CN102985519A - 润滑油组合物和无级变速器用润滑油组合物 - Google Patents
润滑油组合物和无级变速器用润滑油组合物 Download PDFInfo
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- CN102985519A CN102985519A CN2011800353559A CN201180035355A CN102985519A CN 102985519 A CN102985519 A CN 102985519A CN 2011800353559 A CN2011800353559 A CN 2011800353559A CN 201180035355 A CN201180035355 A CN 201180035355A CN 102985519 A CN102985519 A CN 102985519A
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- Prior art keywords
- lubricating oil
- composition
- oil
- quality
- longifolene
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- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 77
- 230000005540 biological transmission Effects 0.000 title claims description 33
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 claims description 34
- 238000013329 compounding Methods 0.000 claims description 32
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 claims description 28
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 claims description 28
- 239000012530 fluid Substances 0.000 claims description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 25
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 claims description 17
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 claims description 17
- 125000002588 longifolene group Chemical group 0.000 claims description 7
- GHSWVHPTAKWNMP-UHFFFAOYSA-N 4-methylidene-5H-azulene Chemical compound C=C1C2=CC=CC2=CC=CC1 GHSWVHPTAKWNMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 45
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
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- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
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- 239000000341 volatile oil Substances 0.000 description 6
- NVEQFIOZRFFVFW-UHFFFAOYSA-N 9-epi-beta-caryophyllene oxide Natural products C=C1CCC2OC2(C)CCC2C(C)(C)CC21 NVEQFIOZRFFVFW-UHFFFAOYSA-N 0.000 description 5
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 3
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- 235000012424 soybean oil Nutrition 0.000 description 3
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
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- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- MQFGIUKCEOGIGS-UHFFFAOYSA-N CC(C)C1=CCC(=C)C1C Chemical compound CC(C)C1=CCC(=C)C1C MQFGIUKCEOGIGS-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明的润滑油组合物配混下述式(1)所示的长叶烯,即(1S,3aR,4S,8aS)-4,8,8-三甲基-9-亚甲基-十氢-1,4-亚甲基薁而成,
Description
技术领域
本发明涉及润滑油组合物和无级变速器用润滑油组合物。
背景技术
作为碳材料,现在仍然多使用来自石油资源的碳材料。但是,资源枯竭这一问题正成为现实,需求与来自石油资源不同的新的碳材料。作为其中之一,有欲利用来自天然植物的油脂、精油作为润滑油的动向。
例如,通过压榨、提取植物等可得到粗油,通过将该粗油蒸馏等进行精制,由此可得到以大豆油、桐油、棕榈油等为代表的植物油脂。这些植物油脂是饱和或不饱和脂肪酸的甘油三酯,用于烹饪、燃料、医疗、润滑油等各种领域中。另外,也公开了以上述植物油脂作为原料通过酯交换法得到低温流动性、氧化稳定性和润滑性优异的润滑油基油的尝试(参照专利文献1)。
另外,来自植物的精油包含醇、醛、酮、酯、酚和烃等作为成分。作为烃,有萜烯、倍半萜烯。在萜烯中,作为链状萜烯类,已知有别罗勒烯、罗勒烯、月桂烯、二氢月桂烯等,作为环状萜烯类,已知有α―蒎烯、β―蒎烯、苧烯、莰烯、α―水芹烯、萜品烯、萜品油烯、3-蒈烯等。萜烯多用于香料等,是具有C10H16的分子式的烃,虽然具有高的水解稳定性、体积电阻率,但粘度、闪点等低,因此不适用于润滑油用途。另一方面,作为倍半萜烯,已知作为链状倍半萜烯的法呢烯等,作为环状倍半萜烯类,已知有柏木烯、β―石竹烯、杜松烯、朱栾倍半萜、罗汉柏烯、愈创木烯等。它们是具有C15H24的分子式的烃,具有高的水解稳定性和高的体积电阻率,进而具有适度的粘度、闪点,因此可作为低粘度的润滑油基材使用。
另外,近年来,由于对环境问题的意识的提高,各国正在强化耗燃料量的规定。为了应对改善该耗燃料量需求的提高,有采用无级变速器(以下也称为CVT)的趋势。由于CVT可无级地变速,通过需要的输出转距可选择最适合的发动机转速,改善耗燃料量的效果大。另外,CVT没有变速震动,没有调高档时的发动机转速的下滑,因此加速性能提高,操作性能也优异。CVT有金属带方式、链方式、牵引传动方式等,任一种方式都要求高的传递效率。因此,需要开发牵引系数高的润滑油,使传递效率提高。其中由于牵引传动通过油膜来传递动力,因此噪音少,最适用于高级汽车。
另一方面,无级变速器用润滑油是用于通过油膜将驱动侧的动力传递至被驱动侧的润滑油,牵引系数越高,传递效率越高。因此在使用条件中,期待其牵引系数充分地大。
另外特别地,牵引传动方式用的润滑油在CVT内也担当作为通常的润滑油的作用,因此为了防止摩擦磨损,即使在高温下,也需要具有尽可能保持充分的油膜的高粘度。
另一方面,为了在北美?北欧等寒冷地区的低温起动性,要求在低温下具有低粘度(低温流动性)。于是,要求牵引传动方式用的润滑油的粘度随温度的变化小,即粘度指数高。为了应对这样的要求,例如,如专利文献2所记载,正在开发粘度指数为0以上,含有双环[2.2.1]庚烷衍生物的牵引传动用流体。
现有技术文献
专利文献
专利文献1日本特开平10-53780号公报
专利文献2日本特开2008-260951号公报。
发明内容
发明要解决的问题
上述的植物油脂为酯,因此易于受到水解,且为极性物质,因此体积电阻率低,不能用于需要绝缘性的领域。进而植物油脂多具有不饱和脂肪酸,氧化稳定性也低。进而尽管植物油脂的粘度指数高,但由于具有-5℃~室温左右这样高的倾点,因此不能在低温环境中使用。即使使用如专利文献1那样的酯交换法也不能改变这一问题。另外,作为来自植物的精油的倍半萜烯即使为烃,也具有不饱和键,因此有氧化稳定性低的问题。
进而,并不能说专利文献2中记载的牵引传动用流体具有充分的低温起动性。另外,作为牵引传动方式用的润滑油,牵引系数也未必令人满意。
本发明的第1目的是提供低倾点、粘度指数高、具有高氧化稳定性、高耐水解性和高体积电阻率的润滑油组合物,本发明的第2目的是提供在高温下的牵引系数高,低温流动性优异,在高温下可保持油膜的无级变速器用润滑油组合物。
解决问题的手段
本发明人等发现由柏木、松树等获得的精油中所含的长叶烯(环状倍半萜烯烃的一种),具有高水解稳定性和高体积电阻率,进而具有适度的粘度、闪点,因此可作为低粘度的润滑油基材使用。进而,长叶烯的烯烃部分为具有体积大的取代基的末端烯烃结构,因此氧化稳定性也高。本发明是基于这些知识而完成的。
即,本发明提供如下的润滑油组合物和无级变速器用润滑油组合物。
(1)润滑油组合物,其特征在于,配混长叶烯而成。
(2)润滑油组合物,其是上述润滑油组合物,其特征在于,以组合物总量为基准,前述长叶烯的配混量为60质量%以上。
(3)润滑油组合物,其是上述润滑油组合物,其特征在于,该组合物中的β-石竹烯的含量为5质量%以下。
(4)无级变速器用润滑油组合物,其特征在于,配混长叶烯而成。
(5)无级变速器用润滑油组合物,其是上述无级变速器用润滑油组合物,其特征在于,配混双环[2.2.1]庚烷二聚体而成。
(6)无级变速器用润滑油组合物,其是上述无级变速器用润滑油组合物,其特征在于,前述长叶烯的纯度为80%以上。
(7)无级变速器用润滑油组合物,其是上述无级变速器用润滑油组合物,其特征在于,该组合物中的β-石竹烯的含量为1质量%以下。
(8)无级变速器用润滑油组合物,其是上述无级变速器用润滑油组合物,其特征在于,适合用作牵引传动用流体。
发明效果
本发明的润滑油组合物是配混长叶烯而成的,因此为低倾点,粘度指数高,具有高氧化稳定性、高耐水解性和高体积电阻率。
另外,本发明的无级变速器用润滑油组合物是配混长叶烯而成的,因此牵引系数高、低温流动性优异、且具有在高温下可保持油膜的高粘度指数。
具体实施方式
本发明的润滑油组合物和无级变速器用润滑油组合物的特征是配混长叶烯而成。即,本发明为含有长叶烯的润滑油。其中,长叶烯指(1S,3aR,4S,8aS)-4,8,8-三甲基-9-亚甲基-十氢-1,4-亚甲基薁,具体来说为具有下述式(1)的结构的化合物。
[化1]
长叶烯在松树、柏木的精油中含有,可通过精制容易地获得高纯度(60~90%纯度)的长叶烯。精制后的长叶烯可直接作为润滑油使用,也可作为润滑油的基油使用。若使用长叶烯作为基油,则可得到低倾点、粘度指数高、具有高氧化稳定性、高耐水解性和高体积电阻率的润滑油组合物。另外,由于长叶烯本身具有适度的粘度,因此润滑性也优异。长叶烯的纯度优选为80%以上,更优选为90%以上,长叶烯的纯度越高,粘度指数越高,氧化稳定性越优异,因此在本发明中长叶烯的纯度越高越优选。
本发明的润滑油组合物和无级变速器用润滑油组合物也可含有上述长叶烯以外的基油。其中,作为本发明的润滑油组合物,为了发挥效果,组合物中长叶烯的配混量优选为60质量%以上,更优选为70质量%以上,进一步优选为80质量%以上,特别优选为90质量%以上。另外,作为本发明的无级变速器用润滑油组合物,为了发挥效果,以全部组合物为基准,长叶烯的配混量优选为5质量%以上,更优选为10质量%以上。
在本发明的润滑油组合物中,作为长叶烯以外的其他基油,例如,可从矿物油、合成油中适宜地选择。
作为矿物油,例如,可列举对石蜡基原油、中间基原油或环烷基原油进行常压蒸馏、或对常压蒸馏残渣油进行减压蒸馏而得到的馏出油,通过利用常规方法对这些馏出油进行精制而得到的精制油,具体来说可列举溶剂精制油、氢化精制油、脱蜡处理油和白土处理油等。
另外,作为合成油,例如,可列举低分子量聚丁烯、低分子量聚丙烯、碳原子数为8到14的α-烯烃的低聚物和它们的氢化物、多元醇酯(例如,三羟甲基丙烷的脂肪酸酯、季戊四醇的脂肪酸酯等)、二元酸酯、芳族聚羧酸酯(例如,偏苯三酸酯、均苯四酸酯等)、磷酸酯等酯化合物、烷基苯、烷基萘等烷基芳香系化合物、硅油、和氟系油(例如,氟碳化合物、全氟聚醚等)等。
这些基油可一种单独使用或将两种以上组合起来使用。
此外,在本发明的无级变速器用润滑油组合物中,作为长叶烯以外的基油,特别地,优选使用合成油,更优选使用双环[2.2.1]二聚体。其中,特别优选配混以下述通式(2)表示的双环[2.2.1]庚烷二聚体而成。
[化2]
上述式中,q、r表示1~5的整数。
以上述通式(2)表示的双环[2.2.1]庚烷二聚体更优选为下述式(3)表示的内-2-甲基-外-3-甲基-外-2-〔(外-3-甲基双环〔2.2.1〕庚-外-2-基)甲基〕双环〔2.2.1〕庚烷,或下述式(4)表示的内-2-甲基-外-3-甲基-外-2-〔(内-3-甲基双环〔2.2.1〕庚-内-2-基)甲基〕双环〔2.2.1〕庚烷。
[化3]
另一方面,在由松树、柏木的精油得到的长叶烯中含有β-石竹烯作为杂质。β-石竹烯的粘度指数低,另外缺乏氧化稳定性,因此含量少是优选的。β-石竹烯指(1R,4E,9S)-4,11,11-三甲基-8-亚甲基-双环[7.2.0]十一碳-4-烯,是具有下述结构的化合物。
[化4]
β-石竹烯若存在于润滑油组合物中,可能会有损氧化稳定性,进而也可能会对粘度指数带来不良影响。因此,在本发明的润滑油组合物中,以组合物总量为基准,β-石竹烯的含量优选为5质量%以下,更优选为3质量%以下。另外,在本发明的无级变速器用润滑油组合物中,以组合物总量为基准,β-石竹烯的含量优选为1质量%以下。
本发明的润滑油组合物和无级变速器用润滑油组合物可配混规定的添加剂。作为添加剂,可列举抗氧化剂、油性剂、极压添加剂、清洁分散剂、粘度指数改进剂、防锈剂、金属钝化剂和消泡剂等。它们可一种单独使用或将两种以上组合起来使用。
作为抗氧化剂,可使用在现有的烃系润滑油中使用的胺系抗氧化剂、酚系抗氧化剂和磷系抗氧化剂、硫系抗氧化剂。这些抗氧化剂可一种单独使用或将两种以上组合起来使用。
作为胺系抗氧化剂,例如,可列举单辛基二苯胺、单壬基二苯胺等单烷基二苯胺系化合物;4,4’-二丁基二苯胺、4,4’-二戊基二苯胺、4,4’-二己基二苯胺、4,4’-二庚基二苯胺、4,4’-二辛基二苯胺、4,4’-二壬基二苯胺等二烷基二苯胺系化合物;四丁基二苯胺、四己基二苯胺、四辛基二苯胺、四壬基二苯胺等多烷基二苯胺系化合物;α-萘胺、苯基-α-萘胺、丁基苯基-α-萘胺、戊基苯基-α-萘胺、己基苯基-α-萘胺、庚基苯基-α-萘胺、辛基苯基-α-萘胺、壬基苯基-α-萘胺等萘胺系化合物。
作为酚系抗氧化剂,例如,可列举2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚等单酚系化合物;4,4’-亚甲基双(2,6-二叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)等二酚系化合物。
作为磷系抗氧化剂,可列举亚磷酸三苯基酯、[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸二乙基酯等。
作为硫系抗氧化剂,例如,可列举2,6-二叔丁基-4-(4,6-双(辛基硫基)-1,3,5-三嗪-2-基氨基)苯酚、五硫化磷与蒎烯的反应物等硫代萜烯系化合物;硫代二丙酸二月桂基酯、硫代二丙酸二硬脂基酯等硫代二丙酸二烷基酯等。
在本发明的润滑油组合物中,以组合物总量为基准,这些抗氧化剂的配混量通常为0.01质量%~10质量%,优选为0.03质量%~5质量%。另外,在本发明的无级变速器用润滑油组合物中,加入保持氧化稳定性所需的最低量即可。若多量加入抗氧化剂,则在高温下的牵引系数降低,因此越少越好,以组合物总量为基准,优选为0.01质量%~1质量%。
作为油性剂,可列举脂肪族醇、脂肪酸或脂肪酸金属盐等脂肪酸化合物、多元醇酯、山梨聚糖酯、甘油酯等酯化合物、脂肪族胺等胺化合物等。从配混效果的观点考虑,以组合物总量为基准,这些油性剂的配混量通常为0.1质量%~30质量%,优选为0.5质量%~10质量%。
作为极压添加剂,可列举硫系极压添加剂、磷系极压添加剂、含有硫和金属的极压添加剂,含有磷和金属的极压添加剂。这些极压添加剂可一种单独使用或将两种以上组合起来使用。作为极压添加剂,只要在分子中至少含有硫原子和磷原子中的任一种,可发挥耐负荷性、耐磨损性即可。作为在分子中含有硫的极压添加剂,例如,可列举硫化油脂、硫化脂肪酸,硫化酯,硫化烯烃、二烃基多硫化合物、噻重氮化合物,烷基硫代氨甲酰化合物,三嗪化合物,硫代萜烯化合物,硫代二丙酸二烷基酯化合物等。
作为在分子中含有磷的极压添加剂,代表性的物质为磷酸三甲苯酯等磷酸酯类和其胺盐。
作为含有硫、磷和金属的极压添加剂,可列举二烷基硫代氨基甲酸锌(Zn-DTC),二烷基硫代氨基甲酸钼(Mo-DTC),二烷基硫代氨基甲酸铅,二烷基硫代氨基甲酸锡,二烷基二硫代磷酸锌(Zn-DTP),二烷基二硫代磷酸钼(Mo-DTP),磺酸钠、磺酸钙等。作为在分子中含有磷的极压添加剂,代表性的物质为磷酸三甲苯酯等磷酸酯类和其胺盐。从配混效果和经济性的观点考虑,以组合物总量为基准,这些极压添加剂的配混量通常为0.01质量%~30质量%,更优选为0.01质量%~10质量%。
作为清洁分散剂,可列举金属磺酸盐,金属水杨酸盐,金属酚盐,琥珀酰亚胺等。从配混效果的观点考虑,以组合物总量为基准,这些清洁分散剂的配混量通常为0.1质量%~30质量%,优选为0.5质量%~10质量%。
作为粘度指数改进剂,例如,可列举聚甲基丙烯酸酯、分散型聚甲基丙烯酸酯、烯烃系共聚物(例如,乙烯-丙烯共聚物等)、分散型烯烃系共聚物、苯乙烯系共聚物(例如,苯乙烯-二烯氢化共聚物等)等。在本发明的润滑油组合物中,从配混效果的观点考虑,以组合物总量为基准,这些粘度指数改进剂的配混量通常为0.5质量%~35质量%,优选为1质量%~15质量%。另外,在本发明的无级变速器用润滑油组合物中,加入在100℃下使粘度为5mm2/s以上的量即可,过多时,牵引系数降低,低温粘度变高,因此,以组合物总量为基准,优选为0.3质量%~5质量%。
作为防锈剂,可列举金属系磺酸盐、琥珀酸酯、烷基胺和单异丙醇胺等烷醇胺等。从配混效果的观点考虑,以组合物总量为基准,这些防锈剂的配混量通常为0.01质量%~10质量%,优选为0.05质量%~5质量%。
作为金属钝化剂,可列举苯并三唑、噻二唑等。从配混效果的角度来看,以组合物总量为基准,这些金属钝化剂的优选配混量通常为0.01质量%~10质量%,优选为0.01质量%~1质量%。
作为消泡剂,可列举甲基硅油、氟硅油,聚丙烯酸酯等。从配混效果的角度来看,以组合物总量为基准,这些消泡剂的配混量通常为0.0005质量%~0.01质量%。
本发明的润滑油组合物可用于如内燃机、液力偶合器、滑动轴承、滚动轴承、含油轴承、流体轴承、压缩装置、链、齿轮、油压、钟表构件、硬盘、制冷机、切削、轧制、挤压拉伸、滚压成形、锻造、热处理、热介质、冷却剂、冷却介质、洗涤、减震器、防锈、制动和密封装置的各种用途中。另外,对于本发明的无级变速器用润滑油组合物,要求高的传递效率,可作为要求牵引系数高的润滑油的金属带方式、链方式、牵引传动方式等无级变速器用的润滑油组合物来使用,即使在高温下也具有可保持充分的油膜的高粘度,因此可特别适合用作通过油膜来传递动力的牵引传动用流体。
实施例
接着,利用实施例1、2和比较例1进一步详细地对本发明的润滑油组合物进行说明,利用实施例3、4和比较例2、3进一步详细地对本发明的无级变速器用润滑油组合物进行说明,但本发明不受这些例子的任何限定。具体来说,如以下所示,制备各样品油并进行各种评价。
〔实施例1〕
用填满了填充材料的40mmφ、120cm的柱子对纯度80%的长叶烯〔Honghe Fine Chemical公司制〕进行精馏,以70%的收率得到了纯度90%的(1S,3aR,4S,8aS)-4,8,8-三甲基-9-亚甲基十氢-1,4-亚甲基薁(沸点145-149℃/30mmHg的馏分)。使用该馏分作为样品油。此外,该馏分中含有2.9质量%的β-石竹烯。
〔实施例2〕
使用纯度60%的长叶烯(ヤスハラケミカル公司制)作为样品油。其中含有14.4质量%的β‐石竹烯。
〔比较例1〕
使用植物油脂(市售大豆油)作为样品油。
〔样品油的性状测定方法〕
按照下述方法,对上述各样品油进行各种性状的测定。结果示于表1。
(1)运动粘度
根据JIS K 2283,测定40℃和100℃下的运动粘度。
(2)粘度指数
根据JIS K 2283进行测定。
(3)15℃密度
根据JIS K 2249进行测定。
(4)倾点
根据JISK 2269进行测定。
(5)体积电阻率
根据JIS C 2101进行测定。
(6)RBOT寿命
向上述各样品油中分别添加0.5质量%的2,6-二叔丁基-4-甲基苯酚。根据JISK 2514,对于那些样品油,测定达到压力下降的终点的时间(分钟)。
[表1]
〔评价结果〕
实施例的样品油与比较例的样品油(大豆油)相比倾点低,可知低温流动性良好。另外,可知实施例的样品油为烃化合物,不是比较例那样的酯化合物,因此耐水解性也良好。
对于β‐石竹烯含量少的实施例1的样品油,可知RBOT的残存时间长,氧化稳定性也良好,作为润滑油使用时寿命长。另外,β‐石竹烯含量少的实施例1的样品油的体积电阻率也高,因此适用于需要绝缘性的用途。进而,还可知对于β‐石竹烯含量少的实施例1的样品油,其粘度指数高,因此随温度变化的粘度变化少,适合作为润滑油。而且,可知对于β‐石竹烯含量少的实施例1的样品油,其氧化稳定性非常良好,作为润滑油的寿命也非常长。
接着,对于本发明的无级变速器用润滑油组合物,根据实施例3、4和比较例2、3进一步详细地说明。
〔制造例1〕
〔双环[2.2.1]庚烷二聚体氢化物(流体1)的制备〕
(1)原料烯烃的制备
在2L的不锈钢制高压釜中,装入巴豆醛561g(8mol)和二环戊二烯352g(2.67mol),在170℃下搅拌3小时进行反应。
将反应溶液冷却至室温后,加入海绵镍催化剂〔川研ファインケミカル(株)制,M-300T〕18g,以氢压0.9MPa?G、反应温度150℃的条件进行4小时的氢化。冷却后,过滤了催化剂后,将滤液减压蒸馏,在105℃/2.66kPa下得到馏分565g。作为将该馏分用质谱、核磁共振谱分析的结果,确认该馏分为2-羟基甲基-3-甲基双环〔2.2.1〕庚烷和3-羟基甲基-2-甲基双环〔2.2.1〕庚烷。接着,将γ-氧化铝〔日挥化学(株)制,N612N〕20g加入到外径20mm、长度500mm的石英玻璃制流通式常压反应管中,以反应温度285℃、质量空速(WHSV)1.1hr-1的条件进行脱水反应,得到了含有2-亚甲基-3-甲基双环〔2.2.1〕庚烷和3-亚甲基-2-甲基双环〔2.2.1〕庚烷55质量%、2,3-二甲基双环〔2.2.1〕庚-2-烯30质量%的2-羟基甲基-3-甲基双环〔2.2.1〕庚烷和3-羟基甲基-2-甲基双环[2.2.1]庚烷的脱水反应产物490g。
(2)二聚体的制备
向1L的四颈烧瓶中加入三氟化硼二乙基醚络合物8g、和上述(1)中得到的烯烃化合物400g,边用机械搅拌器搅拌,边在0℃下进行6小时的二聚化反应。用稀NaOH水溶液和饱和食盐水洗涤该反应混合物,得到烯烃化合物。
(3)氢化步骤
向1L高压釜中加入上述(2)中得到的烯烃化合物300g和氢化用镍/硅藻土催化剂〔日挥化学(株)制,N-113〕12g,以氢压3MPa?G、反应温度80℃、反应时间5小时的条件,进一步以反应温度180℃、反应时间4小时的条件进行氢化,反应结束后,通过过滤除去催化剂,将滤液在减压下蒸馏,由此得到作为目的物的二聚体氢化物240g。将得到的流体作为流体1。
〔实施例3〕
〔长叶烯(流体2)的制备〕
用填满了填充材料的40mmφ、120cm的柱子将纯度80%的长叶烯〔Honghe Fine Chemical公司制〕进行精馏,以70%的收率得到了纯度90%的4,8,8-三甲基-9-亚甲基十氢-1,4-亚甲基薁(沸点145-149℃/30mmHg的馏分)。将得到的流体作为流体2。
〔实施例4〕
配混85质量%的制造例1的流体1和15质量%的实施例3的流体2,作为流体3。
〔制造例2〕
〔流体4的合成〕
根据国际公开公报WO2003/014268中记载的方法,合成α-甲基苯乙烯线性二聚体氢化物。
向具有回流冷凝器、搅拌装置和温度计的500ml四颈烧瓶中加入活性白土(水泽化学工业(株)制“ガレオンアースNS”)4g、二甘醇单乙基醚10g和α-甲基苯乙烯200g,加热至反应温度105℃,搅拌4小时。反应结束后,将生成液用气相色谱进行分析,可知转化率为70%,目的物α-甲基苯乙烯线性二聚体的选择率为95%,副产物α-甲基苯乙烯环状二聚体的选择率为1%,三聚体等高沸点物选择率为4%。将该反应混合物加入到1L高压釜中,加入氢化用镍/硅藻土催化剂(日挥化学(株)制,“N-113”)15g,进行氢化(氢压3MPa?G,反应温度250℃,反应时间5小时)。过滤反应物,浓缩后,进行减压蒸馏,由此得到了99%纯度的α-甲基苯乙烯线性二聚体氢化物,即2,4-二环己基-2-甲基戊烷125g(流体4)。
〔比较例2〕
〔环辛烯二聚体氢化物(流体5)的合成〕
根据前述专利文献1(日本特开2008-260951号公报)实施例13中记载的方法合成。
向1升四颈烧瓶中加入三氟化硼1.5水络合物100g、庚烷200ml,在20℃下边搅拌边用4小时滴加环辛烯450g,进行二聚化反应。
用稀NaOH水溶液和饱和食盐水洗涤该反应混合物,馏去庚烷后,和氢化用镍/硅藻土催化剂(日挥化学(株)制,“N-113”)15g一起加入到1升高压釜中,进行氢化(氢压3MPa,反应温度200℃,反应时间3小时)。反应结束后,通过过滤除去催化剂,将滤液在减压下进行蒸馏,由此得到作为目的物的二聚体的氢化物210g(流体5)。
〔比较例3〕
将比较例2的流体5混合于制造例2的流体4中,以使其含量为全部流体中的15重量%,得到流体6。
〔样品油的性状测定方法〕
按照下述方法,对上述各样品油(流体1~6)进行各种性状的测定。结果示于表1。
(1)运动粘度
根据JIS K 2283,测定40℃、100℃下的运动粘度。
(2)粘度指数
根据JIS K 2283进行测定。
(3)15℃密度
根据JIS K 2249进行测定。
(4)-40℃粘度
根据ASTM D2983进行测定。
(5)牵引系数
120℃下的牵引系数的测定是利用双圆筒滚动滑动摩擦试验机进行的。即,接触的相同尺寸的圆筒(直径52mm,厚度6mm,被驱动侧为曲率半径10mm的鼓型,驱动侧为没有凸起的平坦型)中一者为恒定速度,而另一者的旋转速度连续地变化,通过纺锤对两个圆筒的接触部分给与98.0N的负荷,测定两圆筒间发生的切向力,即牵引力,求出牵引系数。该圆筒由轴承钢SUJ-2镜面抛光而制成,平均圆周速度为6.8m/s,最大赫兹接触压力为1.23GPa。另外,在测定流体温度(油温)120℃下的牵引系数时,通过用加热器加热油罐,使油温从40℃升温至140℃,求出滑率为5%下的牵引系数。
[表2]
〔评价结果〕
实施例3、4的样品油与比较例2、3的样品油相比,粘度指数和牵引系数均大。另外,可知对于配混了长叶烯的实施例4的流体3,与不含长叶烯的制造例1的流体1、制造例2的流体4相比,-40℃下的粘度大幅地变小,另一方面,120℃下的牵引系数可维持大的状态。
Claims (8)
1. 润滑油组合物,其特征在于,配混长叶烯而成。
2. 权利要求1所述的润滑油组合物,其特征在于,以组合物总量为基准,上述长叶烯的配混量为60质量%以上。
3. 权利要求1或2所述的润滑油组合物,其特征在于,该组合物中的β-石竹烯的含量为5质量%以下。
4. 无级变速器用润滑油组合物,其特征在于,配混长叶烯而成。
5. 权利要求4所述的无级变速器用润滑油组合物,其特征在于,配混双环[2.2.1]庚烷二聚体而成。
6. 权利要求4或5所述的无级变速器用润滑油组合物,其特征在于,上述长叶烯的纯度为80%以上。
7. 权利要求4~6中任一项所述的无级变速器用润滑油组合物,其特征在于,该组合物中的β-石竹烯的含量为1质量%以下。
8. 权利要求4~7中任一项所述的无级变速器用润滑油组合物,其特征在于,该组合物为牵引传动用流体。
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CN113302266A (zh) * | 2019-01-17 | 2021-08-24 | 路博润公司 | 牵引流体 |
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