CN101040035A - 在曲轴箱油中作为燃料经济性改进剂和抗磨剂的酒石酸衍生物及其制备 - Google Patents
在曲轴箱油中作为燃料经济性改进剂和抗磨剂的酒石酸衍生物及其制备 Download PDFInfo
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- CN101040035A CN101040035A CNA2005800348432A CN200580034843A CN101040035A CN 101040035 A CN101040035 A CN 101040035A CN A2005800348432 A CNA2005800348432 A CN A2005800348432A CN 200580034843 A CN200580034843 A CN 200580034843A CN 101040035 A CN101040035 A CN 101040035A
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- oil
- acid
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- lubricant
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- 239000003921 oil Substances 0.000 title claims description 69
- 239000003795 chemical substances by application Substances 0.000 title claims description 34
- 239000000446 fuel Substances 0.000 title abstract description 16
- 238000002360 preparation method Methods 0.000 title description 21
- 150000003892 tartrate salts Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 239000000314 lubricant Substances 0.000 claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 oleyl acid amides Chemical class 0.000 claims description 47
- 150000001412 amines Chemical class 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000007859 condensation product Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 229960002317 succinimide Drugs 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 claims description 5
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 claims description 5
- 150000001639 boron compounds Chemical class 0.000 claims description 5
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000013530 defoamer Substances 0.000 claims description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 3
- AVVIDTZRJBSXML-UHFFFAOYSA-L calcium;2-carboxyphenolate;dihydrate Chemical compound O.O.[Ca+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O AVVIDTZRJBSXML-UHFFFAOYSA-L 0.000 claims description 2
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical compound [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 4
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- 150000001721 carbon Chemical group 0.000 description 18
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- 150000002466 imines Chemical class 0.000 description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 description 13
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- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
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- GRMNJXQBRPJVQV-UHFFFAOYSA-N 2,3-dihydroxybutanediamide Chemical compound NC(=O)C(O)C(O)C(N)=O GRMNJXQBRPJVQV-UHFFFAOYSA-N 0.000 description 9
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229920013639 polyalphaolefin Polymers 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 229940095064 tartrate Drugs 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000001118 alkylidene group Chemical group 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 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 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical group 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000008431 aliphatic amides Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000011591 potassium Substances 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- CIRMGZKUSBCWRL-LHLOQNFPSA-N (e)-10-[2-(7-carboxyheptyl)-5,6-dihexylcyclohex-3-en-1-yl]dec-9-enoic acid Chemical compound CCCCCCC1C=CC(CCCCCCCC(O)=O)C(\C=C\CCCCCCCC(O)=O)C1CCCCCC CIRMGZKUSBCWRL-LHLOQNFPSA-N 0.000 description 2
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- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([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 description 1
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- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
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- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
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- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003336 secondary aromatic amines Chemical class 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- 150000003899 tartaric acid esters Chemical class 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/72—Esters of polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/16—Amides; Imides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
在低硫、低灰分和低磷润滑剂中使用本发明的酒石酸化合物的制剂降低磨损和摩擦，并且改善燃料经济性。
Description
发明背景
本发明涉及低硫、低灰分、低磷的润滑剂组合物和润滑内燃机，提供改进的燃料经济性和燃料经济性的保持以及提供磨损和摩擦减少的方法。
燃料经济性极其重要，例如可以通过减少发动机内的摩擦来促进燃料经济性改进的润滑剂具有重要价值。本发明提供包含添加剂封包的低硫、低灰分、低磷的润滑剂组合物，其导致内燃机中燃料经济性改进。这一改进通过提供添加剂封包来实现，在该添加剂封包中摩擦改进剂组分专门或者主要是酒石酰亚胺或酒石酰胺或其组合。
US 4,237,022，Barrer，1980年12月2日，公开了可用作润滑剂和燃料中的添加剂以有效减少尖叫声和摩擦并改善燃料经济性的酒石酰亚胺。
US 4,952,328，Davis等，1990年8月28日，公开了内燃机用的润滑油组合物，其包含(A)润滑粘度的油，(B)通过琥珀酸酰化剂与某些胺反应制成的羧酸衍生物，和(C)碱性的磺酸或羧酸的碱金属盐。一个润滑剂组合物例子(润滑剂III)包含具有粘度指数改进剂的基础油；碱性的烷基化苯磺酸镁；高碱性的烷基苯磺酸钠；碱性的烷基化苯磺酸钙；琥珀酰亚胺分散剂；以及二硫代磷酸的锌盐。
US 4,326,972，Chamberlin，1982年4月27日，公开了改进内燃机燃料经济性的润滑剂组合物。该组合物包含特定的经硫化的组合物(基于羧酸酯)以及碱性的碱金属磺酸盐。附加的成分可以包括至少一种油可分散的清净剂或分散剂、粘度改进剂和特定的磷酸盐。
发明内容
本发明提供适合于润滑内燃机的低硫、低磷、低灰分的润滑剂组合物，其包含下列组分：
(a)润滑粘度的油，和
(b)式I所示物质与具有约8-约30个碳原子的醇或胺及其组合的缩合产物；
其中各个R独立地是H或烃基，或者其中R基团一起成环；并且其中如果R是H，所述缩合产物任选地通过酰化或与硼化合物反应而进一步官能化；
其中所述润滑剂组合物具有至多约1.0的硫酸化灰分值，至多约0.08wt％的磷含量和至多约0.4wt％的硫含量。
本发明进一步提供润滑内燃机的方法，其包括向发动机提供所述润滑剂组合物。
发明详述
以下将通过非限制性的说明描述各种优选的特征和实施方案。
本发明提供如上所述的组合物。该组合物往往在一种情况下具有0.4wt％以下的总硫含量，在另一种情况下是0.3wt％以下，在另一种情况下是0.2wt％以下，在另一种情况下是0.1wt％以下。本发明组合物中硫的主要来源往往是源于常规的稀释油。总硫含量的通常范围是0.1-0.01wt％。
所述组合物往往具有小于或等于该组合物的800ppm的总磷含量，在另一种情况下等于或小于500ppm，在另一种情况下等于或小于300ppm，在另一种情况下等于或小于200ppm，在另一种情况下等于或小于100ppm。总磷含量的通常范围是500-100ppm。
所述组合物往往具有该组合物的1.0wt％以下的如ASTM D-874确定的总硫酸化灰分含量，在一种情况下等于或小于0.7wt％，在另一种情况下等于或小于0.4wt％，在另一种情况下等于或小于0.3wt％，在另一种情况下等于或小于0.05wt％。总硫酸化灰分含量的通常范围是0.7-0.05wt％。
润滑粘度的油
所述低硫、低磷、低灰分的润滑油组合物包含一般以主要量(即大于约50wt％的量)存在的一种或多种基础油。一般而言，基础油的存在量大于该润滑油组合物重量的约60％，或大于约70％，或大于约80％。基础油的硫含量通常小于0.2wt％。
所述低硫、低磷、低灰分润滑油组合物可以具有100℃下至多约16.3mm2/s的粘度，在一种实施方案中是100℃下5-16.3mm2/s(cSt)，在一种实施方案中是100℃下6-13mm2/s(cSt)。一种实施方案中，所述润滑油组合物具有0W、0W-20、0W-30、0W-40、0W-50、0W-60、5W、5W-20、5W-30、5W-40、5W-50、5W-60、10W、10W-20、10W-30、10W-40或10W-50的SAE粘度等级。
所述低硫、低磷、低灰分润滑油组合物可以具有至多4mm2/s(cSt)通过ASTM D4683过程测定的150℃下的高温/高剪切粘度，在一种实施方案中至多是3.7mm2/s(cSt)，在一种实施方案中是2-4mm2/s(cSt)，在一种实施方案中是2.2-3.7mm2/s(cSt)，在一种实施方案中是2.7-3.5mm2/s(cSt)。
用于所述低硫、低磷、低灰分润滑剂组合物的基础油可以是天然油、合成油或其混合物，只要所述油的硫含量不超过对本发明的低硫、低磷、低灰分润滑油组合物所要求的上述硫浓度限制即可。可用的天然油包括动物油和植物油(如蓖麻油、猪油)，矿物润滑油(如液体石油)以及链烷烃、环烷烃或混合链烷烃-环烷烃型的经溶剂处理或酸处理的矿物润滑油。源自煤或页岩的油也是可用的。合成润滑油包括烃油，如聚合和共聚的烯烃(如聚丁烯、聚丙烯、丙烯异丁烯共聚物等)；聚(1-己烯)、聚(1-辛烯)、聚(1-癸烯)等及其混合物；烷基苯(如十二烷基苯、十四烷基苯、二壬基苯、二-(2-乙基己基)苯，等等)；聚苯(如联苯、三联苯、烷基化的聚苯等)；烷基化的二苯醚以及它们的衍生物、类似物和同系物等等。
已通过酯化、醚化等使其端羟基改性的氧化烯聚合物和共聚物及其衍生物构成可用的另一类已知合成润滑油。其例子是通过环氧乙烷或环氧丙烷的聚合制备的油，这些聚氧化烯聚合物的烷基和芳基醚(如平均分子量约1000的甲基聚异丙二醇醚，分子量约500-1000的聚乙二醇的二苯醚，分子量约1000-1500的聚丙二醇的二乙醚等)；或其一元或多元羧酸酯，例如四甘醇的乙酸酯、混合C3-8脂肪酸酯或羧酸二酯。
可以使用的另一类适合的合成润滑油包括二羧酸(如邻苯二甲酸、琥珀酸、烷基琥珀酸、烯基琥珀酸、马来酸、壬二酸、辛二酸、癸二酸、富马酸、己二酸、亚油酸二聚物、丙二酸、烷基丙二酸、烯基丙二酸等)与各种醇(如丁醇、己醇、十二烷醇、2-乙基己醇、乙二醇、二甘醇单醚、丙二醇等)的酯。这些酯的具体例子包括己二酸二丁酯、癸二酸二(2-乙基己基)酯、富马酸二正己酯、癸二酸二辛酯、壬二酸二异辛酯、壬二酸二异癸酯、邻苯二甲酸二辛酯、邻苯二甲酸二癸酯、癸二酸双二十烷基酯、亚油酸二聚物的2-乙基己基二酯、以及通过使1摩尔癸二酸与2摩尔四甘醇和2摩尔2-乙基己酸反应形成的复合酯等。
可用作合成油的酯类还包括由C5-C12一元羧酸与多元醇和多元醇醚，诸如新戊二醇、三羟甲基丙烷、季戊四醇、二季戊四醇和三季戊四醇等制成的那些。
所述油可以是聚α-烯烃(PAO)。通常，PAO源于具有4-30个、或4-20个、或6-16个碳原子的单体。可用的PAO的实例包括源于辛烯、癸烯、其混合物等的那些。这些PAO可以具有100℃下2-15、或3-12、或4-8mm2/s(cSt)的粘度。可用PAO的实例包括100℃下4mm2/s(cSt)的聚α-烯烃，100℃下6mm2/s(cSt)的聚α-烯烃，以及它们的混合物。可以使用矿物油与一种或多种前述PAO的混合物。
可以将未精制的、精制的和再精制的油用于本发明的润滑剂中，所述油是上文所述类型的天然或合成油(以及这些中任意两种或更多种的混合物)。未精制的油是从天然或合成来源直接得到而不经进一步提纯处理的那些。例如，直接得自干馏操作的页岩油，直接得自一次蒸馏的石油或直接得自酯化方法的酯油，这些直接得到并且没有进一步处理就使用的油是未精制的油。精制油与未精制的油相似，不同之处在于它们已在一个或多个提纯步骤中经历进一步处理而改善了一种或多种性能。许多此类提纯技术是所属领域技术人员已知的，如溶剂萃取、二次蒸馏、酸萃取或碱萃取、过滤、渗滤等。再精制的油是通过对已经使用的精制油施用与获得精制油所用的那些相似方法得到的。上述再精制的油也称为回收的或再加工的油，往往另外经过针对清除用过的添加剂和油分解产物的技术的处理。
另外，通过费-托气体至液体合成工艺制成的油是已知的，并可以使用。
摩擦改进剂
本发明的酒石酰亚胺、酒石酰胺或它们的组合可以通过酒石酸与一种或多种胺的反应制成，例如式RR’NH的胺，其中R和R’各自独立地表示H、1-150个碳原子的烃基基团、或-R”OR，只要R和R’中的碳原子总数至少是8，其中R”是2-6个碳原子的二价亚烷基，R是5-150个碳原子的烃基。
适合于本发明的酒石酰亚胺、酒石酰胺或其组合的胺包括式RR’NH表示的那些，其中R和R’表示H或1-150个碳原子的长链烃基，只要R和R’中的碳原子总数至少是8。在一种实施方案中，R或R’包含8-26个碳原子，在另一实施方案中，包含12-18个碳原子。
本发明的酒石酰亚胺、酒石酰胺或其组合通过酒石酸与一种或多种相应的胺反应而方便地制成。用于制备本发明酒石酰亚胺或酒石酰胺的酒石酸可以是市售类型的(从Sargent Welch得到)，可能以一种或多种异构体形式存在，如J-酒石酸、/-酒石酸或内消旋酒石酸，这往往取决于来源(天然的)或合成方法(如由马来酸制备)。这些衍生物也可以由本领域技术人员容易知晓的该二酸的官能等同物制成，如酯、酰氯、酸酐等。
本发明的酒石酰亚胺、酒石酰胺或其组合根据制备酒石酰亚胺或酒石酰胺中所用具体的胺而可以是固体、半固体或油状物。为了在包括润滑和燃料组合物的油质组合物中用作添加剂，酒石酰亚胺或酒石酰胺必须在所述油质组合物中可溶和/或可稳定分散。因而，例如欲用于油中的组合物在它们所要用到的油中是油溶性的和/或可稳定分散的。用于本说明书和所附权利要求中的术语“油溶性的”并非一定表示所述的所有组合物在所有油中可以所有比例混溶或可溶。相反，意在表示所述组合物在其欲发挥作用的油中(矿物油、合成油等)可溶解至允许该溶液表现一种或多种所期望性能的程度。类似地，所述“溶液”并非一定是严格物理或化学意义上的真溶液。相反，它们可以是微乳液或胶态分散体，对于本发明目的而言显示出充分接近真溶液的性能，以为了实用在本发明的上下文中可以与它们互换。
如前所述，本发明的酒石酰亚胺、酒石酰胺或其组合可用作润滑剂的添加剂，在该润滑剂中它们主要用作锈蚀和腐蚀抑制剂、摩擦改进剂、抗磨剂和破乳化剂。它们可以用于各种基于不同润滑粘度油的润滑剂中，所述润滑粘度的油包括天然和合成润滑油及其混合物。这些润滑剂包括曲轴箱润滑油，其用于火花点火式和压缩点火式内燃机，包括汽车和卡车发动机、二冲程发动机、航空活塞发动机、海运和铁路柴油机等等。它们也可以用于燃气发动机、固定动力发动机(stationary power engines)和涡轮机等。自动传动液、驱动桥润滑剂、齿轮润滑剂、金属加工润滑剂、液压系统工作液和其它润滑油以及润滑脂组合物也可以受益于在其中加入本发明的组合物。
其它摩擦改进剂可能存在于本发明的润滑剂中，可以包括甘油单油酸酯、油烯基酰胺、二乙醇脂肪胺和它们的混合物。可用的一列摩擦改进剂包括在US 4,792,410中。
可以通过各种本领域公知的方法制备甘油的脂肪酸酯。这些酯中的多数以工业规模制造，如甘油单油酸酯和甘油单牛油酸酯。可用于本发明的酯是油溶性的，优选由C8-C22脂肪酸或其混合物(如在天然产物中得到的)制成。所述脂肪酸可以是饱和或不饱和的。在天然来源的酸中的某些化合物可以包括含有一个酮基的十八碳三烯4-酮酸。可用的C8-C22脂肪酸是式R-COOH的那些，其中R是烷基或烯基。
甘油的脂肪酸单酯是可用的。可以使用单酯和二酯的混合物。单酯和二酯的混合物可以包含至少约40％的单酯。可以使用包含约40wt％-约60wt％单酯的甘油的单酯和二酯混合物。例如，可以使用含45wt％-55wt％单酯和55％-45％二酯的混合物的市售甘油单油酸酯。
可用的脂肪酸是油酸、硬脂酸、异硬脂酸、棕榈酸、肉豆蔻酸、棕榈油酸、亚油酸、月桂酸、亚麻酸和桐酸，以及源自天然产物牛油、棕榈油、橄榄油、花生油的酸。
在US 4,280,916中详细论述了脂肪酸酰胺。适合的酰胺是C8-C24脂肪单羧酸酰胺，并且是众所周知的。使脂肪酸基化合物与氨反应产生脂肪酰胺。脂肪酸和由其衍生的酰胺可以是饱和的或不饱和的。重要的脂肪酸包括月桂酸C12、棕榈酸C16和硬脂酸C18。其它重要的不饱和脂肪酸包括油酸、亚油酸和亚麻酸，其全部都是C18。在一种实施方案中，本发明的脂肪酰胺是源于C18不饱和脂肪酸的那些。
脂肪胺和二乙氧基化的长链胺(如N，N-二(2-羟基乙基)-牛油胺)本身一般可用作本发明的组分。这两种胺是可购得的。脂肪胺和乙氧基化的脂肪胺在US 4,741,848中有详细描述。
其它
抗氧化剂(即氧化抑制剂)，包括受阻酚类抗氧化剂，如2，6-二叔丁基苯酚和受阻酚酯，如下式所示类型：
在特定的实施方案中，
其中R3是直链或带支链的含2-10个碳原子的烷基，在一种实施方案中含2-4个碳原子，在另一实施方案中含4个碳原子。在一种实施方案中，R3是正丁基。在另一实施方案中，R3可以有8个碳原子，如Ciba的IrganoxL-135TM中那样。这些抗氧化剂的制备可以在专利6,559,105中找到。
其它抗氧化剂可以包括芳族仲胺抗氧化剂，如二烷基(如二壬基)二苯胺，硫化的酚类抗氧化剂，油溶性的铜化合物，含磷抗氧化剂，钼化合物(如二硫代氨基甲酸钼)，有机硫化物、二硫化物和多硫化物(如硫化的丁二烯与丙烯酸丁酯的Diels Alder加合物)。抗氧化剂的详尽列表在US 6,251,840中找到。
本发明中一起使用的EP/抗磨剂通常是二烷基二硫代磷酸锌的形式。尽管存在极其大量的可以与这种功能流体一起使用的不同类型的抗磨剂，但是本发明人已经发现二烷基二硫代磷酸锌类抗磨剂与其它组分一起特别好地发挥作用，从而获得所需特性。在一种实施方案中，所述二烷基二硫代磷酸盐中至少50％烷基(源于醇)是仲烷基，即源于仲醇。在另一实施方案中，至少50％烷基源于异丙醇。
无灰清净剂和分散剂根据其构成能在燃烧后产生非挥发性物质，如氧化硼或五氧化二磷。然而，无灰清净剂和分散剂通常不含金属，因此燃烧时不会产生含金属的灰分。许多类型的无灰分散剂是本领域已知的。即使所述物质可能与来自其它来源的金属离子原位结合，但它们通称作“无灰”。
(1)“羧酸分散剂”是含至少34个、优选至少54个碳原子的羧酸酰化剂(酸、酸酐、酯等)的反应产物，该酰化剂与含氮化合物(如胺)、有机羟基化合物(如脂族化合物，包括一元醇和多元醇，或芳族化合物，包括酚和萘酚)和/或碱性无机物质反应。这些反应产物包括羧酸酯分散剂的酰亚胺、酰胺和酯反应产物。
羧酸酰化剂包括脂肪酸、异脂族酸(如8-甲基-十八烷酸)，二聚酸、加成的二羧酸(不饱和脂肪酸与不饱和羧基试剂的4+2和2+2加成产物)、三聚酸、加成三羧酸(Empol1040，Hystrene5460和Unidyme60)和烃基取代的羧酸酰化剂(来自烯烃和/或聚烯烃)。在一种实施方案中，羧酸酰化剂是脂肪酸。脂肪酸一般包含8-30或12-24个碳原子。羧酸酰化剂在US 2,444,328、3,219,666、4,234,435和6,077,909中有教导。
所述胺可以是一元胺或多元胺。一元胺通常具有至少一个含1-24个碳原子、或1-12个碳原子的烃基。一元胺的实例包括脂肪(C8-30)胺(ArmeensTM)，伯醚胺(primary ether amines)(SURFAM胺)，叔脂族伯胺(PrimenesTM)，羟胺(伯、仲或叔烷醇胺)，醚N-(羟基烃基)胺和羟基烃基胺(EthomeensTM和PropomeensTM)。多元胺包括烷氧基化的二胺(EthoduomeensTM)，脂肪二胺(DuomeensTM)，亚烷基多元胺(亚乙基多元胺)，含羟基的多元胺，聚氧亚烷基多元胺(JeffaminesTM)，缩合多元胺(至少一种羟基化合物与含至少一个伯或仲氨基的至少一种多元胺反应物之间的缩合产物)，以及杂环多元胺。可用的胺包括在US4,234,435(Meinhart)和US 5,230,714(Steckel)中公开的那些。
作为分散剂来源的多元胺主要包括一般符合下式的亚烷基胺
其中t是通常小于10的整数，A是氢或通常具有至多30个碳原子的烃基，以及该亚烷基通常是具有少于8个碳原子的亚烷基。该亚烷基胺主要包括亚甲基胺、亚乙基胺、亚己基胺、亚庚基胺、亚辛基胺、其它多亚甲基胺。它们的具体例子是：乙二胺、二亚乙基三胺、三亚乙基四胺、亚丙基二胺、1，10-癸二胺、1，8-辛二胺、二(七亚甲基)三胺、三亚丙基四胺、四亚乙基五胺、三亚甲基二胺、五亚乙基六胺、二(三亚甲基)三胺。更高级的同系物，如通过缩合两种或更多种以上列举的亚烷基胺得到的那些同样是可用的。特别适用的是四亚乙基五胺。
所述亚乙基多胺，也称作多亚乙基多胺，是特别有用的。它们在化学技术百科全书(Encyclopedia of Chemical Technology)中标题“EthyleneAmines”(Kirk和Othmer，第5卷，第898-905页，Interscience Publishers，New York(1950))下有相当详细的描述。
羟烷基取代的亚烷基胺，即在氮原子上具有一个或多个羟烷基取代基的亚烷基胺同样是可用的。所述胺的实例包括N-(2-羟乙基)乙二胺，N，N’-二(2-羟乙基)乙二胺，1-(2-羟乙基)哌嗪，单羟丙基-哌嗪，二羟丙基取代的四亚乙基五胺，N-(3-羟丙基)-四亚甲基二胺和2-十七烷基-1-(2-羟乙基)-咪唑啉。
更高级的同系物，如由以上列举的亚烷基胺或羟烷基取代的亚烷基多胺通过氨基或羟基缩合得到的那些，同样是可用的。缩合的多元胺通过至少一种羟基化合物与含至少一个伯或仲氨基的至少一种多元胺反应物之间的缩合反应形成，在US 5,230,714和5,296,154(Steckel)中对它们有描述。
这些“羧酸分散剂”的实例在英国专利1,306,529和包括下列专利的许多美国专利中得到描述：3,219,666，3,316,177，3,340,281，3,351,552，3,381,022，3,433,744，3,444,170，3,467,668，3,501,405，3,542,680，3,576,743，3,632,511，4,234,435，6,077,909和6,165,235。
(2)琥珀酰亚胺分散剂是一种羧酸分散剂。它们是烃基取代的琥珀酸酰化剂与有机羟基化合物或含至少一个连接到氮原子上的氢的胺、或所述羟基化合物和胺的混合物的反应产物。术语“琥珀酸酰化剂”指的是烃取代的琥珀酸或产生琥珀酸的化合物(该术语也包括该酸本身)。所述物质通常包括烃基取代的琥珀酸、酸酐、酯(包括半酯)和酰卤。
琥珀酸基分散剂具有众多化学结构，通常包括结构如
在以上结构中，各个R1独立地是烃基，如
为500或700至10,000的聚烯烃衍生的基团。通常该烃基是烷基，往往是分子量为500或700至5000、或1500或2000至5000的聚异丁基。或者表示为R1基团可以包含40-500个碳原子，例如至少50个，如50-300个碳原子，如脂族碳原子。R2是亚烷基，通常是亚乙基(C2H4)。所述分子通常源于烯基酰化剂与多元胺的反应，并且除了所示的简单的酰亚胺结构以外，两个部分之间可以存在众多的连接，包括各种酰胺和季铵盐。琥珀酰亚胺分散剂在US4,234,435、3,172,892和6,165,235中有更全面的描述。
作为取代基来源的聚烯烃通常是2-16个碳原子、一般2-6个碳原子的可聚合烯烃单体的均聚物和共聚物。与琥珀酸酰化剂反应以形成羧酸分散剂组合物的胺可以是如上所述的一元胺或多元胺。
琥珀酰亚胺分散剂如此称呼，因为它通常主要以酰亚胺官能团形式包含氮，尽管它可以以胺盐、酰胺、咪唑啉及其混合物的形式。为制备琥珀酰亚胺分散剂，任选地在升高的温度(通常是80℃直至该混合物或产物的分解点；通常是100℃-300℃)下通常是液体、基本上惰性的有机液体溶剂/稀释剂的存在下，通常除去水，加热一种或多种产生琥珀酸的化合物以及一种或多种胺。
制备本发明琥珀酰亚胺分散剂的过程的其它细节和实例例如包括在US 3,172,892，3,219,666，3,272,746，4,234,435，6,440,905和6,165,235中。
(3)“胺分散剂”是相对高分子量的脂族卤化物与胺、优选多亚烷基多胺的反应产物。其实例描述在例如下列美国专利中：3,275,554，3,438,757，3,454,555和3,565,804。
(4)“曼尼希分散剂”是其中烷基含至少30个碳原子的烷基酚与醛(尤其是甲醛)和胺(尤其是多亚烷基多胺)的反应产物。下列美国专利中所述的物质作为实例：3,036,003，3,236,770，3,414,347，3,448,047，3,461,172，3,539,633，3,586,629，3,591,598，3,634,515，3,725,480，3,726,882和3,980,569。
(5)经后处理的分散剂是通过使羧酸、胺或曼尼希分散剂与如二巯基噻二唑、脲、硫脲、二硫化碳、醛、酮、羧酸、烃取代的琥珀酸酐、腈环氧化物、硼化合物、磷化合物等的反应物反应得到。这类示例性的物质在下列美国专利中得到描述：3,200,107，3,282,955，3,367,943，3,513,093，3,639,242，3,649,659，3,442,808，3,455,832，3,579,450，3,600,372，3,702,757和3,708,422。
(6)聚合物分散剂是以下单体的共聚物：油溶性单体，如甲基丙烯酸癸酯、乙烯基癸基醚和高分子量烯烃与含有极性取代基的单体，如丙烯酸氨基烷基酯或丙烯酰胺和聚(氧乙烯)取代的丙烯酸酯。聚合物分散剂的实例在下列美国专利中得到公开：3,329,658，3,449,250，3,519,656，3,666,730，3,687,849和3,702,300。
所述组合物还可以包含一种或多种清净剂，其通常是盐，尤其是高碱性的盐。高碱性的盐，或高碱性的物质是单相、均匀的牛顿体系，其特征在于金属含量超过按照该金属和具体的与该金属反应的酸性有机化合物的化学计量存在的金属量。该高碱性的物质通过使酸性物质(通常是无机酸或低级羧酸，优选二氧化碳)与包含下列组分的混合物反应制得：酸性有机化合物、含有至少一种所述酸性有机物质的惰性有机溶剂(如矿物油、石脑油、甲苯、二甲苯)的反应介质、化学计量过量的金属碱以及促进剂。
可用于制造本发明高碱性组合物的酸性有机化合物包括羧酸、磺酸、含磷的酸、酚类或其混合物。优选地，酸性有机化合物是羧酸或具有磺酸基或硫代磺酸基的磺酸(如烃基取代的苯磺酸)和烃基取代的水杨酸。可用于制造本发明高碱性组合物的另一类化合物是salixarates。对可用于本发明的salixarates的描述可以在出版物WO 04/04850中找到。
可用于制造高碱性盐的金属化合物一般是任意的第1族或第2族金属化合物(CAS版元素周期表)。该金属化合物的第1族金属包括第Ia族碱金属(如钠、钾、锂)以及第Ib族金属，如铜。第1族金属优选钠、钾、锂和铜，优选钠或钾，更优选钠。金属碱的第2族金属包括第2a族碱土金属(如镁、钙、锶、钡)以及第2b族金属如锌或镉。优选第2族金属是镁、钙、钡或锌，优选镁或钙，更优选钙。
本发明的高碱性清净剂的实例包括、但是不限于磺酸钙、苯酚钙、水杨酸钙、salixarate钙及其混合物。
如果存在，高碱性物质、即清净剂的含量在一种实施方案中是组合物重量的0.05-3％，或0.1-3％，或0.1-1.5％，或0.15-1.5wt％。
用于减少或防止稳定泡沫形成的消泡剂包括硅氧烷或有机聚合物。这些和其它消泡组合物的实例在“泡沫控制剂(Foam Control Agents)”中得到描述，Henry T.Kerner(Noyes Data Corporation，1976)，第125-162页。
本发明的组合物实际上是通过将润滑剂提供至内燃机(如固定式燃气动力内燃机)，以使得在发动机运行过程中润滑剂传送至发动机的关键部件，由此润滑发动机的形式用作润滑剂。
如本文中所用的，术语“烃基取代基”或“烃基基团”按其普通意义使用，这是本领域技术人员公知的。具体地，它指的是具有直接与分子的其余部分相连的碳原子以及主要具有烃特征的基团。烃基基团的实例包括：烃取代基，即脂族(如烷基或烯基)、环脂族(如环烷基、环烯基)取代基，以及芳族-、脂族-、和环脂族取代的芳族取代基，以及其中环通过分子的另一部分构成的环状取代基(如两个取代基一起成环)；取代的烃取代基，即含有非烃基团的取代基，在本发明的范围中该非烃基团(如卤素(尤其是氯和氟)、羟基、烷氧基、巯基、烷基巯基、硝基、亚硝基和硫醚基)不会改变取代基的主要烃特征；杂取代基，即在具有主要是烃特征的同时，在本发明的范围中在由碳原子构成的环或链中包含除碳以外原子的取代基。杂原子包括硫、氧、氮，并且包括如吡啶基、呋喃基、噻吩基和咪唑基的取代基。一般而言，在烃基中对于每10个碳原子存在不多于2个、优选不多于1个非烃取代基；通常，在烃基基团中没有非烃取代基。
已知上述物质中的一些在最终的制剂中可以相互作用，以致最终制剂的组分可能与最初加入的那些不同。例如，金属离子(例如清净剂的金属离子)可以迁移至其它分子的其它酸性或阴离子位上。由此形成的产物，包括在按预期应用使用本发明的组合物中形成的产物，可能无法进行简单的描述。尽管如此，所有这些改性和反应产物都包括在本发明的范围内；本发明包括通过混合上述组分制成的组合物。
实施例
本发明将通过下列实施例进一步进行说明，该实施例给出特别有利的实施方案。虽然提供这些实施例来说明本发明，但是它们并非意在限制本发明。
润滑剂在按ILSAC GF-4燃料经济性和耐久性规范定义的SequenceVIB燃料经济性测试中进行评价。
在润滑粘度的油中制备下列制剂，其中添加剂组分的量按重量百分比，包括常规的稀释油。
表I
| 实施例 | 比较例1 | 比较例2 | 实施例3 |
| 琥珀酰亚胺分散剂 | 5.1 | 5 | 5 |
| 二烷基二硫代磷酸锌 | 0.84 | 0.86 | 0.86 |
| 抗氧化剂 | 2.44 | 2.2 | 2.2 |
| 倾点下降剂 | 0 | 0 | 0.3 |
| 高碱性的磺酸钙清净剂 | 1.53 | 1.53 | 1.53 |
| 粘度指数改进剂 | 8.15 | 8.15 | 8 |
| 硼酸烷基酯 | 0 | 0.05 | 0.05 |
| 摩擦改进剂 | 0 | 0.1 | 0.1 |
| 甘油单油酸酯 | n.p | 0.4 | n.p |
| 油烯基胺酒石酰亚胺 | n.p | n.p | 0.5 |
| Sequence VIB发动机 |
| 初始燃料经济性(合格≥1.5) | 1.5 | 1.8 | 1.9 |
| 耐久性(合格≥1.5) | 1.2 | 1.4 | 1.9 |
*n.p.＝在制剂中不存在
该结果表明，在低硫、低灰分和低磷的曲轴箱润滑剂中使用油烯基胺酒石酰亚胺的制剂，与使用常规摩擦改进剂甘油单油酸酯的制剂相比，显著改善了燃料经济性，如在Sequence VIB发动机测试中证明的那样。
在4球低磷/硫(4Ball Low PS)测试、高频往复设备1％氢过氧化枯烯(HFRR 1％CHP)测试和Cameron-Plint高温往复磨损测试中，就磨损和摩擦减少进一步评价润滑剂。
该4Ball Low PS过程采用ASTM D4172中的相同测试条件，加入氢过氧化枯烯(CHP)作为润滑剂预应力(prestress)。4球磨损测试的基础操作可以描述为以三角形图案锁定3个固定的0.5直径钢珠轴承。将第4个钢珠轴承抵着该3个固定的钢珠装载并旋转。用显微镜测量这3个固定钢珠各自上的磨损痕迹，并取平均值从而确定以毫米计的平均磨损痕迹直径。
HFRR 1％CHP测试用于评价磷和硫含量减少的润滑剂的摩擦和磨损性能。测量通过使用在平钢板上滑动的往复钢珠轴承而造成的磨损痕迹直径和百分比膜厚。该测试使用1％氢过氧化枯烯(CHP)与高频往复磨损设备一起进行，该设备是可购得的磨擦学试验设备。
Cameron-Plint高温往复磨损测试用于评价润滑剂的摩擦和磨损性能。磨损痕迹直径和百分比膜厚通过使用在平钢板上滑动的往复钢珠轴承而得到。该测试利用Cameron-Plint往复磨损设备进行，它是可购得的磨擦学试验设备。
在润滑粘度的油中制备下列制剂，其中添加剂组分的量按重量百分比计，除非另作说明：0.15％倾点下降剂(包括约35％稀释油)，8％粘度指数改进剂(包括约91％稀释油)，0.89％稀释油，5.1％琥珀酰亚胺分散剂(包括约47％稀释油)，0.48％二烷基二硫代磷酸锌(除比较例3包含0.98％以外)(各个中包括约9％稀释油)，1.53％高碱性的磺酸钙清净剂(包括约42％稀释油)，0.1％甘油单油酸酯(包括约0％稀释油)，抗氧化剂(包括约5％稀释油)，90-100ppm商购消泡剂，以及余量的基础油。
向上述制剂中加入如下表中所示组分，并在4Ball Low PS测试、高频往复设备1％氢过氧化枯烯测试和Cameron-Plint高温往复磨损测试中运行。结果示于下表中。
表II
| 比较例30.1％P | 比较例40.05％P | 实施例50.05％P | 实施例60.05％P | 实施例70.05％P | 实施例80.05％P | 实施例90.05％P | 实施例100.05％P | |
| 其它组分 | ||||||||
| [1，3]二氧戊环C12-C14烷基酒石酸酯 | 0.5 | |||||||
| 油烯基酒石酰亚胺 | 0.5 | |||||||
| 油烯基酒石酰亚胺 | 1 | |||||||
| 带支链的C13烷基酒石酸酯 | 1 | |||||||
| 十三烷基丙氧基胺酒石酰亚胺 | 1 | |||||||
| 硼酸化的十三烷基丙氧基胺酒石酰 | 1 |
| 亚胺 | ||||||||
| 测试 | ||||||||
| 1.4Ball LowPS测试 | ||||||||
| 平均磨痕直径(mm) | 0.59 | 0.61，0.77 | 0.51 | 0.7 | n.r. | n.r. | 0.45 | 0.41 |
| 2.HFRR 1％CHP测试 | ||||||||
| 磨损痕迹直径(μm) | 161，185 | 285，295，435 | 236 | 251 | 260 | 286 | 297 | 183 |
| 膜厚(％) | 94，83 | 1，1，23 | 86 | 66 | 58 | 56 | 97 | 50 |
| 3.Cameron-Plint高温往复磨损测试 | ||||||||
| 磨损痕迹直径(μm) | 339 | 661 | n.r. | n.r. | 375 | 352 | n.r. | n.r. |
| 膜厚(％) | 100 | 62 | n.r. | n.r. | 100 | 99 | n.r. | n.r. |
注：n.r.＝未报道
结果表明，在低硫、低灰分和低磷润滑剂中使用本发明的酒石酸衍生化合物的制剂(实施例5-10)，与不含酒石酸衍生化合物、具有0.05wt％传递到组合物的磷的低SAPS制剂(比较例4)相比，减少了磨损。与磷含量较高的常规GF-3制剂(比较例3)相比，它们进一步提供了相当的磨损保护。
以上提及的各篇文献通过引用并入本文。除了实施例中或者地另作明确说明以外，本说明书中表示的物质的量、反应条件、分子量、碳原子数等等的所有数值量要理解为由措辞“约”修饰。除非另作说明，本文中提及的各化学品或组合物应当解释为商品级材料，其可能包含异构体、副产物、衍生物以及通常理解为存在于商品级材料中的其它物质。然而，除非另作说明，各化学组分的量不包括商品物质中通常可能存在的任何溶剂或稀释油。应当理解的是，本文中提出的上限与下限、范围和比例限制可以独立地组合。类似地，本发明各要素的范围和量可以与任何其它要素的范围或量一起使用。如本文中所用的，“基本上由……组成”允许包含不会实质影响所研究的组合物的基本和新特性的物质。
Claims (17)
1.一种适合用在内燃机中的低硫、低磷、低灰分的润滑剂组合物，其包含：
(a)润滑粘度的油，和
(b)式I所示物质与具有约8-约30个碳原子的醇或胺及其组合的缩合产物；
其中各个R独立地是H或烃基，或者其中R基团一起成环；并且其中如果R是H，所述缩合产物非必要地通过酰化或与硼化合物反应而进一步官能化；
其中所述润滑剂组合物具有至多约1.0的硫酸化灰分值，至多约0.08wt％的磷含量和至多约0.4wt％的硫含量。
2.权利要求1的组合物，其中所述缩合产物的量是约0.05-约5.0wt％。
3.权利要求2的组合物，其中所述缩合产物的量是约0.1-约2.0wt％。
4.权利要求2的组合物，其中所述缩合产物的量是约0.25-约1.25wt％。
5.权利要求1的组合物，其进一步包含二烷基二硫代磷酸金属盐。
6.权利要求1的组合物，其中所述二烷基二硫代磷酸金属盐是二烷基二硫代磷酸锌，其中至少约50％烷基是仲烷基。
7.权利要求1的组合物，其进一步包含分散剂。
8.权利要求7的组合物，其中所述分散剂是琥珀酰亚胺。
9.权利要求1的组合物，其进一步包含至少一种含钙高碱性清净剂。
10.权利要求9的组合物，其中所述含钙高碱性清净剂选自磺酸钙、苯酚钙、水杨酸钙、salixarate钙及其混合物。
11.权利要求1的组合物，其进一步包含至少一种抗氧化剂。
12.权利要求11的组合物，其中所述抗氧化剂选自受阻酚、芳胺及其混合物。
13.权利要求1的组合物，其进一步包含不是(b)的其它摩擦改进剂。
14.所述其它摩擦改进剂选自甘油单油酸酯、油烯基酰胺、二乙醇脂肪胺及其混合物。
15.权利要求1的组合物，其进一步包含消泡剂。
16.一种润滑内燃机的方法，其包括向所述发动机提供润滑粘度的油以及式I所示物质与具有约8-约30个碳原子的醇或胺及其组合的缩合产物；
其中所述产物中各个R独立地是H或烃基，或者其中R基团一起成环；并且其中如果R是H，则所得羟基通过酰化或与硼化合物反应而进一步官能化；
其中所述润滑剂组合物具有至多约1.0的硫酸化灰分值，至多约0.08wt％的磷含量和至多约0.4wt％的硫含量。
17.制造润滑剂组合物的方法，其包括：
(a)将润滑粘度的油以及式I所示物质与具有约8-约30个碳原子的醇或胺及其组合的缩合产物混合；
其中在所述产物中各个R独立地是H或烃基，或者其中R基团一起成环；并且其中如果R是H，则所得羟基通过酰化或与硼化合物反应而进一步官能化；
从而得到润滑剂组合物，其中所述润滑剂组合物具有至多约1.0的硫酸化灰分值，至多约0.08wt％的磷含量和至多约0.4wt％的硫含量。
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| JP4234979B2 (ja) * | 2002-11-06 | 2009-03-04 | 新日本石油株式会社 | 省燃費型内燃機関用潤滑油組成物 |
| US7696136B2 (en) * | 2004-03-11 | 2010-04-13 | Crompton Corporation | Lubricant compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters |
| US7807611B2 (en) * | 2004-10-12 | 2010-10-05 | The Lubrizol Corporation | Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof |
| US7651987B2 (en) * | 2004-10-12 | 2010-01-26 | The Lubrizol Corporation | Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof |
| CA2670475A1 (en) * | 2006-11-28 | 2008-06-05 | The Lubrizol Corporation | Tartaric acid derivatives as fuel economy improvers and antiwear agents in crankcase oils and preparation thereof |
-
2004
- 2004-10-12 US US10/963,082 patent/US7651987B2/en active Active
-
2005
- 2005-10-11 EP EP05812393.6A patent/EP1802730B1/en active Active
- 2005-10-11 WO PCT/US2005/036569 patent/WO2006044411A1/en active Application Filing
- 2005-10-11 JP JP2007535908A patent/JP5178197B2/ja not_active Expired - Fee Related
- 2005-10-11 CN CN2012100218464A patent/CN102604697A/zh active Pending
- 2005-10-11 CN CN2005800348432A patent/CN101040035B/zh not_active Expired - Fee Related
- 2005-10-11 CA CA002582618A patent/CA2582618A1/en not_active Abandoned
-
2009
- 2009-12-03 US US12/630,213 patent/US20100081592A1/en not_active Abandoned
-
2011
- 2011-02-03 US US13/020,166 patent/US8133290B2/en not_active Expired - Fee Related
-
2012
- 2012-02-03 JP JP2012021589A patent/JP2012087317A/ja not_active Withdrawn
- 2012-02-03 JP JP2012021590A patent/JP2012087318A/ja not_active Withdrawn
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102272275B (zh) * | 2008-11-05 | 2015-02-04 | 卢布里佐尔公司 | 润滑内燃机的方法 |
| CN102482605A (zh) * | 2009-05-13 | 2012-05-30 | 卢布里佐尔公司 | 内燃机润滑剂 |
| CN105695040A (zh) * | 2009-05-13 | 2016-06-22 | 路博润公司 | 内燃机润滑剂 |
| CN102459542B (zh) * | 2009-06-04 | 2013-12-11 | 卢布里佐尔公司 | 含摩擦改进剂和粘度改进剂的润滑组合物 |
| CN102459542A (zh) * | 2009-06-04 | 2012-05-16 | 卢布里佐尔公司 | 含摩擦改进剂和粘度改进剂的润滑组合物 |
| CN102725385B (zh) * | 2009-11-30 | 2015-05-27 | 路博润公司 | 含有摩擦改进剂的稳定混合物 |
| CN102725385A (zh) * | 2009-11-30 | 2012-10-10 | 卢布里佐尔公司 | 含有摩擦改进剂的稳定混合物 |
| CN102753660A (zh) * | 2009-12-14 | 2012-10-24 | 卢布里佐尔公司 | 含抗磨剂的润滑组合物 |
| CN102918139A (zh) * | 2010-05-12 | 2013-02-06 | 卢布里佐尔公司 | Hths流体中的酒石酸衍生物 |
| CN102918139B (zh) * | 2010-05-12 | 2014-07-23 | 卢布里佐尔公司 | Hths流体中的酒石酸衍生物 |
| CN103443255A (zh) * | 2011-02-16 | 2013-12-11 | 路博润公司 | 润滑传动系装置的方法 |
| CN103649279A (zh) * | 2011-05-26 | 2014-03-19 | 卢布里佐尔公司 | 含有摩擦改进剂的稳定混合物 |
| CN103649279B (zh) * | 2011-05-26 | 2016-05-04 | 路博润公司 | 含有摩擦改进剂的稳定混合物 |
| CN109906265A (zh) * | 2016-07-22 | 2019-06-18 | 路博润公司 | 用于润滑组合物的脂族四面体硼酸盐化合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012087318A (ja) | 2012-05-10 |
| CN101040035B (zh) | 2012-03-28 |
| EP1802730B1 (en) | 2019-08-07 |
| JP2012087317A (ja) | 2012-05-10 |
| US20110131868A1 (en) | 2011-06-09 |
| US20100081592A1 (en) | 2010-04-01 |
| US7651987B2 (en) | 2010-01-26 |
| JP2008516055A (ja) | 2008-05-15 |
| EP1802730A1 (en) | 2007-07-04 |
| WO2006044411A1 (en) | 2006-04-27 |
| CA2582618A1 (en) | 2006-04-27 |
| JP5178197B2 (ja) | 2013-04-10 |
| US20060079413A1 (en) | 2006-04-13 |
| CN102604697A (zh) | 2012-07-25 |
| US8133290B2 (en) | 2012-03-13 |
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