红花籽油、芝麻油、大豆油、葵花籽油、牛脂以及这些油的组合物。
只要抗氧化剂体系提供的氮也满足上述其他参数,本文所述润滑油组合物中抗氧化剂的总量可提供高达约400ppm的氮或高达约300ppm的氮或高达约200ppm的氮或高达约100至约400ppm的氮,例如,至少一种抗氧剂提供的氮重量比与润滑油组合物中总氮重量比的关系约为0.15:1至0.4:1,在其他方法中,该关系约为0.16:1至0.36:1,或在另一些方法中,该关系约为0.18:1至0.32:1,这说明AES约为7或更高或者约为8或更高。在更多方法中,本文所述润滑油组合物中分散剂体系提供的氮与至少一种抗氧化剂提供的氮的重量比应控制在约1.8:1至约5.3:1的范围内,或在其他方法中,应控制在约1.82:1至约5.27:1的范围内,并且在另一些方法中,应控制在约2.4:1至约4.7:1的范围内,以便帮助获得约7或更高或者约8或更高AES值。如图2和图4所示,根据M271EVO测试,此类关系还令人惊讶地显示了污泥控制的最小和最大影响。
润滑油组合物还可包括可选洗涤剂体系,该洗涤剂体系包括一种或多种中性、低基或高基洗涤剂或其混合物。在这些方法中,洗涤剂可提供高达3500ppm的金属,并且在流体中,具有约0至150的总TBN。适当的洗涤剂底物包括酚盐、含硫酚盐、磺酸盐、杯芳烃、水杨酸盐、水杨酸盐、羧酸、磷酸、单-和/或二-硫代磷酸、烷基酚、硫偶联的烷基酚化合物或亚甲基桥连酚。合适的洗涤剂及其制备方法在许多专利出版物中有更详细地描述,包括美国专利7,732,390和其中引用的参考文献。洗涤剂基材可以用碱金属或碱土金属盐腌,例如,但不限于钙、镁、钾、钠、锂、钡、锌或其混合物。在一种方法中,洗涤剂可以用镁盐。
适当洗涤剂可以包括石油磺酸和长链单-或二-烷基芳基磺酸的碱金属或碱土金属盐(例如钙或镁),其中芳基是苄基、甲苯基和二甲苯基。其他适当洗涤剂的实例包括但不限于以下洗涤剂的低碱性/中性和高碱性变体:苯酚钙、含钙硫的苯酚钙、磺酸钙、杯酸钙、水杨酸钙、水杨酸钙、羧酸钙、磷酸钙、单-和/或二-硫代磷酸钙、烷基苯酚钙、钙硫偶联的烷基苯酚化合物、钙亚甲基桥连的苯酚、苯酚镁、含镁硫的苯酚镁、磺酸镁、杯酸镁、水杨酸镁、水杨酸镁、羧酸镁、磷酸镁、单-和/或二-硫代磷酸镁镁硫偶联的烷基酚化合物、镁亚甲基桥连酚、酚钠、含硫酚钠、磺酸钠、杯芳烃钠、柳酸钠、水杨酸钠、羧酸钠、磷酸钠、单-和/或二-硫代磷酸钠、烷基酚钠、钠硫偶联的烷基酚钠化合物或亚甲基桥连酚钠。在一种方法中,洗涤剂为磺酸镁。
洗涤剂的含量可以约0wt%至约10wt%,或约0.1wt%至约8wt%,或约1wt%至约4wt%,或约1wt%至约2wt%,或约0.5至约4wt%,或甚至约0.75至约3wt%。在其他方法中,润滑油组合物中可提供一定量的洗涤剂,以便向润滑油组合物提供约450至约2200ppm的金属,并且向润滑油组合物提供约0.4至约1.5wt%的肥皂含量。在其他方法中,洗涤剂的量足以向润滑油组合物提供约450至约2200ppm的金属,并且向润滑油组合物提供约0.4至约0.7wt%的肥皂含量。
在现有技术中,高碱性洗涤剂添加剂众所周知,可以是碱金属或碱土金属高碱性洗涤剂添加剂。可通过金属氧化物或金属氢氧化物与底物和二氧化碳气体反应制备此类洗涤剂添加剂。底物通常为酸,例如脂肪族取代磺酸、脂肪族取代羧酸或脂肪族取代苯酚。
适当高碱性洗涤剂的实例包括但不限于高碱性酚钙、高碱性含硫酚钙、高碱性磺酸钙、高碱性钙、高碱性成盐钙、高碱性水杨酸钙、高碱性钙羧酸、高碱性钙磷酸、高碱性钙单硫代磷酸和/或二硫代磷酸、高碱性钙烷基酚、高碱性钙硫偶联烷基酚化合物、高碱性钙亚甲基桥连酚、高碱性酚镁、高碱性含硫酚镁高碱性镁羧酸、高碱性镁磷酸、高碱性镁单-和/或二-硫代磷酸、高碱性镁烷基酚、高碱性镁硫偶联烷基酚化合物或高碱性镁亚甲基桥连酚。
高碱性洗涤剂的润滑油组合物中的总洗涤剂量至少为30wt%至约70wt%。在其他方法中,低碱性/中性洗涤剂的润滑油组合物中的总洗涤剂量为约30wt%至约70wt%。在各种方法中,洗涤剂体系可以是中性和高碱性洗涤剂的组合物,包括为组合物提供约200ppm至约3500ppm钙和约300ppm至约2000ppm镁的高碱性磺酸钙和更多中性磺酸镁。
低碱性/中性洗涤剂的TBN高达175mg KOH/g或者高达150mg KOH/g。低碱性/中性洗涤剂可包括含钙或镁的洗涤剂。适当低碱性/中性洗涤剂的实例包括但不限于磺酸钙、酚酸钙、水杨酸钙、磺酸镁、酚酸镁和水杨酸镁。在一些实施方案中,低碱性/中性洗涤剂是含钙洗涤剂和/或含镁洗涤剂的混合物。
在某些实施方案中,按照润滑油组合物的总重量,一种或多种低碱性/中性洗涤剂向润滑油组合物提供约50ppm至约1000ppm的镁,而高碱性洗涤剂可向所述润滑油组合物提供约1000ppm至约2000ppm的钙。在一些实施方案中,按照润滑油组合物的总重量,一种或多种低碱性/中性含钙洗涤剂向润滑油组合物提供75至小于800ppm、100至600ppm或125至500ppm(按重量计)的钙或镁。
润滑油组合物
上述分散剂体系、抗氧化剂体系、可选抗磨体系和可选洗涤剂体系可以结合大量基础油混合物或润滑粘度的基础油混合物(如下所述)以及一种或多种其他可选添加剂,以产生润滑油组合物。在各种方法中,润滑油组合物包括约50wt%或以上的基础油混合物、约60wt%或以上、约70wt%或以上或者约80wt%或以上至约95wt%或以下、约90wt%或以下、约85wt%或以下的基础油混合物,下文将进一步讨论此类混合物。
基础油混合物:所述润滑油组合物中使用的基础油可以是润滑粘度的油,并且,选自美国石油学会(API)基础油互换性指南中规定的I-V组中的任何基础油。五种基础油类别如下:
表1
第一类、第二类和第三类为矿物油加工原料。第四类基础油包含由烯烃不饱和烃聚合而成的真正合成分子物质。许多第五类基础油也是真正的合成产品,可包括二酯、多元醇酯、聚烷基二醇、烷基化芳烃、聚磷酸酯、聚乙烯醚和/或聚苯醚等,但也可以是天然油,如植物油。应注意的是,尽管第三类基础油来自矿物油,但是对这些流体进行了严格加工,使其物理性质与一些真正合成油(如PAO)非常相似。因此,本行业中,将从第三类基础油中提取的油称为合成油。第二类+可包括高粘度指数的第二类基础油。
所公开的润滑油组合物中使用的基础油混合物可以是矿物油、动物油、植物油、合成油、合成油混合物或其混合物。适当油可来自加氢裂化、加氢、加氢精制、未精制、精制和再精制油及其混合物。
未精炼油是指从天然、矿物或合成源中提取的油,未经或几乎未经进一步净化处理。精炼油与未精炼油相似,不同之处在于它们经过一个或多个净化处理步骤,所述净化处理可改善一种或多种性能。适当净化方法的实例为溶剂萃取、二次蒸馏、酸或碱萃取、过滤、渗滤等。精炼到食用品质的油可能有用,也可能无用。食用油也可称为白油。在一些实施方案中,润滑油组合物不含食用油或白油。
再精炼油也称为再生油或再加工油。这些油与精炼油相似,采用相同或类似的工艺方法。通常,通过直接清除废添加剂和油分解产物的方法,对这些油进行额外处理。
矿物油可包括通过钻探或从植物和动物或其任何混合物中获得的油。例如,此类油可包括但不限于蓖麻油、猪油、橄榄油、花生油、玉米油、大豆油和亚麻籽油以及矿物润滑油,例如液体石油以及溶剂处理或酸处理的石蜡、环烷或混合石蜡环烷类矿物润滑油。如果需要,这种油类可以部分或完全氢化。也可使用从煤或页岩中提取的油类。
有用的合成润滑油可包括烃油,例如聚合、低聚或共聚烯烃(例如,聚丁烯、聚丙烯、丙烯异丁烯共聚物);聚(1-己烯)、聚(1-辛烯)、1-癸烯的三聚体或低聚物,例如聚(1-癸烯),这些物质通常被称为α-烯烃,以及它们的混合物;烷基苯(例如十二烷基苯、十四烷基苯、二壬基苯、二-(2-乙基己基)苯);聚苯基(例如联苯、三联苯、烷基化聚苯基);二苯烷烃、烷基化二苯烷烃、烷基化二苯醚和烷基化二苯硫醚及其衍生物、类似物和同系物或其混合物。聚-α-烯烃通常是氢化材料。
其它合成润滑油包括多元醇酯、二酯、含磷酸的液体酯(例如,磷酸三甲苯酯、磷酸三辛酯和癸烷膦酸的二乙酯),或聚合四氢呋喃。合成油可以通过费托反应生产,并且通常可能是加氢异构化的费托烃或蜡。在一个实施方案中,可通过费托气制油合成程序以及其他气制油来制备油。
润滑油组合物中所含基础油的主要量可从基团I、基团II、基团III、基团IV、基团V以及上述两种或两种以上的组合组成的基团中选择,其中,基础油的主要量不是由于在组合物中提供添加剂组分或粘度指数改进剂而产生的基础油。润滑油组合物中所含基础油的主要量可从基团II、基团III、基团IV、基团V以及上述两种或两种以上的组合组成的基团中选择,其中,基础油的主要量不是由于在组合物中提供添加剂组分或粘度指数改进剂而产生的基础油。
存在润滑粘度的油的量可以是从100重量%总量减去包括粘度指数改进剂和/或倾点下降剂和/或其它顶部处理添加剂的性能添加剂的量后剩余的余量。例如,航空及工业用高性能润滑油中可能存在的润滑粘度的油可以是主要量,例如大于约50重量%,大于约60重量%,大于约70重量%,大于约80重量%,大于约85重量%,或大于约90重量%。
可选添加剂:
此处的润滑油组合物还可包括多种可选添加剂,只要保持氮和氮源的所述关系,根据需要与上面讨论的分散剂体系、抗氧化剂体系和抗磨体系组合,以满足性能标准。以下段落中描述了这些可选添加剂。
可选分散剂:润滑油组合物可任选包括一种或多种附加的分散剂或其混合物。分散剂通常被称为无灰型分散剂,这是因为在混入润滑油组合物之前,它们不含成灰金属,并且,当加入润滑剂中时,它们通常不产生任何灰分。无灰型分散剂的特点是连接在相对高分子量的碳氢链上的极性基团。典型的无灰分散剂包括N-取代的长链烯基琥珀酰亚胺。N-取代的长链烯基琥珀酰亚胺的实例包括聚异丁烯琥珀酰亚胺,聚异丁烯取代基的数均分子量在约350至约50,000、或约5,000、或约3,000范围内,如通过GPC所测定。琥珀酰亚胺分散剂及其制备已被公开,例如在第7,897,696号的美国专利或第4,234,435号美国专利。烯基取代基可以由含有约2至约16个、或约2至约8个、或约2至约6个碳原子的可聚合单体制备。琥珀酰亚胺分散剂通常是由多胺,通常是聚(亚乙基胺)形成的酰亚胺。
优选的胺选自多胺和羟胺。可被使用的多胺例子包括但不限于:二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)和高级同系物,例如五乙胺六胺(PEHA)等。
合适的重多胺是多亚烷基多胺的混合物,其包含少量低级多胺低聚物,例如TEPA和PEHA(五亚乙基六胺),但主要是具有6个或更多个氮原子的低聚物,每个分子具有2个或更多个伯胺,并且比常规多胺混合物具有更广泛的支化。重多胺最好包括每个分子含有7个或更多氮,每个分子含有2个或更多伯胺的多胺低聚物。重多胺包含超过28重量%。%(例如>32wt。%)总氮和当量重量为120-160克/当量的伯胺基团。
在一些方法中,合适的多胺通常称为PAM,并包含亚乙基胺的混合物,其中TEPA和五亚乙基六胺(PEHA)是多胺的主要部分,通常小于约80%。
通常,PAM的每克伯胺当量为8.7-8.9毫当量/克(每伯胺当量的当量重量为115至112克),和约33-34重量%总氮含量。%.PAM低聚物的较重馏分几乎不含TEPA和只有非常少量的PEHA,但主要包含具有超过6个氮和更广泛支化,可以生产具有改进分散性的分散剂。
在一个实施方案中,本公开发明还包含至少一种衍生自聚异丁烯的聚异丁烯琥珀酰亚胺分散剂,其数均分子量】为约350至约50,000,或至约5000,或至约3000,如通过GPC所测定。聚异丁烯琥珀酰亚胺可以单独使用,也可以与其他分散剂联合使用。
在一些实施方案中,当包含聚异丁烯时,可具有大于50mol%、大于60mol%、大于70mol%、大于80mol%或大于90mol%的末端双键含量。这种PIB也被称为高反应性PIB(“HR-PIB”)。通过GPC测定的数均分子量为约800至约5000的HR-PIB适用于本公开发明的实施方案。常规PIB通常具有小于50mol%、小于40mol%、小于30mol%、小于20mol%或小于10mol%的末端双键含量。
通过GPC测定的数均分子量为约900至约3000的HR-PIB可能是合适的。这种HR-PIB已上市销售,或可通过异丁烯在非氯化催化剂如三氟化硼存在下的聚合来合成,如Boerzel等人的第4,152,499号美国专利和Gateau等人的第5,739,355号美国专利中所述。当用于上述热烯反应时,由于反应性增加,HR-PIB可导致反应中更高的转化率以及更少量的沉积物形成。第7,897,696号美国专利中描述了一种合适的方法。
在一个实施方案中,本公开发明进一步包含至少一种衍生自聚异丁烯琥珀酸酐(“PIBSA”)的分散剂。PIBSA每聚合物可具有平均约1.0至约2.0个琥珀酸基团。
烯基或烷基琥珀酸酐的%活性可使用色谱技术进行测定。第5,334,321号美国专利的第5栏和第6栏中描述了该方法。
使用第5,334,321号美国专利第5栏和第6栏中的等式,计算%活性物中的聚烯烃百分转化率。
除非另有说明,否则所有百分比均为重量百分比,所有分子量均为使用市售聚苯乙烯标准物(数均分子量为180至约18,000作为校准参考)通过凝胶渗透色谱法(GPC)测定的数均分子量。
在一个实施方案中,分散剂可衍生自聚α-烯烃(PAO)琥珀酸酐。在一个实施方案中,分散剂可以衍生自烯烃马来酸酐共聚物。作为实例,分散剂可被描述为聚-PIBSA。在一个实施方案中,分散剂可衍生自接枝到乙烯-丙烯共聚物上的酸酐。
一类合适的含氮分散剂可衍生自烯烃共聚物(OCP),更具体地,可与马来酸酐接枝的乙烯-丙烯分散剂。可与官能化OCP反应的含氮化合物的更完整列表在第7,485,603号7,786,057;7,253,231;6,107,257;和第5,075,383号美国专利进行了描述。和/或可商购获得。
一类合适的分散剂也可以是曼尼希碱。曼尼希碱是由较高分子量的烷基取代苯酚、聚亚烷基多胺和如甲醛的醛缩合形成的物质。在第3,634,515号美国专利更详细地描述了曼尼希碱。
一类合适的分散剂也可以是高分子量酯或半酯酰胺。合适的分散剂也可以通过常规方法与各种试剂中的任何一种反应进行后处理。其中包括硼、尿素、硫脲、二巯基噻二唑、二硫化碳、醛、酮、羧酸、烃取代的琥珀酸酐、马来酸酐、腈、环氧化物、碳酸酯、环状碳酸酯、受阻酚酯和磷化合物。US 7,645,726、US 7,214,649和US 8,048,831的全部内容在此作为参考。
除了碳酸盐和硼酸的后处理之外,这两种化合物都可以采用各种旨在改善或赋予不同性质的后处理方法进行后处理或进一步的后处理。这种后处理包括第5,241,003号美国专利第27-29栏中所总结的内容,在此通过引入作为参考。这种处理包括:用无机亚磷酸或酸酐处理(例如,第3,403,102美国专利和第4,648,980号美国专利);有机磷化合物(例如第3,502,677号美国专利);五硫化二磷;如上所述的硼化合物(例如,第3,178,663和4,652,387号美国专利);羧酸、多元羧酸、酸酐和/或酰卤(例如,第3,708,522和4,948,386号美国专利);环氧化物聚环氧化物或硫代环氧化物(例如,第3,859,318和5,026,495号美国专利);醛或酮(例如,第3,458,530号美国专利);二硫化碳(例如,第3,256,185美国专利);缩水甘油(例如,第4,617,137号美国专利);尿素、硫脲或胍(例如,第3,312,619号美国专利);3,865,813;和GB 1,065,595英国专利);有机磺酸(例如,第3,189,544号美国专利和GB 2,140,811英国专利);烯基氰化物(例如,第3,278,550和,366,569号美国专利);双烯酮(例如,第3,546,243号美国专利);二异氰酸酯(例如,第3,573,205号美国专利);烷烃磺内酯(例如,第3,749,695号美国专利);1,3-二羰基化合物(例如,第4,579,675号美国专利);烷氧基化醇或酚的硫酸盐(例如,第3,954,639号美国专利);环状内酯(例如,第4,617,138号美国专利;4,645,515;4,668,246;4,963,275;第4,971,711号美国专利);环状碳酸酯或硫代碳酸酯,线性单碳酸酯或聚碳酸酯,或氯甲酸酯(例如,第4,612,132号美国专利);4,647,390;4,648,886;4,670,170);含氮羧酸(例如,第4,971,598号美国专利和GB 2,140,811英国专利);羟基保护的氯代二羰基氧基化合物(例如,第4,614,522号美国专利);内酰胺、硫代内酰胺、硫代内酯或二硫代内酯(例如,第4,614,603第4,666,460号美国专利);环状碳酸酯或硫代碳酸酯,线性单碳酸酯或聚碳酸酯,或氯甲酸酯(例如,第4,612,132号美国专利);4,647,390;4,646,860;和4,670,170);含氮羧酸(例如,第4,971,598号美国专利和GB 2,440,811英国专利);羟基保护的氯代二羰基氧基化合物(例如,第4,614,522号美国专利);内酰胺、硫代内酰胺、硫代内酯或二硫代内酯(例如,第4,614,603第4,666,460号美国专利);环状氨基甲酸酯、环状硫代氨基甲酸酯或环状二硫代氨基甲酸酯(例如,第4,663,062第4,666,459号美国专利);羟基脂肪族羧酸(例如,第4,482,464号美国专利);4,521,318;4,713,189);氧化剂(例如,第4,379,064号美国专利);五硫化二磷和聚亚烷基多胺的组合(例如,第3,185,647号美国专利);羧酸或醛或酮与硫或氯化硫的组合(例如,第3,390,086号美国专利);3,470,098);肼和二硫化碳的组合(例如,第3,519,564号美国专利);醛和酚的组合(例如,第3,649,229号美国专利);5,030,249;5,039,307);醛和二硫代磷酸的O-二酯的组合(例如,第3,865,740号美国专利);羟基脂族羧酸和硼酸的组合(例如,第4,554,086号美国专利);羟基脂族羧酸,然后是甲醛和苯酚的组合(例如,第4,636,322号美国专利);羟基脂肪族羧酸和脂肪族二羧酸的组合(例如,第4,663,064号美国专利);甲醛和苯酚然后是乙醇酸的组合(例如,第4,699,724号美国专利);羟基脂族羧酸或草酸和二异氰酸酯的组合(例如,第4,713,191号美国专利);无机酸或磷酸酐或其部分或全部硫类似物与硼化合物的组合(例如,第4,857,214号美国专利);有机二酸然后是不饱和脂肪酸,然后是亚硝基芳族胺,接着可选择地硼化合物,然后是乙醇酸化剂的组合(例如,第4,973,412号美国专利);醛和三唑的组合(例如,第4,963,278号美国专利);醛和三唑然后是硼化合物的组合(例如,第4,981,492号美国专利);环内酯和硼化合物的组合(例如,第4,963,275和4,971,711号美国专利);上述专利的全部内容在此并入本文。
合适的分散剂的TBN可为基于无油的约10至约65mg KOH/g分散剂,如果在含有约50%稀释油的分散剂样品上测量,其相当于约5至约30TBN。TBN是用ASTMD2896的方法来测量的。
在其他实施方案中,任选的分散剂添加剂可以是烃基取代的琥珀酰胺或琥珀酰亚胺分散剂。在一些方法中,烃基取代的琥珀酰胺或琥珀酰亚胺分散剂可以衍生自与聚亚烷基多胺反应的烃基取代酰化剂,并且其中琥珀酰胺的烃基取代基或琥珀酰亚胺分散剂是数均分子量为约250至约5,000的直链或支链烃基,所述数均分子量通过使用聚苯乙烯作为校准参比通过GPC测定的。
在一些方法中,用于形成分散剂的聚亚烷基多胺具有下式
其中每个R和R’独立地是二价C1至C6亚烷基接头,每个R1和R2独立地是氢、C1至C6烷基,或与它们所连接的氮原子一起形成任选地与一个或多个芳族或非芳族环稠合的5-或6-元环,并且n是0至8的整数。在其它方法中,聚亚烷基多胺选自由平均具有5-7个氮原子的多乙烯多胺、三乙烯四胺、四乙烯五胺及其组合的混合物组成的基团。
基于润滑油组合物的最终重量,可以以提供至多约20wt%的量使用可选分散剂(如果存在)。基于润滑油组合物的最终重量,分散剂可以使用的另一种量可能是约0.1重量%至约15重量%,或约0.1重量%至约10重量%,或约1重量%至约10重量%,或约1重量%至约8重量%,或约1重量%至约6重量%。在一些实施方案中,润滑油组合物使用混合分散剂体系。可以使用单一类型或两种或多种类型的分散剂以任何所需比例的混合物。
额外的抗氧化剂:本文的润滑油组合物也可选择地包含一种或多种其他抗氧化剂。抗氧化剂化合物是已知的,包括例如酚盐、酚盐硫化物、硫化烯烃、磷硫化萜烯、硫化酯、芳香胺、烷基化二苯胺(例如壬基二苯胺、二壬基二苯胺、辛基二苯胺、二辛基二苯胺)、苯基-α-萘胺、烷基化苯基-α-萘胺、受阻非芳香胺、酚、受阻酚、油溶性钼化合物、大分子抗氧化剂或其混合物。抗氧化剂化合物可以单独使用或组合使用。
受阻酚抗氧化剂可含有仲丁基和/或叔丁基作为空间位阻基团。酚基可以进一步被烃基和/或连接到第二个芳族基团的桥基取代。合适的受阻酚抗氧化剂的实例包括2,6-二叔丁基苯酚、4-甲基-2,6-二叔丁基苯酚、4-乙基-2,6-二叔丁基苯酚、4-丙基-2,6-二叔丁基苯酚或4-丁基-2,6-二叔丁基苯酚或4-十二烷基-2,6-二叔丁基苯酚。在一个实施方案中,受阻酚抗氧化剂可以是酯,并且可以包括:例如购自BASF的IrganoxTML-135,或衍生自2,6-二叔丁基酚和丙烯酸烷基酯的附加产物,其中烷基可以包含约1至约18个、或约2至约12个、或约2至约8个、或约2至约6个、或约4个碳原子。另一种市售受阻酚抗氧化剂可以是酯,并且可以包括购自Albemarle公司的EthanoxTM 4716。
有用的抗氧化剂可包括二芳基胺和高分子量酚。在一个实施方案中,润滑油组合物可以包含二芳基胺和高分子量酚的混合物,使得每种抗氧化剂可以以足以提供基于润滑油组合物最终重量的至多约5重量%的量存在。在一个实施方案中,抗氧化剂可以是约0.3-约1.5%二芳基胺和约0.4-约2.5%高分子量酚的混合物,基于润滑油组合物的最终重量。
可被硫化以形成硫化烯烃的合适烯烃的实施方案包括丙烯、丁烯、异丁烯、聚异丁烯、戊烯、己烯、庚烯、辛烯、壬烯、癸烯、十一碳烯、十二碳烯、十三碳烯、十四碳烯、十五碳烯、十六碳烯、十七碳烯、十八碳烯、十九碳烯、二十碳烯或其混合物。在一个实施方案中,十六碳烯、十七碳烯、十八碳烯、十九碳烯、二十碳烯或其混合物以及它们的二聚体、三聚体和四聚体是特别有用的烯烃。或者,烯烃可以是二烯如1,3-丁二烯和不饱和酯如丙烯酸丁酯的第尔斯-阿尔德加成物。
另一类硫化烯烃包括硫化脂肪酸及其酯。脂肪酸通常得自植物油或动物油,通常含有约4至约22个碳原子。合适的脂肪酸及其酯的例子包括甘油三酯、油酸、亚油酸、棕榈油酸或其混合物。通常,脂肪酸得自猪油、妥尔油、花生油、大豆油、棉籽油、葵花籽油或其混合物。脂肪酸和/或酯可以与烯烃如α-烯烃混合。
在另一个可供选择的实施方案中,除了上述酚类和/或胺类抗氧化剂之外,抗氧化剂组合物还包含含钼抗氧化剂。当使用这三种抗氧化剂的组合时,优选酚、胺和含钼的比例为(0至2):(0至2):(0至1)。
一种或多种抗氧化剂可以约0重量%至约20重量%,或约0.1重量%至约10重量%,或约1重量%至约5重量%的范围在润滑油组合物中存在。
其他抗氧化剂:本文的润滑油组合物也可选择地包含一种或多种其他抗氧化剂。合适的附加抗磨剂的实例包括但不限于金属硫代磷酸酯;二烷基二硫代磷酸金属盐;磷酸酯或其盐;磷酸酯;亚磷酸盐;含磷羧酸酯、醚或酰胺;硫化烯烃;含硫代氨基甲酸酯的化合物,包括硫代氨基甲酸酯、亚烷基偶联的硫代氨基甲酸酯和双(S-烷基二硫代氨基甲酰基)二硫化物;和它们的混合物。合适的抗磨剂可以是二硫代氨基甲酸钼。含磷抗磨剂在欧洲专利612 839中有更全面的描述。二烷基二硫代磷酸盐中的金属可以是碱金属、碱土金属、铝、铅、锡、钼、锰、镍、铜、钛或锌。有用的抗磨剂可以是二烷基二硫代磷酸锌。
合适的抗磨剂的其他实例包括钛化合物、酒石酸盐、酒石酸三酰胺、磷化合物的油溶性胺盐、硫化烯烃、亚磷酸酯(如亚磷酸二丁酯)、膦酸酯、含硫代氨基甲酸酯的化合物,如硫代氨基甲酸酯、硫代氨基甲酸酰胺、硫代氨基甲酸醚、亚烷基偶联的硫代氨基甲酸酯和双(S-烷基二硫代氨基甲酰基)二硫化物。酒石酸盐或酒石酰亚胺可以含有烷基酯基团,其中烷基上的碳原子总数可以是至少8个。在一个实施方案中,抗磨剂可以包括柠檬酸盐。
抗磨剂以以约0重量%至约15重量%,或约0.01重量%至约10重量%,或约0.05重量%至约5重量%,或约0.1重量%至约3重量%的范围在润滑油组合物中存在。
含硼化合物:本文的润滑油组合物可任选地含有一种或多种含硼化合物。含硼化合物的实例包括硼酸酯、硼酸化脂肪胺、硼酸化环氧化物、硼酸化洗涤剂和硼酸化分散剂,例如硼酸化琥珀酰亚胺分散剂,如第5,883,057号美国专利中所公开的。如果存在含硼化合物,其用量足以提供润滑油组合物的至多约8重量%、约0.01重量%至约7重量%、约0.05重量%至约5重量%、或约0.1重量%至约3重量%。
额外的洗涤剂:润滑油组合物可以任选地进一步包含一种或多种额外的中性、低碱性或高碱性洗涤剂及其混合物。合适的其他去污剂基质包括酚盐、含硫酚盐、磺酸盐、杯芳烃、水杨酸盐、水杨酸盐、羧酸、磷酸、单-和/或二-硫代磷酸、烷基酚、硫偶联的烷基酚化合物或亚甲基桥连酚。合适的洗涤剂及其制备方法在许多专利出版物中有更详细地描述,包括US7,732,390和其中引用的参考文献。
洗涤剂基材可以用碱金属或碱土金属盐腌,例如,但不限于钙、镁、钾、钠、锂、钡或其混合物。在一些实施方案中,洗涤剂不含钡。在一些实施方案中,洗涤剂可以含有痕量的其他金属,例如镁或钙,含量为例如50ppm或更低、40ppm或更低、30ppm或更低、20ppm或更低、或10ppm或更低。合适的清净剂可以包括石油磺酸和长链单-或二-烷基芳基磺酸的碱金属或碱土金属盐,其中芳基是苄基、甲苯基和二甲苯基。合适清净剂的实例包括但不限于苯酚钙、含钙硫的苯酚钙、磺酸钙、杯酸钙、水杨酸钙、水杨酸钙、羧酸钙、磷酸钙、单-和/或二-硫代磷酸钙、烷基苯酚钙、钙硫偶联的烷基苯酚化合物、钙亚甲基桥连的苯酚、苯酚镁、含镁硫的苯酚镁、磺酸镁、杯酸镁、水杨酸镁、水杨酸镁、羧酸镁、磷酸镁、单-和/或二-硫代磷酸镁镁硫偶联的烷基酚化合物、镁亚甲基桥连酚、酚钠、含硫酚钠、磺酸钠、杯芳烃钠、柳酸钠、水杨酸钠、羧酸钠、磷酸钠、单-和/或二-硫代磷酸钠、烷基酚钠、钠硫偶联的烷基酚钠化合物或亚甲基桥连酚钠。
高碱性清净剂添加剂是本领域众所周知的,可以是碱金属或碱土金属高碱性清净剂添加剂。可通过金属氧化物或金属氢氧化物与底物和二氧化碳气体反应制备此类洗涤剂添加剂。底物通常为酸,例如脂肪族取代磺酸、脂肪族取代羧酸或脂肪族取代苯酚。
润滑油组合物的高碱性清净剂可具有约200mg KOH/克或更大的总碱值(TBN),或作为进一步的实例,约250mg KOH/克或更大,或约350mg KOH/克或更大,或约375mgKOH/克或更大,或约400mg KOH/克或更大。
合适高碱性洗涤剂的实例包括,但不限于,高碱性酚钙、高碱性含硫酚钙、高碱性磺酸钙、高碱性钙、高碱性成盐钙、高碱性水杨酸钙、高碱性钙羧酸、高碱性钙磷酸、高碱性钙单硫代磷酸和/或二硫代磷酸、高碱性钙烷基酚、高碱性钙硫偶联烷基酚化合物、高碱性钙亚甲基桥连酚、高碱性酚镁、高碱性含硫酚镁高碱性镁羧酸、高碱性镁磷酸、高碱性镁单-和/或二-硫代磷酸、高碱性镁烷基酚、高碱性镁硫偶联烷基酚化合物或高碱性镁亚甲基桥连酚。
高碱性酚钙清净剂具有至少约150mg KOH/g、至少约225mg KOH/g、至少约225mgKOH/g至约400mg KOH/g、至少约225mg KOH/g至约350mg KOH/g或约230mg KOH/g至约350mgKOH/g的总碱值,所有均通过ASTM D-2896的方法测定。当这种洗涤剂组合物在惰性稀释剂中形成时,例如加工油,通常是矿物油,总碱值反映了包括可能包含在洗涤剂组合物中稀释剂和任何其它物质(例如,促进剂等)的整个组合物的碱度。
高碱性清洁剂的金属与底物的比例可为1.1∶1、2∶1、4∶1、5∶1、7∶1、10∶1。在一些实施方案中,清洁剂有效减少或防止发动机或传动装置及齿轮等其它汽车部件生锈。清洁剂在润滑油组合物中的含量在大约0wt%~大约10wt%,或0.1wt%~大约8wt%,1wt%~大约4wt%,更大值或4wt%~大约8wt%。
极压剂:本文的润滑油组合物也可选择地包含一种或多种极压剂。可溶于油中的极压(EP)剂包括含硫和氯硫的EP剂、氯代烃EP剂和磷EP剂。这种极压剂的实例包括氯化蜡;有机硫化物和多硫化物,例如二苄基二硫化物、二(氯苄基)二硫化物、二丁基四硫化物、硫化油酸甲酯、硫化烷基苯酚、硫化双戊烯、硫化萜烯和狄尔斯-阿尔德反应加成物;磷硫化烃,例如硫化磷与松节油或油酸甲酯的反应产物;亚磷酸二烃基酯和三烃基酯等磷酸酯类,例如亚磷酸二丁酯、亚磷酸二庚酯、亚磷酸二环己基酯、亚磷酸戊基苯基酯;亚磷酸二戊基苯酯、亚磷酸十三烷基酯、亚磷酸二硬脂酯和聚丙烯取代的亚磷酸苯酯;金属硫代氨基甲酸酯类,例如二辛基二硫代氨基甲酸锌和庚基苯酚二酸钡;烷基和二烷基磷酸的胺盐,包括例如二烷基二硫代磷酸与环氧丙烷的反应产物的胺盐;和它们的混合物。
摩擦改进剂:本文的润滑油组合物也可选择地包含一种或多种其他摩擦改进剂。合适的摩擦改进剂可以包括含金属和不含金属的摩擦改进剂,并且可以包括但不限于咪唑啉、酰胺、胺、琥珀酰亚胺、烷氧基化胺、烷氧基化醚胺、氧化胺、酰胺基胺、腈、甜菜碱、季胺、亚胺、胺盐、氨基胍、链烷醇酰胺、膦酸酯、含金属化合物、甘油酯、硫化脂肪化合物和烯烃、葵花油、其它天然存在的植物或动物油、二羧酸酯、多元醇和一种或多种脂肪族或芳香族羧酸的酯或偏酯等。
合适的摩擦改进剂可以包含选自直链、支链或芳族烃基或其混合物的烃基,并且可以是饱和或不饱和的。烃基可以由碳、氢或硫、氧等杂原子组成。烃基可以具有大约12至25个碳原子。在一些实施方案中,摩擦改进剂可以是长链脂肪酸酯。在另一个实施方案中,长链脂肪酸酯可以是单酯或阿迪酯或甘油三酯。摩擦改进剂可以是长链脂肪酰胺、长链脂肪酯、长链脂肪环氧化物衍生物或长链咪唑啉。
其他合适的摩擦改性剂可以包括有机的、无灰的(无金属的)、无氮的有机摩擦改进剂。这种摩擦改进剂可以包括通过羧酸和酸酐与链烷醇反应生成的酯,并且通常包括共价键合到亲油烃链上的极性端基(例如羧基或羟基)。甘油单油酸酯(GMO)是有机无灰无氮摩擦改进剂的一个实例,它可以包含油酸的单酯、二酯和三酯。美国第6,723,685号专利中描述了其他合适的摩擦改进剂,在此全文引入作为参考。
胺类摩擦改进剂可包括胺类或多胺类。这种化合物可以具有直链的烃基,饱和的或不饱和的,或它们的混合物,并且可以含有约12至约25个碳原子。适用的摩擦改进剂的其它实例包括烷氧基化胺和烷氧基化醚胺。这种化合物可以具有直链的烃基,饱和的、不饱和的或它们的混合物。它们可以含有约12至约25个碳原子。实例包括乙氧基化胺和乙氧基化醚胺。
胺和酰胺可以原样使用,或者以与硼化合物如氧化硼、卤化硼、偏硼酸盐、硼酸或1-2-3-烷基硼酸盐的加合物或反应产物的形式使用。美国第6,300,291号专利中描述了其他合适的摩擦改进剂,在此全文引入作为参考。
摩擦改性剂可以选择地以例如大约0wt%~大约10wt%,或大约0.01wt%~8wt%,或大约0.1wt%~大约4wt%的范围存在。
含钼化合物:本文的润滑油组合物可任选地含有一种或多种含钼化合物。油溶性钼化合物可以具有抗磨剂、抗氧化剂、摩擦改性剂或其混合物的功能性能。油溶性钼化合物可以包括二硫代氨基甲酸钼、二烷基二硫代磷酸钼、二硫代次膦酸钼、钼化合物的胺盐、钼黄原酸盐、硫黄原酸钼、硫化钼、羧酸钼、烷氧基钼、三核有机钼化合物和/或它们的混合物。硫化钼包括二硫化钼。二硫化钼可以以稳定分散的形式存在。在一个实施方案中,油溶性钼化合物可以选自二硫代氨基甲酸钼、二烷基二硫代磷酸钼、钼化合物的胺盐及其混合物。在一个实施方案中,油溶性钼化合物可以是二硫代氨基甲酸钼。
可以使用的钼化合物的合适实例包括以商品名销售的商业材料,例如R.T.Vanderbilt有限公司的二硫代氨基甲酸氧硫化钼822TM、二硫代氨基甲酸氧硫化钼TMA、二硫代氨基甲酸氧硫化钼2000TM和二硫代氨基甲酸氧硫化钼855TM,以及艾迪科公司的Sakura-Lube S-165、S-200、S-300、S-310G、S-525、S-600、S-700和S-710,以及它们的混合物。合适的钼化合物还在US 5,650,381;US RE 37,363 E1;US RE 38,929 E1;和US RE 40,595 E1中有描述,在此进行全文引用。
另外,钼化合物可以是酸性钼化合物。包括钼酸、钼酸铵、钼酸钠、钼酸钾和其它碱金属钼酸盐和其它钼盐,例如钼酸钠氢、MoOCl4、MoO2Br2、Mo2O3Cl6、三氧化钼或类似的酸性钼化合物。或者,可以通过碱性氮化合物的钼/硫络合物向组合物提供钼,例如在美国第4,263,152号;4,285,822;4,283,295;4,272,387;4,265,773;4,261,843;第4,259,195和第4,259,194号;以及第WO 94/06897专利中有描述,其全部内容在此进行引用。
另一类合适的有机钼化合物是三核钼化合物,例如通式为Mo3SkLnQz的化合物及其混合物,其中S代表硫,L代表独立选择的具有有机基团的配体,所述有机基团具有足够数量的碳原子以使化合物可溶于或可分散于油中,n为1-4,k为4-7,Q选自中性给电子化合物,例如水、胺、醇、膦和醚,z为0-5,包括非化学计量值。在所有配体的有机基团中,至少有21个碳原子,如至少25个、至少30个或至少35个碳原子。其他合适的钼化合物在美国第6,723,685专利中有描述,在此公开材料中全文引入作为参考。
油溶性钼化合物可以通过提供大约0.5ppm~2000ppm钼、大约1ppm~700ppm钼、大约1ppm~550ppm钼、大约5ppm~300ppm钼或大约20ppm~约250ppm的钼存在。
过渡金属氟化物:在另一个实施方案中,油溶性化合物可以含过渡金属化合物或准金属。过渡金属可以包括但不限于钛、钒、铜、锌、锆、钼、钽、钨等。合适的准金属包括但不限于硼、硅、锑、碲等。
在一个实施方案中,油溶性含过渡金属的化合物可以用作抗磨剂、摩擦改进剂、抗氧化剂、沉积控制添加剂,或者这些功能中的一种以上。在一个实施方案中,油溶性含过渡金属的化合物可以是油溶性钛化合物,例如钛(IV)醇盐。在可用于或可用于制备本发明的油溶性材料的含钛化合物中,所公开的技术包括Ti(IV)氧化物等各种Ti(IV)化合物;硫化钛(IV);硝酸钛(IV);钛(IV)醇盐,例如甲醇钛、乙醇钛、丙醇钛、异丙醇钛、丁醇钛、2-乙基己氧基钛;和其它钛化合物或复合物,包括但不限于苯酚钛;羧酸钛,例如2-乙基-1-3-己二酸钛(IV)或柠檬酸钛或油酸钛;和异丙醇钛(IV)(三乙醇氨基)。所公开的技术中包含的其它形式的钛包括磷酸钛,例如二硫代磷酸钛(如二烷基二硫代磷酸钛)和磺酸钛(例如烷基苯磺酸盐),或者通常是钛化合物与各种酸性物质形成盐(例如油溶性盐)的反应产物。因此,钛化合物可以从有机酸、醇和乙二醇等物质中得到。钛化合物可能还以包含Ti-O-Ti结构的二聚体或低聚体的形式存在。这种钛材料是可商购的,或者可以通过对本领域技术人员来说显而易见的合适的合成技术容易地制备、它们在室温下可以以固体或液体形式存在,这取决于特定的化合物。它们也可以在合适的惰性溶剂中以溶液形式提供。
在一个实施方案中,钛可以作为Ti改性的分散剂提供,例如琥珀酰亚胺分散剂。可以通过在钛醇盐和烃基取代的丁二酸酐之间形成钛混合酸酐,例如烯基(或烷基)丁二酸酐,来制备此类材料。所得到的钛酸丁二酸中间体可以直接使用,也可以与任何材料反应,例如(a)多胺基琥珀酰亚胺/酰胺分散剂,具有自由的、可凝结的-NH功能;(b)多胺基琥珀酰亚胺/酰胺分散剂的组分,即烯基-(或烷基-)琥珀酸酐和多胺,(c)通过取代的琥珀酸酐与多元醇、氨基醇、多胺或其混合物反应制备的含羟基的聚酯分散剂。或者,钛酸盐-琥珀酸盐中间体可以与其它试剂如醇、氨基醇、醚醇、聚醚醇或多元醇、或脂肪酸反应,其产物或者直接用于将Ti赋予润滑剂,或者进一步与如上所述的琥珀酸分散剂反应。例如,1份(以摩尔计算))钛酸四异丙酯可以与约2份(以摩尔计算)聚异丁烯取代的琥珀酸酐在140-150℃下反应5-6小时,以提供钛改性的分散剂或中间体。所得材料(30g)可进一步与聚异丁烯取代丁二酸酐和聚乙烯多胺混合物(127克+稀释油)在150℃下反应1.5小时,生成钛改性丁二酰亚胺分散剂。
另一种含钛化合物可以是钛醇盐和C6到C25羧酸的反应产物。反应产物可以由以下公式表示:
式中,n为2、3、4中选取的整数,R为含有5~24个碳原子的烃基,或用公式:
其中m+n=4,n为1-3,R4为具有1-8个碳原子的烷基部分,R1选自含有约6-25个碳原子的烃基,R2和R3相同或不同,选自含有约1-6个碳原子的烃基,或者钛化合物可以用下公式表示:
其中x为0-3,R1选自含约6-25个碳原子的烃基,R2和R3相同或不同,都选自含约1-6个碳原子的烃基,R4选自H或C6-C25羧酸部分。
合适的羧酸可以包括但不限于己酸、辛酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、花生酸、油酸、芥酸、亚油酸、亚麻酸、环己烷羧酸、苯乙酸、苯甲酸、新癸酸等。
在一个实施方案中,油溶性钛化合物可以通过提供0~3000ppm重量的钛或25~大约1500ppm重量的钛或约35ppm~500ppm重量的钛或大约50ppm~300ppm重量的钛的量存在于润滑油组合物中。
黏度指数改进剂:本文的润滑油组合物还可以任选含有一种或多种粘度指数改进剂。合适的粘度指数改进剂可包括聚烯烃、烯烃共聚物、乙烯/丙烯共聚物、聚异丁烯、氢化苯乙烯-异戊二烯聚合物、苯乙烯/马来酸酯共聚物、氢化苯乙烯/丁二烯共聚物、氢化异戊二烯聚合物、α-烯烃马来酸酐共聚物、聚甲基丙烯酸酯、聚丙烯酸酯、聚烷基苯乙烯、氢化烯基芳基共轭二烯共聚物或其混合物。粘度指数改进剂可以包括星形聚合物,合适的例子描述在美国公开号20120101017A1中有相关描述。
除了粘度指数改进剂或代替粘度指数改进剂,本文的润滑油组合物还可以任选含有一种或多种分散剂粘度指数改进剂。合适的粘度指数改进剂可以包括官能化的聚烯烃,例如,已经用酰化剂(例如马来酸酐)和胺的反应产物官能化的乙烯-丙烯共聚物;用胺官能化的聚甲基丙烯酸酯,或与胺反应的酯化马来酸酐-苯乙烯共聚物。
粘度指数改进剂和/或分散剂粘度指数改进剂的总量可以大约是润滑油组合物的0wt%~20wt%,0.1wt%~15wt%,0.1wt%~12wt%,或0.5wt%~10wt%。
其他可选添加剂:可以选择其他添加剂来执行润滑液所需的一种或多种功能。此外,一种或多种提及的添加剂可以是多功能的,并提供除此处所述功能之外的功能。
根据本公开内容的润滑油组合物可以任选地包含其他性能添加剂。其它功能助剂可以是除了此处公开的特定添加剂之外的添加剂,和/或可以包含一种或多种金属钝化剂、粘度指数改进剂、清净剂、无灰TBN增强剂、摩擦改性剂、抗磨剂、缓蚀剂、防锈剂、分散剂、分散剂粘度指数改进剂、极压剂、抗氧化剂、抑泡剂、破乳剂、乳化剂、倾点下降剂、密封溶胀剂及其混合物。通常,全配方润滑油将含有一种或多种这些性能添加剂。
合适的金属钝化剂可以包括苯并三唑的衍生物(通常为甲苯基三唑)、二巯基噻二唑衍生物、1,2,4-三唑、苯并咪唑、2-烷基二硫代苯并咪唑或二硫化二苯并噻唑;泡沫抑制剂,包括丙烯酸乙酯和丙烯酸2-乙基己酯以及任选的乙酸乙烯酯的共聚物;反乳化剂,包括磷酸三烷基酯、聚乙二醇、聚环氧乙烷、聚环氧丙烷和(环氧乙烷-环氧丙烷)聚合物;倾点下降剂,包括马来酸酐-苯乙烯的酯、聚甲基丙烯酸酯、聚丙烯酸酯或聚丙烯酰胺。
合适的泡沫抑制剂包括硅基化合物,例如硅氧烷。
合适的倾点下降剂可以包括聚甲基丙烯酸甲酯或其混合物。根据润滑油组合物的最终重量,倾点抑制剂的存在量足以提供约0wt%~约1wt%、约0.01wt%~约0.5wt%或约0.02wt%~约0.04wt%的润滑油组成物。
合适的防锈剂可以是具有抑制黑色金属表面腐蚀性能的单一化合物或化合物的混合物。适用于本公开材料的防锈剂的非限制性实例包括油溶性高分子量有机酸,例如2-乙基己酸、月桂酸、肉豆蔻酸、棕榈酸、油酸、亚油酸、亚麻酸、山嵛酸和蜡酸,以及油溶性多元羧酸,包括二聚酸和三聚酸,例如由妥尔油脂肪酸、油酸和亚油酸生产的那些。其他合适的腐蚀抑制剂包括分子量范围为大约600~3000的长链α,ω-二羧酸和烯基琥珀酸,其中烯基含有约10个或更多个碳原子,例如四丙烯基琥珀酸、十四烯基琥珀酸和十六烯基琥珀酸。另一种有用的酸性腐蚀抑制剂是链烯基中具有约8至约24个碳原子的链烯基琥珀酸与醇如聚乙二醇的半酯。相应的这种烯基琥珀酸的半酰胺也是有用的。一种有用的防锈剂是高分子量有机酸。
根据润滑油组合物的最终重量,如果存在防锈剂,其用量足以提供约0wt%~约5wt%,约0.01wt%~约3wt%,约0.1wt%~约2wt%基于润滑油组合物的最终重量。
一般情况下,包括中性至高碱性和硫化的苯酚烷基酯产品的合适的润滑剂可以包括下表所列范围内的添加剂组分。
表2:可适用的润滑油组合物
以上每种组分的百分比代表每种组分的重量百分比,基于最终润滑油组合物的重量。润滑油组合物的剩余部分由一种或多种基础油组成。用于配制本文所述组合物的添加剂可以单独或以各种子组合形式混入基础油中。然而,使用添加剂浓缩物(即添加剂加上稀释剂,例如烃溶剂)同时混合所有组分可能是合适的。全配方润滑剂通常包含添加剂包,在本文中称为分散剂/抑制剂包或DI包,其将提供配方中所需的特性。
本文中的润滑剂被配置用于各种类型的润滑剂产品,例如汽车润滑剂和/或润滑脂、内燃机油、混合发动机油、电动发动机润滑剂、传动系润滑剂、传动装置润滑剂、齿轮油、液压润滑剂、拖拉机液压油、金属加工液、涡轮发动机润滑剂、固定式发动机润滑剂、拖拉机润滑剂、摩托车润滑剂、动力转向液、离合器液、车轴液、湿式制动液等。合适的发动机类型可包括但不限于重型柴油机、客车、轻型柴油机、中速柴油机或船用发动机。内燃机可以是柴油燃料发动机、汽油燃料发动机、天然气燃料发动机、生物燃料发动机、混合柴油/生物燃料发动机、混合汽油/生物燃料发动机、酒精燃料发动机、混合汽油/酒精燃料发动机、压缩天然气(CNG)燃料发动机或其混合物。柴油发动机可能是压缩点火发动机。汽油发动机可能是火花引燃的发动机。内燃机也可以与电源或电池电源结合使用。如此配置的发动机通常被称为混合动力发动机。内燃机可以是二冲程、四冲程或旋转式发动机。合适的内燃机包括船用柴油发动机(例如内陆船用)、航空活塞式发动机、低负荷柴油发动机以及摩托车、汽车、机车和卡车发动机。发动机可以与涡轮增压器连接。
用于内燃机的润滑油组合物可以适用于任何发动机润滑剂,而不考虑硫、磷或硫酸化灰分(ASTM D-874)的含量。发动机油润滑油的含硫量可为约1wt%或更少,或约0.8wt%或更少,或约0.5wt%或更少,或约0.3wt%或更少,或约0.2wt%或更少。在一个实施方案中,硫含量可以在约0.001wt%~约0.5wt%,或0.01wt%~约0.3wt%。磷含量可能是大约0.2wt%或更少,或0.1wt%或更少,或约0.085wt%或更少,或约0.08wt%或更少,甚至约0.06wt%或更少,约0.055wt%或更少,或约0.05wt%或更少。在一个实施方案中,磷含量可以大约是50ppm~1000ppm,或325ppm~850ppm。总硫酸盐灰分含量可约为2wt%或更少,或约为1.5wt%或更少,或约为1.1wt%或更少,或约为1wt%或更少,或约为0.8wt%或更少,或约为0.5wt%或更少。在一个实施方案中,硫酸盐灰分含量可约为0.05wt%~约0.9wt%,或约0.1wt%或约为0.2wt%~约0.45wt%。在另一个实施方案中,硫含量约为0.4wt%或更少,磷含量约为0.08wt%或更少,硫酸盐灰分约为1wt%或更少。在另一个实施方案中,硫含量约为0.3wt%或以下,磷含量约为0.05wt%或以下,硫酸盐灰分约为0.8wt%或以下。
此外,本说明的润滑剂可能适用于满足一个或以上行业规范要求(例如,ILSACGF-3、GF-4、GF-5、GF-6、PC-11、CF、CF-4、CH-4、CK-4、FA-4、CJ-4、CI-4+、CI-4、API SG、SJ、SL、SM、SN、SN+、ACEA A1/B1、A2/B2、A3/B3、A3/B4、A5/B5、C1、C2、C3、C4、C5、E4/E6/E7/E9、Euro 5/6、JASO DL-1、低SAPS、中SAPS),或原始设备制造商规范(例如,Dexos1TM、Dexos2TM、MB-Approval 229.1、229.3,229.5、229.51/229.31、229.52、229.6、229.71、226.5、226.51、228.0/.1、228.2/.3、228.31、228.5、228.51、228.61、大众501.01、502.00、503.00/503.01、504.00、505.00、505.01、506.00/506.01、507.00、508.00、509.00、508.88、509.99、宝马Longlife-01、Longlife-01FE、Longlife-04、Longlife-12FE、Longlife-14FE+、Longlife-17FE+、保时捷A40、C30、标致雪铁龙汽车B71 2290、B71 2294、B71 2295、B71 2296、B712297、B71 2300、B71 2302、B71 2312、B71 2007、B71 2008、雷诺RN0700、RN0710、RN0720、福特WSS-M2C153-H、WSS-M2C930-A、WSS-M2C945-A、WSS-M2C913A、WSS-M2C913-B、WSS-M2C913-C、WSS-M2C913-D、WSS-M2C948-B、WSS-M2C948-A、GM 6094-M、克莱斯勒MS-6395、菲亚特9.55535G1、G2、M2、N1、N2、Z2、S1、S2、S3、S4、T2、DS1、DSX、GH2、GS1、GSX、CR1、捷豹路虎STJLR.03.5003,STJLR.03.5004、STJLR.03.5005、STJLR.03.5006、STJLR.03.5007、STJLR.51.5122),或本文未提及的过去或未来的任何PCMO或HDD规范。在客车机油(PCMO)申请的一些实施方案中,成品流体中的磷含量为1000ppm或以下、或900ppm或以下、或800ppm或以下。
在一个实施方案中,润滑油组合物是机油,其中润滑油组合物可以具有:(i)硫含量约为0.5wt%或以下;(ii)磷含量约为0.1wt%或以下;以及(iii)硫酸盐灰分含量约为1.5wt%或以下。
在一个实施方案中,润滑油组合物适用于2冲程或4冲程船用柴油内燃机。在一个实施方案中,船用柴油内燃机为2冲程发动机。在一些实施方案中,由于存在一个或以上的原因,导致润滑油组合物不适用于2冲程或4冲程船用柴油内燃机。这些原因包括但不限于:船用机油硫含量较高,以及船用机油总碱值(TBN)含量较高(例如,船用机油总碱值约为40以上)。
在一些实施方案中,润滑油组合物适用于使用硫含量较低燃料的发动机(例如,燃料中的硫含量约为1~5%)。公路用车燃料中的硫含量约为15ppm(或硫含量约为0.0015%)。
实例
以下实例用于说明本公开的实例性实施方案。在这些实例中,以及本申请的其他地方,除非另有说明,否则,所有比率、部分和百分比均按重量计算。这些实例仅用于说明目的,不用于限制本文已公开的本发明的范围。
实例1
润滑油组合物的制备如表3和表4所示。表5所示为符合M271国际能效评估组织发动机点火试验(CEC L-107-19)规定的对发动机平均油泥(AES)的影响。用于这些评估的每种流体(无论是发明式还是比较式),均包括下述内容:
-分散剂1是一种聚异丁烯琥珀酰亚胺分散剂,其中聚异丁烯取代基的分子量大于1900;
-分散剂2是一种聚异丁烯琥珀酰亚胺分散剂,其中聚异丁烯取代基的分子量小于1900;
-分散剂3是一种经马来酸酐和硼酸反应后的聚异丁烯琥珀酰亚胺分散剂;
-抗氧化剂1是一种烷基化二苯胺类抗氧化剂;
-抗氧化剂2是一种受阻酚类抗氧化剂;
该流体还包括等量的二烷基二硫代磷酸锌(ZDDP)、钙和镁磺酸盐洗涤剂、消泡剂、稀释剂、摩擦改进剂、倾点分散剂、粘度改进剂和基础油混合物,目标KV100约为10.5cSt。该流体中总碱值含量约为7.1~8.7mgKOH/g。
表3
表4:
表5:发动机平均油污(CEC L-107-19)
如表3、表4和表5所示,虽然比较流体G和H的成分与发明样品相似,但是比较流体G和H不符合与流体中总氮或氮源相关的一种或以上关系,根据M271发动机点火试验结果,该润滑油与发动机平均油污相关。此外,虽然发明流体A至F均满足与氮和氮源相关的独特流体参数要求,但令人惊讶的是,在M271发动机点火试验中,其性能几乎是发动机平均油污的两倍。此外,图1至4所示为所获得的跟来自发明和比较流体中的氮和氮源相关的发动机平均油污,其中显示了本文成分所特有的最小和最大影响。
需要注意的是,在本说明书和所附权利要求书中使用的单数形式“a”、“an”和“the”,包括复数指称(明确并毫不含糊地限定于一个指称情形除外)。因此,例如,当提到“一种抗氧化剂”时,应包括两种或以上不同的抗氧化剂。本文使用的术语“包括”及其语法变体不受限制。因此,引用列表中的项目不排除其他类似项目(可替代或添加至列表项目)。
就本说明书和所附权利要求书而言,除非另有其他规定,否则,所有表示数量、百分比或比例的数字,以及本说明书和权利要求书中使用的其他数值,均应被理解为在所有实例中通过术语“大约”进行了修改。因此,除非另有相反规定,否则,以下说明书和所附权利要求书中规定的数值参数均是近似值,可以根据本公开所寻求获得的所需特性而发生变化。至少,不应试图将等效原则的应用限制在权利要求书的范围内,每个数值参数至少应根据所报告的有效数字的数目和应用普通的四舍五入法进行理解。
应理解为,本文所公开的每种成分、化合物、取代基或参数应被解释为仅单独使用或与本文所公开的每种其他成分、化合物、取代基或参数中的一种或以上结合使用。
此外,还应进一步理解为,本文所公开的每个区间均应被解释为对所公开区间内具有相同有效数字之数的每个特定值的公开。因此,例如,从1至4的区间将被解释为对值1、2、3和4以及这些值的任何区间的明确公开。
此外,还应进一步理解为,对于相同的成分、化合物、取代基或参数而言,应将本文所公开的每个区间的每个下限解释为与本文所公开的每个区间的每个上限和每个区间内的每个特定值相结合。因此,本公开应被解释为通过将每个区间的每个下限与每个区间的每个上限或每个区间内的每个特定值相结合,或将每个区间的每个上限与每个区间内的每个特定值相结合的方式对所有区间进行公开。也就是说,还可以进一步理解为,本文还讨论了在大区间内端点值之间的任何区间。因此,从1至4的区间也意味着从1至3、1至2、2至4、2至3等区间。
此外,本说明或实例中公开的每种成分、化合物、取代基或参数的特定数量/值将被解释为对区间下限或上限的公开,并可以与本申请其他地方公开的相同成分、化合物、取代基或参数的一个区间的任何其他下限或上限,或特定数量/值,以形成该成分、化合物、取代基或参数的的一个区间。
虽然已经描述了特定的实施方案,但对于申请人或其他熟练技术人员而言,可能会发生没有预见到或目前无法预见的备选方案、修改、变更、改进和实质性等价物。因此,已提交并可修改的所附权利要求书将包含所有此类备选方案、修改、变更、改进和实质性等价物。
Claims (15)
1.一种有效减少发动机油泥的润滑油组合物,所述润滑油组合物包括:
一种具有润滑粘度的基础油;
由分散剂体系和抗氧化剂体系提供的氮;
分散剂体系至少包括一种被烃基取代的琥珀酰亚胺分散剂,通过将一种被烃基取代的酰化剂与一种氮源发生反应而获得;
抗氧化剂体系至少包括一种胺类抗氧化剂;
所述分散剂体系提供的氮与润滑油组合物中总氮的重量比约为0.6:1至0.85:1;以及
由分散剂体系提供的至少约75%的氮是一次氮或二次氮,而不是反应后的氮。
2.权利要求书1的润滑油组合物,进一步构成由抗氧化剂体系的至少一种胺类抗氧化剂提供的氮与润滑油组合物中的总氮的重量比,即大约0.15:1至0.4:1;和/或分散剂体系提供的氮与至少一种绿支安抗氧化剂提供的氮的重量比,即大约1.8:1至5.3:1;和/或依据CEC L-107-19,进一步构成发动机平均油泥值,即大约7至10。
3.权利要求书1的润滑油组合物,进一步包括某种磷源,它包括一种或以上含磷化合物,这些含磷化合物是从一种硫代磷酸盐、二硫代磷酸盐、金属磷酸盐、金属硫代磷酸盐、金属二硫代磷酸盐、磷酸盐、亚磷酸盐、磷酸酯及其盐和混合物中独立筛选出来的。
4.权利要求书1的润滑油组合物,进一步包括一种洗涤剂体系,它至少包括一种含金属洗涤剂,可为成分提供含量高达3500ppm的金属,并且合并总碱值约为0至500。
7.权利要求书1的润滑油组合物,其中,酰化剂为顺丁烯二酸酐;氮源为从多乙烯多胺的混合物中筛选出的聚亚烷基多胺(平均含有5个氮原子)、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺或其组合;所述烃基取代基的数均分子量约为1000~2,500。
8.权利要求书1的润滑油组合物,其中,分散剂体系包括至少两种烃基取代的琥珀酰亚胺分散剂;和/或其中经第一烃基取代的琥珀酰亚胺分散剂可通过将经烃基取代的酰化剂与氮源反应而获得;其中第一分散剂的烃基取代基的数均分子量至少为1900,并且经第二烃基取代的琥珀酰亚胺分散剂可通过将经烃基取代的酰化剂与氮源反应而获得;其中第二分散剂的烃基取代基的数均分子量应低于1900;和/或其中仅一种经烃基取代的丁二酰亚胺分散剂是与硼源和/或马来酸酐反应后获得的。
9.权利要求书8的润滑油组合物,其中,分散剂体系包含的非反应后的分散剂约为反应后的分散剂数量的2至4倍;和/或其中分散剂体系为润滑油组合物提供的总硼量不超过约300ppm。
10.权利要求书3的润滑油组合物,其中,存在的磷源可为润滑油组合物提供大约900ppm的磷。
11.权利要求书3的润滑油组合物,其中,一种或以上含磷化合物是从一种金属磷酸盐、一种金属硫代磷酸盐、金属二硫代磷酸盐或其组合中独立筛选出来的。
12.权利要求书11的润滑油组合物,其中,一种或多种含磷化合物是一种金属二硫代磷酸盐,它的烷基内含有12至32个碳原子,每个烷基平均含有3至8个碳原子;和/或其中一种或多种含磷化合物包括第一种金属二硫代磷酸盐,其中烷基来自仲醇;第二种金属硫代磷酸盐,其烷基来自伯醇;和/或其中一种或多种含磷化合物的金属是从基团合中独立筛选出来的,该基团包括铝、铅、锡、钼、锰、镍、铜、钛、钨、锆或锌。
13.权利要求书1的润滑油组合物,其中,至少一种为润滑油组合物提供氮的抗氧化剂是一种胺类抗氧化剂,它是从一种芳香胺、一种烷基化二苯胺、一种苯基-α-萘胺、一种烷基化苯基-α-萘胺、一种受阻非芳香胺或其组合中筛选出来的。
14.权利要求书13的润滑油组合物,其中,润滑油组合物包括第二种抗氧化剂,它是从一种酚类抗氧化剂、一种硫化烯烃、一种胺类抗氧化剂或其组合中筛选出来的。
15.权利要求书4的润滑油组合物,其中,洗涤剂体系包括一种或多种含金属石碳酸盐、含硫石碳酸盐、磺酸盐、calixarates、salixarates、水杨酸盐、羧酸、磷酸、单和/或二硫代磷酸、烷基酚、硫耦合烷基酚化合物、亚甲基桥苯酚或其组合。
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US17/339,286 US11479736B1 (en) | 2021-06-04 | 2021-06-04 | Lubricant composition for reduced engine sludge |
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