CN108203615B - 一种低灰型润滑油组合物 - Google Patents
一种低灰型润滑油组合物 Download PDFInfo
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- CN108203615B CN108203615B CN201611186880.1A CN201611186880A CN108203615B CN 108203615 B CN108203615 B CN 108203615B CN 201611186880 A CN201611186880 A CN 201611186880A CN 108203615 B CN108203615 B CN 108203615B
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- lubricating oil
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 238000005260 corrosion Methods 0.000 claims abstract description 46
- 230000007797 corrosion Effects 0.000 claims abstract description 44
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 239000003599 detergent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- -1 alkyl salicylate Chemical compound 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000002199 base oil Substances 0.000 claims abstract description 9
- 230000000994 depressogenic effect Effects 0.000 claims abstract description 8
- 229960001860 salicylate Drugs 0.000 claims abstract description 7
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229960002317 succinimide Drugs 0.000 claims description 10
- 229920002367 Polyisobutene Polymers 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 239000002530 phenolic antioxidant Substances 0.000 claims description 4
- 229920013639 polyalphaolefin Polymers 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 34
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000005461 lubrication Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 22
- 239000002585 base Substances 0.000 description 19
- 239000000654 additive Substances 0.000 description 14
- 239000010705 motor oil Substances 0.000 description 13
- 239000011575 calcium Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 244000304337 Cuminum cyminum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000982 Malva neglecta Species 0.000 description 1
- 235000000060 Malva neglecta Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- OTGHWLKHGCENJV-UHFFFAOYSA-N glycidic acid Chemical compound OC(=O)C1CO1 OTGHWLKHGCENJV-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C10M169/04—Mixtures of base-materials and additives
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Abstract
本发明涉及一种低灰型润滑油组合物。该润滑油组合物包含由150～160mgKOH/g的中碱值烷基水杨酸盐和≥240mgKOH/g的高碱值硫化烷基酚盐组成的清净剂体系；B腐蚀抑制剂；C无灰分散剂；D抗氧抗腐剂ZDDP；E辅助抗氧剂；F降凝剂；G粘度指数改进剂；H基础油。该润滑油组合物的硫酸盐灰分含量不大于0.5％(重量比)，碱值不小于5mgKOH/g,通过腐蚀试验(CBT)等要求，并具有优良的抗氧化、抗硝化、抗磨损及抗腐蚀等性能，可为国内外重负荷、大功率的四冲程移动式燃气发动机提供良好润滑。且该润滑油组合物配方简单，成本低，调制方便。
Description
技术领域
本发明涉及一种低灰型润滑油组合物，硫酸盐灰分不大于0.5％(重量比)，碱值不小于5mgKOH/g,具有良好的抗腐蚀性能，通过腐蚀试验(CBT)，并满足重负荷移动式燃气发动机油和GB11122-2006中CF级别要求，属于润滑油及润滑油添加剂技术领域。
背景技术
近年来，随着世界能源危机出现和人们环保意识增强，代用清洁燃料-天然气得到日益关注。随着燃气发动机技术的进步和配套设施的完善，燃气发动机被广泛应用。
燃气发动机的使用工况与普通燃料(汽油或柴油)发动机有很大差别，因此，传统的发动机油很难满足燃气发动机的润滑要求，需要专门的燃气发动机润滑油。目前世界上还没有燃气发动机油的统一标准和台架评定方法，各主要发动机生产商(OEM)根据自身发动机特点和实际使用工况对燃气发动机油提出了特殊要求。比如康明斯CES20074规格中就要求硫酸盐灰分不大于0.5％(重量比)，碱值不小于5mgKOH/g，钙含量不大于1200ppm，磷含量在600～800ppm之间，锌含量在600～850ppm之间，并通过CBT试验。
在传统润滑油配方中，硫酸盐灰分受清净剂和抗氧抗磨抗腐剂二烷基二硫代磷酸锌(ZDDP)影响，磷含量由ZDDP决定，降低润滑油中硫酸盐灰分、和磷含量往往需要降低配方中的清净剂和ZDDP。但油品的抗腐蚀性能是依靠清净剂和ZDDP来提供的。也就是说，燃气发动机油降低清净剂和ZDDP的加量后，通过腐蚀试验将是一大挑战。
美国专利US7,183,241介绍了一种长寿命低磷燃气发动机润滑油配方，其硫酸盐灰分含量在0.2-2.0％(重量比)之间，配方包含高碱值金属性清净剂(磺酸钙或烷基水杨酸钙)、二烷基二硫代氨基甲酸锌和二烷基二硫代磷酸锌混合物、无灰抗磨抗氧化剂。
美国专利US7,795,191介绍了一种硫含量为0.01％-0.3％(重量比)，磷含量为0.01％-0.1％(重量比)和硫酸盐灰分含量在0.1％-1.2％(重量比)之间的润滑油组合物，配方包含0.1％-10％(重量比)分散性粘度指数改进剂，如路博润添加剂公司的LZ7720C，罗曼克斯公司的Viscoplex 6-954，Viscoplex 6-054。抗氧抗腐剂二硫代磷酸锌首选路博润的LZ1097和LZ1395，雪佛龙的OLOA267和OLOA269R，乙基公司的HITEC7197，其次可选的是路博润的LZ677A，LZ1095，LZ1371，LZ1370，LZ1373，雪佛龙的OLOA262，OLOA260和乙基公司的HITEC7169。
美国专利US6,645,923介绍了一种低灰型(硫酸盐灰分为0.1％-0.6％，重量比)和中灰型(硫酸盐灰分0.6％-1.5％，重量比)燃气发动机油，配方包含一种碱值低于95mgKOH/g的水杨酸盐和一种碱值高于250mgKOH/g的碱金属盐的，无灰分散剂和抗磨剂。
日本专利JP2001158896介绍了一种适用于燃气发动机的润滑油配方，其硫酸灰分含量在0.1-1.0％(重量比)之间，磷含量在0.01-0.1％(重量比)之间，配方包含金属清净剂、硼化无灰分散剂、胺型或酚型抗氧剂以及无灰二硫代氨基甲酸化合物。
中国专利CN1594519介绍了一种气体燃料发动机润滑油，硫酸盐灰分要求≤1.0％(重量比)，其配方包含低硫石蜡基础油、抗氧添加剂、极压抗磨剂、抗泡沫添加剂、降凝剂和抗乳化添加剂。
美国专利US2,719,125,US2,719,126和US3,087,932中指出1,3,4-噻二唑的衍生物、能解决润滑油的抗腐蚀问题，使油品通过CBT试验；此类添加剂的加量建议不超过0.2％(质量分数)。
美国专利US11,463,532提到在双聚异丁烯丁二酰亚胺上连接对苯二甲酸有助于润滑油的抗腐蚀性能。
美国专利US11,292,403中，清净剂硫化烷基酚盐被硼化后形成硼化硫化烷基酚盐，具有良好的抗腐蚀性能，在全配方中加入0.22％后，铅腐蚀从179.2ppm，降低到3.2ppm。
美国US11,168,702专利指出环氧丙酸，别名缩水甘油，加入润滑油全配方中，有利于润滑油腐蚀性能，特别是加量增大时，可以有效地降低腐蚀。其中环氧丙酸，别名缩水甘油，以0.15％(质量分数)加入润滑油全配方中，铅腐蚀从原来的282ppm降低到228ppm，铜腐蚀从原来的24ppm降低到16ppm，当加量增大到0.75％(质量分数)时，铅和铜腐蚀分别为42ppm和8ppm。
本申请与上述专利相比，首先本申请在低灰型燃气发动机油基础上，硫酸盐灰分不大于0.5％(重量比)，碱值不小于5mgKOH/g比低灰型燃气发动机油产品(硫酸盐灰分0.1-0.6％(重量比)，碱值3-6mgKOH/g)更加苛刻，同时具有良好的抗腐蚀性能，通过腐蚀试验(CBT)；其次本专利在采用特定清净剂体系和一种腐蚀抑制剂，解决了低灰型燃气发动机油的腐蚀问题。
发明内容
本发明的目的是提供一种以金属清静剂、无灰分散剂和抗氧抗磨剂等为添加剂调制一种性价比良好，低灰型润滑油组合物，硫酸盐灰分不大于0.5％(重量比)，碱值不小于5mgKOH/g,具有良好的抗腐蚀性能，通过腐蚀试验(CBT)，并满足Q/SY RH2240-2013重负荷移动式燃气发动机油和GB11122-2006中CF级别要求。
为达到上述目的，本发明提供一种低灰型润滑油组合物，以该润滑油组合物的质量为100％计，所述润滑油组合物包含的组分及各组分的质量百分数如下：
A由150～160mgKOH/g的中碱值烷基水杨酸盐和≥240mgKOH/g的高碱值硫化烷基酚盐组成的清净剂体系，1.0-2.5％；
B腐蚀抑制剂，0.1-0.4％；
C无灰分散剂，4.0-8.0％；
D抗氧抗腐剂ZDDP，0.4-1.0％；
E辅助抗氧剂，0.1-1.5％；
F降凝剂，0.01-1.0％；
G粘度指数改进剂，0-12％；
H基础油，73.6-94.4％。
本发明所述的低灰型润滑油组合物，所述组分A中的烷基水杨酸盐的分子结构优选为：
其中，R为含14～18个碳原子的烷基，M为Ca、Ba或Zn。
本发明所述的低灰型润滑油组合物，所述组分A中的硫化烷基酚盐的分子结构优选为：
式中R为含14～18个碳原子的烷基，x和n为整数，M为Ca、Mg或Zn。
本发明所述的低灰型润滑油组合物，所述组分B优选为异辛基酸性磷酸酯十八胺盐。
本发明所述的低灰型润滑油组合物，所述组分C优选为硼化双烯基丁二酰亚胺和/或多聚异丁烯丁二酰亚胺；
所述硼化双烯基丁二酰亚胺的硼含量大于等于0.45％，分子量为800～1800，其分子结构为：
或
其中，PIB的分子量为600～1400，n为6～10的整数；
所述多聚异丁烯丁二酰亚胺的氮含量大于等于1.0％，分子量为800～1800，其分子结构为：
其中，PIB的分子量为600～1400，n为6～10的整数。
本发明所述的低灰型润滑油组合物，所述组分D优选为二烷基二硫代磷酸锌，其分子结构为：
式中，R＝CmH2m+1，m＝3-8。
本发明所述的低灰型润滑油组合物，所述组分E优选为酚型抗氧剂和/或胺型抗氧剂；
所述酚型抗氧剂的分子结构为：
式中，R为6～14个碳原子的烷基；
所述胺型抗氧剂的分子结构为：
式中，R为4～14个碳原子的烷基。
本发明所述的低灰型润滑油组合物，所述组分F优选为聚α烯烃。
本发明所述的低灰型润滑油组合物，所述组分G优选为乙丙共聚物或聚甲基丙烯酸酯。
本发明所述的低灰型润滑油组合物，所述组分H优选为矿物油、加氢基础油或合成基础油。
本发明所述的低灰型润滑油组合物，其中还包括抗泡剂。
在本发明的润滑油组合物中：
金属清净剂选用特定的150～160mgKOH/g的中碱值烷基水杨酸盐和≥240mgKOH/g的高碱值硫化烷基酚盐的组合，用以提高润滑油组合物的清净性，特别是高温清净性，同时满足油品对灰分、碱值以及抗腐蚀性能的要求。
选用特定的腐蚀抑制剂，用于改善油品的抗腐蚀性能，同时可以改善油品的抗磨损性能。
无灰分散剂的使用，可提高油品的分散性能，特别是可以提高油品的高温分散性能和抗磨性能，而且可以使油品具有良好的节油性能，并使油品在衰败过程中产生的极性组分能够很好的分散在油品中，而不致于沉积。该组分均可从兰州润滑油研究开发中心开发生产的无灰分散剂，也可从国内外类似的商品中获得，但使用中应保持润滑油组合物中氮含量保持不变。
组合物中将酚、胺型辅助抗氧剂与二烷基二硫代磷酸锌复合使用，其以不同的抗氧化作用机理相互配合共同抑制了润滑油的高温氧化，赋予该组合物优异的高温抗氧化性能和抑制油品沉积物生成的能力。
调制润滑油时，除了加入本发明的添加剂外，单级油还需加入降凝剂和抗泡剂，而多级油需加入降凝剂、粘度指数改进剂和抗泡剂。
粘度指数改进剂较适宜的是乙烯-丙烯共聚物，但使用中要保持较好的剪切稳定性指数。
降凝剂可从国内外商品聚α-烯烃降凝剂或倾点下降剂中得到。
抗泡剂一般是商品甲基硅油T901。
选择性能好的添加剂组分还不能完全解决本发明所要解决的问题。本发明利用添加剂组分之间相互作用的原理，力求使各功能添加剂除了充分发挥其自身的性能优点外，在满足发动机油各项性能要求方面，尽可能使各功能添加剂组分间产生较强的“协合效应”，避免出现“对抗效应”。
判断润滑油组合物是否满足GB11122-2006中CF柴油机油的要求，需进行Caterpillar 1M-PC试验及CRCR L-38轴瓦腐蚀试验。
本发明采用了板式成焦器试验和热管氧化试验模拟Caterpillar 1M-PC发动机活塞清净性,板式成焦器试验是通过油品在高温下连续飞溅在铝板上，通过试验后，铝板上的成焦量来表征油品，以mg计算，数据越小越好；采用微氧化试验(CMOT)来评定油品的氧化诱导期，由此证明其抗氧化性能，该方法是向金属试件中注入微量的油样，将盛放试件的试管放在规定温度的油浴中，通入定量的流动空气并保持一定的时间，待取出试件后，清洗试件并过滤洗液，对试件和过滤膜进行称重，得到试验后沉积物和油泥的重量，再经微机处理，得出沉积物增长曲线并得到油样的氧化诱导期，试验结果以min计算，时间越长越好；采用微焦化试验来评价油品的高温沉积物倾向，用于证明油品的高温抗沉积物性能，该方法以试验油在规定温度下形成凝胶态的试验时间作为试验结果，也以min计算，结果越大越好；采用磨斑直径试验来评价油品的抗磨损性能；采用腐蚀试验(CBT)来证明油品的抗腐蚀性能。
本发明组合物为低灰设计，具有优良的粘温特性和低温性能；具有优异的抗氧化、抗硝化性能；具有良好的清净分散性能和高温分散性。还有优异的抗磨损、抗腐蚀性能。
具体实施方式
下面的实例是为了进一步说明本发明的方法，但不应受此限制。
中碱值烷基水杨酸钙：为路博润-兰炼添加剂有限公司生产的T109；
髙碱值硫化烷基酚钙：为路博润-兰炼添加剂有限公司生产的T115B；
低碱值合成磺酸钙：为锦州石化分公司添加剂厂生产的T104；
酚型辅助抗氧剂：为汽巴公司生产的L135；
胺型辅助抗氧剂：为汽巴公司生产的L57；
聚α烯烃降凝剂：为路博润-兰炼添加剂有限公司生产的LZL803B；
乙丙共聚物粘度指数改进剂：为兰州润滑油厂生产的RHY614；
市售复合剂：为雪佛龙股份有限公司生产的OLOA1255Z；
加氢基础油：为大庆炼化生产的HVIH6。
实施例1
表1给出了不同清净剂配方体系对CBT的影响进一步说明本发明。表1中实施例11和实施例12为中碱值烷基水杨酸钙与髙碱值硫化烷基酚钙体系，对比例11-对比例14为其它清净剂体系，对比例和实施例均在满足硫酸盐灰分和碱值要求基础上。表2为CBT试验结果。
表1
表2
由表1和表2可知，不同的清净剂配方体系，对油品的抗腐蚀性能影响不同，实施例采用的是中碱值烷基水杨酸钙和髙碱值硫化烷基酚钙清净剂体系，该体系与其它清净剂体系相比，其油品的CBT结果好，说明该体系可以提高油品的抗腐蚀性能。
实施例2
表3给出了特定腐蚀抑制剂对CBT的影响进一步说明本发明。表3中实施例21-实施例24给出了添加不同量腐蚀抑制剂后对CBT的影响。表4为CBT试验结果。
表3
表4
由表3和表4可见，加入通常用做极压抗磨剂的异辛基酸性磷酸酯十八胺盐，作为特定的腐蚀抑制剂，可有效改善油品的腐蚀性能，实施例22和23在异辛基酸性磷酸酯十八胺盐加入量为0.2,0.4时，都通过了CBT试验。但加入量再增加，为0.6时，不能通过CBT试验，说明异辛基酸性磷酸酯十八胺盐的加入量不能过大。
实施例3
表5给出了一系列的实验配方来进一步说明本发明。在表5中，对比例31为利用市售复合剂调制的商业用油，该复合剂目前是世界上使用最广泛的燃气复合剂，被用来作为评价别的油品标准。实施例31和实施例32为本发明的全组分10W-40低灰型燃气发动机润滑油，它含有中碱值烷基水杨酸盐、髙碱值硫化烷基酚盐、腐蚀抑制剂、硼化双烯基丁二酰亚胺无灰分散剂、高分子无灰分散剂、二烷基二硫代磷酸锌、酚型辅助抗氧剂和胺型辅助抗氧剂等。组分及含量见表5，由此得到的典型数据列于表6，表7。
表5
表6
由表5和表6可知，对比例31采用雪佛龙市售复合剂OLOA1255Z调合而成，从表6可以看出，对比例31不能满足硫酸盐灰分和碱值的要求，同时不能通过CBT试验。实施例31和实施例32在满足硫酸盐灰分和碱值要求的同时，通过CBT试验，说明其抗腐蚀性能优于对比例31，同时其他性能，如高温清净性，热氧化稳定性，抗磨损等性能基本相当。
表7
由表7数据可知，实施例31所得油品通过了Caterpillar 1M-PC试验和CRCR L-38轴瓦腐蚀试验。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明的保护范围。
Claims (9)
1.一种低灰型润滑油组合物，其特征在于，以该润滑油组合物的质量为100％计，所述润滑油组合物包含的组分及各组分的质量百分数如下：
A由150～160mgKOH/g的中碱值烷基水杨酸盐和≥240mgKOH/g的高碱值硫化烷基酚盐组成的清净剂体系，1.0-2.5％；
B腐蚀抑制剂，0.1-0.4％；
C无灰分散剂，4.0-8.0％；
D抗氧抗腐剂ZDDP，0.4-1.0％；
E辅助抗氧剂，0.1-1.5％；
F降凝剂，0.01-1.0％；
G粘度指数改进剂，0-12％；
H基础油，73.6-94.4％；
其中，以上组分含量之和为100％，所述组分B为异辛基酸性磷酸酯十八胺盐，所述组分C为硼化双烯基丁二酰亚胺和多聚异丁烯丁二酰亚胺。
2.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分A中的烷基水杨酸盐的分子结构为：
其中，R为含14～18个碳原子的烷基，M为Ca、Ba或Zn。
3.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分A中的硫化烷基酚盐的分子结构为：
式中R为含14～18个碳原子的烷基，x和n为整数，M为Ca、Mg或Zn。
4.根据权利要求1所述的低灰型润滑油组合物，其特征在于，
所述硼化双烯基丁二酰亚胺的硼含量大于等于0.45％，分子量为800～1800，其分子结构为：
其中，PIB的分子量为600～1400。
5.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分D为二烷基二硫代磷酸锌，其分子结构为：
式中，R＝CmH2m+1，m＝3-8。
6.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分E为酚型抗氧剂和/或胺型抗氧剂；
所述酚型抗氧剂的分子结构为：
式中，R为6～14个碳原子的烷基；
所述胺型抗氧剂的分子结构为：
式中，R为4～14个碳原子的烷基。
7.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分F为聚α烯烃。
8.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分G为乙丙共聚物或聚甲基丙烯酸酯。
9.根据权利要求1所述的低灰型润滑油组合物，其特征在于，所述组分H为矿物油、加氢基础油或合成基础油。
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