CN104520415B - 润滑油组合物 - Google Patents
润滑油组合物 Download PDFInfo
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- CN104520415B CN104520415B CN201380041992.6A CN201380041992A CN104520415B CN 104520415 B CN104520415 B CN 104520415B CN 201380041992 A CN201380041992 A CN 201380041992A CN 104520415 B CN104520415 B CN 104520415B
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Abstract
本发明提供一种润滑油组合物,其含有:润滑油基础油和酯添加剂,所述酯添加剂选自作为脂肪酸3,4‑环氧环己基烷基酯的第1酯和作为3,4‑环氧环己基羧酸烷基酯的第2酯的至少1种,且前述酯添加剂的含量以润滑油组合物总量作为基准计为0.01~5.0质量%。
Description
技术领域
本发明涉及在润滑油基础油中配混分子内具有环氧结构的酯的润滑油组合物,尤其涉及一种润滑油组合物,其配混作为脂肪酸3,4-环氧环己基烷基酯和/或作为3,4-环氧环己基羧酸烷基酯的酯,通过捕捉随着润滑油或者冷冻机器的情况下的润滑油与制冷剂的混合流体的劣化而生成的酸性物质来大幅提高稳定性。
背景技术
产业机械、车辆、冷冻机器等机械系统中有各种轴承、活塞缸、齿轮、驱动系等各种各样的滑动部,不间断地反复摩擦。这些滑动部若发生润滑不良,则润滑系统、或者包含其的机械系统就变得不能发挥出所期望的作用。因此,滑动部根据其使用环境·条件而使用各种润滑油等作为润滑剂。
从长期可靠性的观点来看,对于这些润滑油谋求高稳定性,但随着使用会由热劣化·氧化劣化而生成酸性物质。所生成的酸性物质进一步加剧劣化,即发挥所谓的自身催化的作用,所以通过早期去除酸性物质可以大幅提高润滑剂的稳定性。
另外,在冷冻机器的领域中,从防止地球变暖的观点来看,具有从地球温室效应系数(global·warming·potential、GWP)较高的目前的氢氟烃(HFC)制冷剂过渡到GWP为1/100以下的氢氟烯烃(HFO)制冷剂的趋势,正在广泛地研究包含HFO的混合制冷剂等。
但是,这些HFO制冷剂的GWP较低,即容易被分解,所以在与冷冻周期中的润滑油的共存下分解,从而生成强酸即氢氟酸(HF),进一步加剧制冷剂和润滑油的劣化,根据情况产生腐蚀摩耗而成为系统故障的原因。因此,通过有效去除氢氟酸或由润滑油的劣化而生成的酸性物质,从而提高制冷剂与润滑油的混合流体的稳定性成为重大课题。
已知冰箱、空调、室内空调等冷冻·空调系统中,作为现有制冷剂,大多使用二氯二氟甲烷(R12)、氢氯二氟甲烷(R22),这些含有氯的制冷剂与压缩机的润滑油混合,长时间使用发生劣化时生成盐酸,所以在压缩机用润滑油(冷冻机油)中添加用于将盐酸捕捉到分子内的苯基缩水甘油醚、环氧烷烃化合物。
其后,为了谋求进一步提高冷冻机油的稳定性,例如专利文献1中揭示了一种冷冻机油,其含有分子内具有2个以上环氧基的缩水甘油醚化合物;专利文献2中提出了一种润滑油,其组合添加使用磷系添加剂和特定的环氧化合物;专利文献3中提出了一种冷冻机油,其添加有磷酸三甲苯酯和包含缩水甘油醚的环氧或者碳二酰亚胺。另外,专利文献4中公开了一种冷冻机油,其将特殊的化学结构的脂环式多元羧酸酯化合物作为润滑油基础油,且其中含有选自由缩水甘油酯型环氧化合物和脂环式环氧化合物组成的组中的至少1种环氧化合物。
但是,这些稳定剂的目的在于捕捉盐酸、抑制作为润滑油基础油的酯的水解,用作生成强酸的氢氟酸的新型HFO制冷剂的效果不充分。另外,对于目前的机器,为了小型轻量化·高效化而大多使用塑料这样的有机系材料,为了减少对这些机器的影响,谋求即便添加量少而效果大的稳定剂。
现有专利文献
专利文献
专利文献1:日本特开平5-17792号公报
专利文献2:日本特开平5-171174号公报
专利文献3:日本特开平9-189453号公报
专利文献4:日本特开2000-345183号公报
发明内容
发明要解决的问题
本发明是鉴于上述现有技术所具有的课题而完成的,目的在于提供一种润滑油组合物,其即使在生成氢氟酸这样的强酸时,通过配混以少的添加量就能发挥充分的效果的稳定剂来提高稳定性,长期可靠性优异。
用于解决问题的方案
本发明人等为了达成上述目的进行深入研究,结果发现,在润滑油基础油中配混特定量的脂肪酸3,4-环氧环己基烷基酯和/或3,4-环氧环己基羧酸烷基酯的酯,从而可以大幅提高润滑油的稳定性。并且,基于已知的见解完成本发明。
即,本发明提供下述[1]~[9]所示的润滑油组合物。
[1]一种润滑油组合物,其含有:润滑油基础油和酯添加剂,所述酯添加剂选自作为脂肪酸3,4-环氧环己基烷基酯的第1酯和作为3,4-环氧环己基羧酸烷基酯的第2酯的至少1种,且前述酯添加剂的含量以润滑油组合物总量作为基准计为0.01~5.0质量%。
[2]根据[1]所述的润滑油组合物,其中,构成上述第1酯的脂肪酸为碳原子数5~20的支链状脂肪酸,上述第2酯的酯基所包含的烷基为碳原子数5~20的支链状烷基。
[3]根据[1]或[2]所述的润滑油组合物,其中,上述第1酯具有如下结构:在构成1,2-环氧环己烷的环己烷环的4位或5位碳原子上,介由碳原子数1~4的直链状亚烷基键合有从脂肪酸的羧基中去除了氢原子的残基。
[4]根据[1]~[3]中任一项所述的润滑油组合物,其中,润滑油组合物的40℃下的运动粘度为5~1000mm2/s。
[5]根据[1]~[4]中任一项所述的润滑油组合物,其中,上述润滑油基础油为选自矿物油系基础油、合成油系基础油和动植物油系基础油的至少1种。
[6]根据[5]所述的润滑油组合物,其中,上述合成油系基础油为选自酯和醚的至少1种。
[7]一种冷冻机用润滑油组合物,其包含[6]所述的润滑油组合物。
[8]根据[7]所述的冷冻机用润滑油组合物,其中,上述合成油系基础油为选自多元醇酯、聚亚烷基二醇和聚乙烯醚的至少1种。
[9]根据[8]所述的冷冻机用润滑油组合物,其与含有不饱和氟代烃的制冷剂一起使用。
发明的效果
根据本发明,可以提供一种润滑油组合物,其即使在生成氢氟酸这样的强酸时,通过配混以少的添加量就能发挥充分的效果来提高稳定性,长期可靠性优异。
例如,将本发明的润滑油组合物用作一般机械、车辆的润滑油时,能够发挥出特别的效果:通过捕捉随着润滑油的使用而由热劣化·氧化劣化生成的酸性物质,从而可以大幅提高稳定性,可以长期稳定地使用。
另外,将本发明的润滑油组合物用作冷冻机器用润滑油时,能够发挥出特别的效果:通过有效地捕捉由润滑油与制冷剂的混合流体的热劣化生成的包含强酸的酸性物质,可以大幅提高稳定性,可以长期稳定地使用。
具体实施方式
本发明的实施方式的润滑油组合物含有:润滑油基础油和酯添加剂,所述酯添加剂选自作为脂肪酸3,4-环氧环己基烷基酯的第1酯和作为3,4-环氧环己基羧酸烷基酯的第2酯的至少1种。前述酯添加剂的含量以润滑油组合物总量作为基准计为0.01~5.0质量%。
对润滑油组合物的物性没有特别的限定,润滑油组合物的40℃下的运动粘度优选为5~1000mm2/s,更优选为5~300mm2/s,进一步优选为5~220mm2/s,最优选为5~150mm2/s。
以下,对于本实施方式的润滑油组合物的构成成分进行详述。
[润滑油基础油]
作为本实施方式的润滑油基础油,可以使用矿物油系基础油、合成油系基础油、动植物油系等润滑油基础油。
对润滑油基础油的物性没有特别的限定,润滑油基础油的40℃下的运动粘度优选为5~1000mm2/s,更优选为5~300mm2/s,进一步优选为5~150mm2/s。润滑油基础油的粘度指数优选为10以上。润滑油基础油的倾点优选为-10℃以下,更优选为-20℃以下。润滑油基础油的闪点优选为120℃以上,更优选为200℃以上。
作为矿物油系基础油,可列举出:烷烃系基础油、环烷烃系基础油、混合基系基础油。任一种基础油均为适当组合溶剂脱沥青、溶剂萃取、加氢精制、加氢裂化、溶剂脱蜡、加氢脱蜡、白土处理等润滑油精制方法将原油常压蒸馏、进而减压蒸馏而得到的润滑油馏分进行处理而获得的精制润滑油馏分,可以适合地使用。通过组合各种原料和各种精制方法,可以得到性状不同的精制润滑油馏分。本实施方式中,可以单独使用1种矿物油系基础油,也可以组合使用2种以上。
另外,作为合成油系基础油,可列举出:酯、醚等含氧化合物系基础油、聚-α-烯烃(PAO)、乙烯-α-烯烃低聚物、烷基苯、烷基萘等烃系基础油。
含氧化合物系基础油之中,酯为具有如下特征的基础油:市售有各种分子结构的化合物,存在具有各自特有的粘度特性、低温特性,且与相同粘度的烃系基础油相比闪点高的特征。酯可以通过醇与脂肪酸进行脱水缩合反应得到,本发明中,在化学稳定性的方面,作为适宜的基础油成分可列举出:二元酸与一元醇的二酯、多元醇(尤其是新戊基多元醇)与一元脂肪酸的多元醇酯、或者多元醇与多元酸与一元醇(或一元脂肪酸)的复合酯。其中,优选稳定性优异的多元醇酯。需要说明的是,此处所说的作为润滑油基础油的酯不包含作为酯添加剂的第1酯和第2酯。
作为醚,可列举出聚亚烷基二醇、聚乙烯醚等。
另外,作为聚亚烷基二醇,可列举出聚丙二醇。从抑制吸湿性的观点来看,聚亚烷基二醇的末端结构的至少一者优选为烷基,特别优选为甲基。另外,从制造容易性和成本的观点来看,优选任一末端为烷基、另一末端为氢原子,特别优选一末端为甲基、另一末端为氢原子。对于主骨架,从润滑性的观点来看,优选包含氧代亚乙基(EO)和氧代亚丙基(PO)的共聚物,氧代亚乙基占氧代亚乙基与氧代亚丙基总和的比例(EO/PO+EO)优选处于0.1~0.8的范围,更优选处于0.3~0.6的范围。另外,从吸湿性、热稳定·化学稳定性的观点来看,EO/(PO+EO)的值优选处于0~0.5的范围,更优选处于0~0.2的范围,最优选为0(即为环氧丙烷均聚物)。
作为聚乙烯醚,例如可列举出具有通式(1)所示的结构单元的物质。
[式中、R1、R2和R3任选相同或不同,分别表示氢原子或碳原子数1~8的烃基,R4表示碳原子数1~10的二价烃基或碳原子数2~20的二价的含醚键氧的烃基,R5表示碳原子数1~20的烃基,m表示使前述聚乙烯醚的m的平均值为0~10的数,R1~R5在每个结构单元中任选相同或不同,1个结构单元中m为2以上时,该结构单元中的多个R4O任选相同或不同。]
聚乙烯醚可以是其结构单元相同的均聚物,也可以是由2种以上的结构单元构成的共聚物,制成共聚物可以平衡良好地调节特性,故优选。
烃油之中,PAO为α-烯烃的聚合物,通过选定α-烯烃的种类和聚合度可以调节PAO的特性。
对于烷基苯,根据烷基的结构有直链型和支链型,由于特性不同,因此根据目的而区别使用。尤其在冷冻机用润滑油的领域中,烷基苯作为润滑油基础油是有用的。
作为动植物油系基础油,可列举出:牛乳脂、牛脂、猪油(猪脂)、羊脂、牛脚油、鲸油、鲑油、鲣油、鲱油、鳕油、菜籽油、棕榈油、红花油、花生油、玉米油、米糠油、木棉籽油、芝麻油、亚麻油、蓖麻油、可可脂、乳木果油、棕榈油、棕榈仁油、椰子油、大麻籽油、大豆油、棉籽油、葵花籽油、山茶油、米油、茶籽油、橄榄油等。
本实施方式中,可以单独使用矿物油系基础油、合成油系基础油和动植物油系基础油之中的1种。另外,为了满足各种用途所要求的各种性能,可以适宜组合2种以上,并且以适宜的比例进行配混。进而,也可以在矿物油系基础油、合成油系基础油或动植物油系基础油的各自之中,组合使用2种以上的润滑油基础油。
[酯添加剂]
本实施方式的润滑油组合物含有酯添加剂,所述酯添加剂选自作为脂肪酸3,4-环氧环己基烷基酯的第1酯和作为3,4-环氧环己基羧酸烷基酯的第2酯的至少1种。
第1酯(脂肪酸3,4-环氧环己基烷基酯)具有3,4-环氧环己基烷基与从脂肪酸的羧酸基(-COOH)中去除了氢原子的残基键合而成的结构。从该残基的键合位置(脂肪酸3,4-环氧环己基烷基酯的1位碳原子)来看,环氧环是由3位和4位的2个碳原子与1个氧原子构成。换言之,第1酯具有如下结构:在构成1,2-环氧环己烷的环己烷环的4位或5位碳原子上,介由亚烷基,键合有从脂肪酸的羧基去除了氢原子的残基。该亚烷基优选为碳原子数1~4的直链状亚烷基。
作为第1酯的优选例子,可列举出下述通式(2)所示的化合物。
[式中、R6表示碳原子数4~19的烃基、n表示1~4的整数。]
通式(2)中的R6优选为烷基,更优选为支链烷基。另外,该烃基的碳原子数为4~19,优选为6~10。作为R6,从作为润滑油的特性平衡来看,特别优选1-乙基戊基、2,4,4-三甲基戊基。
另外,通式(2)中,-(CH2)n-的重复数n为1~4的整数,优选为1或2。
第2酯(3,4-环氧环己基羧酸烷基酯)具有如下结构:构成1,2-环氧环己烷的环己烷环的4位或5位碳原子直接键合酯基。从该残基的键合位置(3,4-环氧环己基羧酸烷基酯的1位碳原子)来看,环氧环是由3位和4位的2个碳原子与1个氧原子构成。
作为第2酯的优选例子,可列举出下述通式(3)所示的化合物。
[式中、R7表示碳原子数5~20的烷基。]
通式(3)中的R7优选为支链烷基。R7的碳原子数为5~20,特别优选为6~10。作为R7,从作为润滑油的特性平衡来看,特别优选2-乙基己基、3,5,5-三甲基己基。
本实施方式中,作为酯添加剂,可以单独使用第1酯和第2酯之中的1种,另外,也可以组合使用2种以上。酯添加剂的含量以润滑油组合物总量为基准计,为0.01~5.0质量%,优选为0.1~2.0质量%。含量不足上述下限值时,由酯添加剂的添加带来的稳定性提高效果变得不充分。另外,含量超过上述上限值时,则对于应用润滑油组合物的机器中所使用的有机材料的溶胀等的影响变大。需要说明的是,此处所说的酯添加剂的含量在使用2种以上的酯添加剂时表示这些酯添加剂的总含量。
[其它添加剂]
在不损害本发明的目的的范围内,为了进一步提高性能,本实施方式的润滑油组合物可以含有抗氧化剂、摩擦调节剂、抗磨剂、极压剂、防锈剂、金属减活剂、消泡剂等添加剂。
分别地,作为抗氧化剂,可列举出:二叔丁基对甲酚这样的酚系化合物、烷基二苯胺这样的胺系化合物等;作为摩擦调节剂,可列举出:脂肪族胺、脂肪族酰胺、脂肪族酰亚胺、醇、酯、酸性磷酸酯胺盐、亚磷酸酯胺盐等;作为抗磨剂,可列举出:磷酸酯、二烷基二硫代磷酸锌等;作为极压剂,可列举出:硫化烯烃、硫化油脂等;作为防锈剂,可列举出:烯基琥珀酸酯或偏酯等;作为金属减活剂,可列举出:苯并三唑等;作为消泡剂,可列举出:聚硅氧烷化合物、酯系消泡剂等。
将本实施方式的润滑油组合物用作一般机械用或车辆用的润滑油时,作为润滑油基础油,可以优选使用矿物油系基础油。需要说明的是,这些用途中,在使用将矿物油系基础油用作润滑油基础油的现有的润滑油时,由于热劣化·氧化劣化造成来自矿物油系基础油的羧酸等酸性物质大量生成。因此,为了抑制该酸性物质的生成而增加添加剂的含量时,机器的腐蚀等成为问题。与此相对,通过本实施方式的润滑油组合物,上述特定的酯添加剂即使少量添加效果也明显,可以不影响润滑油的其它特性而大幅提高稳定性,可以降低腐蚀性。
另外,对于冷冻机器的情况,从前述那样防止地球变暖的观点来看,有从GWP较高的目前的HFC制冷剂过渡到HFO制冷剂等低GWP的制冷剂的趋势,正在谋求与之相应的润滑油。本实施方式的润滑油组合物作为与低GWP的制冷剂一起使用的冷冻机用润滑油组合物是非常有用的。
对于制冷剂进一步详述,现在,1,1,1,2-四氟乙烷(HFC-134a、R134a)广泛用于冰箱和空调,二氟甲烷(HFC-32、R32)与五氟乙烷(HFC-125、R125)的1/1的混合制冷剂即R410A广泛用于室内空调。作为使用这些制冷剂的冷冻机用润滑油(冷冻机油)的润滑油基础油,优选为具有适度的相互溶解性的酯、聚醚,特别优选为多元醇酯、聚亚烷基二醇、聚乙烯醚。但是,由于这些制冷剂的GWP较高,所以根据所谓的F-气体法规而使用受到制限。
作为其替代品,研究包含低GWP的含有不饱和烃的氢氟烯烃(HFO)的制冷剂的制冷剂,成为最有希望的候补。作为不饱和烃,有2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、1,2,3,3,3-五氟丙烯(HFO-1225ye)等。这些HFO制冷剂具有在分子内容易被分解的烯烃结构,因此具有GWP低但稳定性低这样的特点。由此,在与冷冻周期(cycle)内的润滑油的共存下劣化而容易生成强酸即氢氟酸(HF),进一步加剧制冷剂和润滑油的劣化,根据情况产生腐蚀摩耗而成为系统故障的原因。
根据本实施方式的润滑油组合物,也可以有效地去除这样的氢氟酸、由润滑油的劣化生成的强酸性物质。即,通过将酸性物质吸收至上述特定的酯添加剂的分子内,即便在HFO制冷剂这样稳定性差的制冷剂与润滑油共存的体系中也可以保持高稳定性。
即,作为本实施方式的润滑油组合物的优选方式,可以例示出与含有不饱和氟代烃的制冷剂一起使用的冷冻机用润滑油组合物。作为进一步优选的方式,可以例示出包含本实施方式的润滑油组合物、和含有不饱和氟代烃的制冷剂的冷冻机用工作流体组合物。需要说明的是,此处所说的“含有不饱和氟代烃的制冷剂”包含仅含有不饱和氟代烃的制冷剂(HFO单独)、以及不饱和氟代烃与其它制冷剂成分的混合制冷剂两者。
实施例
以下,基于实施例和比较例,对本发明进一步进行具体说明,但本发明不受以下的实施例的任何限制。
[实施例1~8、比较例1~6]
实施例1~8和比较例1~6中,分别使用以下示出的润滑油基础油和添加剂,制备具有表1、2所示组成的润滑油组合物。需要说明的是,表1、2中的添加剂的含量是以润滑油组合物总量为基准的含量。
(A)润滑油基础油
(A1)多元醇酯(POE):季戊四醇、与2-乙基己酸和3,5,5-三甲基己酸以质量比计为1:1的混合酸的酯(40℃下的运动粘度68.0mm2/s、粘度指数90、倾点-40℃、闪点260℃)
(A2)二酯(DE):癸二酸二辛脂(40℃下的运动粘度11.6mm2/s、粘度指数150、倾点-50℃、闪点220℃)
(A3)聚亚烷基二醇(PAG):两末端用甲基进行醚封闭的聚氧丙烯(平均分子量1000、40℃下的运动粘度46.0mm2/s、粘度指数190、倾点-45℃、闪点218℃)
(A4)矿物油:烷烃系精制矿物油(40℃下的运动粘度22.0mm2/s、粘度指数95、倾点-15℃、闪点210℃)
(A5)菜籽油:精制菜籽油(40℃下的运动粘度32.0mm2/s、粘度指数200、倾点-25℃、闪点330℃)
需要说明的是,运动粘度是基于JIS K2283、倾点是基于JIS K2269、闪点是基于JIS K2265进行测定的。
(B)酯添加剂
作为实施例的添加剂使用如下的物质。
(B1)3,5,5-三甲基己酸3,4-环氧环己基甲酯
(B2)异硬脂酸3,4-环氧环己基甲酯
(B3)3,4-环氧环己烷-1-羧酸3,5,5-三甲基己酯
(B1)是用以下的方法合成的。
将3-环己烯-1-甲醇(东京化成工业株式会社制造)300.0g、3,5,5-三甲基己酸(协和发酵化学株式会社制造,商品名“ISONONANOIC ACID”)352.6g、和对甲苯磺酸(江南化工株式会社制造)0.7g,一边搅拌一边升温至120℃,接着从120℃缓缓升温至150℃并使其反应12小时。其后,在150℃下经3小时缓缓减压至10Torr(约1330Pa),从反应溶液中去除未反应的原料。
使得到的反应溶液恢复至室温,加入乙酸乙酯562.4g、蒸馏水1124.9g、和氢氧化钠0.1g,搅拌30分钟并进行碱洗涤。其后静置,使有机层与水层分液后提取去除水层。向上述有机层加入蒸馏水1124.9g,进行搅拌30分钟并水洗。其后静置,使有机层和水层分液后提取去除水层,实施2次该操作。将回收的有机层移至茄型瓶,使用蒸发仪在120℃、10Torr(约1330Pa)的条件下进行上述有机层的脱溶剂,得到3,5,5-三甲基己酸3-环己烯甲酯511.0g。
接着,将上述得到的3,5,5-三甲基己酸3-环己烯甲酯484.6g、和乙酸乙酯969.1g在30℃下一边搅拌一边用2小时滴加30重量%过氧乙酸的乙酸乙酯溶液(水分率0.41重量%)554.8g,进一步搅拌5小时。其后,向反应后的溶液中加入蒸馏水2008.4g并搅拌30分钟,进行水洗。其后静置,使有机层和水层分液后提取去除水层,实施4次该操作。接着,使用蒸发仪在150℃、10Torr(约1330Pa)的条件下进行上述有机层的脱溶剂,得到3,5,5-三甲基己酸3,4-环氧环己基甲酯505.0g。
(B2)是使用异硬脂酸(东京化成工业株式会社制造)代替3,5,5-三甲基己酸,与(B1)同样地进行合成的。
(B3)是用以下的方法合成的。
将3-环己烯-1-羧酸甲酯(东京化成工业株式会社制造)285.0g、3,5,5-三甲基己醇(协和发酵化学株式会社制造,商品名“Nonanol”)322.6g、和钛酸四丁酯0.03g,一边搅拌一边升温至100℃,接着从100℃缓缓升温至200℃并使其反应15小时。其后,在150℃下经1小时缓缓减压至10Torr(约1330Pa),从反应溶液中去除未反应的原料,得到3-环己烯-1-羧酸3,5,5-三甲基己酯482.2g。
接着,将上述得到的3-环己烯-1-羧酸3,5,5-三甲基己酯450.0g、和乙酸乙酯900.0g在30℃下一边搅拌一边用2小时滴加30重量%过氧乙酸的乙酸乙酯溶液(水分率0.41重量%)554.8g,进一步搅拌5小时。其后,向反应后的溶液中加入蒸馏水1865.2g并搅拌30分钟,进行水洗。其后静置,使有机层与水层分液后提取去除水层,实施4次该操作。接着,使用蒸发仪在120℃、10Torr(约1330Pa)的条件下进行上述有机层的脱溶剂,得到3,4-环氧环己烷-1-羧酸3,5,5-三甲基己酯450.0g。
(C)其它添加剂
(C1)(3,4-环氧)环己烷羧酸3,4-环氧环己基甲酯
(C2)2,2-二甲基辛酸缩水甘油酯
(C3)叔丁基苯甲酸缩水甘油酯
(热稳定性试验)
将实施例1~8和比较例1~6的润滑油组合物作为试样油,用以下的方法实施热稳定性试验。
称量将含水量调节至1000ppm的试样油90g于高压釜中,封入催化剂(铁、铜、铝的线,外径均为1.6mm×50mm)与HFO-1234yf制冷剂10g、空气50cc后,加热到175℃,测定100小时后的试样油的外观和酸值(JIS C2101)。将热稳定性试验前的试样油(新油)的酸值以及热稳定性试验后的试样油的外观和酸值示于表1、2。
[表1]
[表2]
由表1和表2可知,实施例-1~8的润滑油组合物即使在与空气、水和生成氢氟酸的HFO-1234yf的共存下的高温下的热稳定性试验中酸值的上升较小,未发现析出物。实施例-1~4的酯基础油和实施例-8的菜籽油的情况显示在水的共存下水解受到抑制,实施例-5~7的未水解的润滑油基础油的情况可以说在空气、水的共存下氧化劣化受到抑制。
另一方面,比较例-1~6的润滑油组合物的情况,全部发现析出、酸值的上升大。由此,本发明的润滑油组合物以少的添加量可以得到与现有的添加剂同样的效果,可以抑制对体系内的有机材料的影响。另外,添加量为同水平时,稳定性得以大幅提高。
产业上的可利用性
本发明的润滑油组合物以少量的添加剂的配混就可以有效捕捉在主要以矿物油为润滑油基础油的液压工作油、机油的情况下随着润滑油的使用由热劣化·氧化劣化生成的酸性物质,以及在主要以含氧化合物为润滑油基础油的冷冻机用润滑油的情况下包含由润滑油与制冷剂的混合流体的热劣化生成的强酸的酸性物质,从而可以大幅提高稳定性,可以适用于一般机械、车辆、冷冻机等。
Claims (5)
1.一种润滑油组合物,其含有:润滑油基础油和作为下述式(2)所表示的脂肪酸3,4-环氧环己基烷基酯的第1酯,
式中、R6表示碳原子数4~19的支链烷基、n表示1~4的整数,
且所述第1酯的含量以润滑油组合物总量作为基准计为0.01~5.0质量%,
所述润滑油基础油为选自矿物油、二元酸与一元醇的二酯、多元醇与一元脂肪酸的多元醇酯、多元醇与多元酸与一元醇的复合酯、多元醇与多元酸与一元脂肪酸的复合酯、聚亚烷基二醇、聚乙烯醚、聚-α-烯烃、乙烯-α-烯烃低聚物、烷基苯、烷基萘,以及动植物油中的至少一种的润滑油基础油。
2.根据权利要求1所述的润滑油组合物,其中,所述第1酯具有如下结构:在构成1,2-环氧环己烷的环己烷环的4位或5位碳原子上,介由碳原子数1~4的直链状亚烷基键合有从脂肪酸的羧基中去除了氢原子的残基。
3.根据权利要求1或2所述的润滑油组合物,其中,所述润滑油组合物的40℃下的运动粘度为5~1000mm2/s。
4.一种冷冻机用润滑油组合物,其包含权利要求1~3任一项所述的润滑油组合物。
5.根据权利要求4所述的冷冻机用润滑油组合物,其与含有不饱和氟代烃的制冷剂一起使用。
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- 2013-08-23 WO PCT/JP2013/072593 patent/WO2014034568A1/ja active Application Filing
- 2013-08-23 EP EP13832967.7A patent/EP2891703B1/en active Active
- 2013-08-23 KR KR1020157002247A patent/KR101983984B1/ko active IP Right Grant
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JP5882860B2 (ja) | 2016-03-09 |
US9546337B2 (en) | 2017-01-17 |
KR20150046010A (ko) | 2015-04-29 |
US20150252281A1 (en) | 2015-09-10 |
EP2891703B1 (en) | 2019-02-27 |
EP2891703A1 (en) | 2015-07-08 |
CN104520415A (zh) | 2015-04-15 |
WO2014034568A1 (ja) | 2014-03-06 |
JP2014047267A (ja) | 2014-03-17 |
KR101983984B1 (ko) | 2019-05-30 |
TW201414828A (zh) | 2014-04-16 |
EP2891703A4 (en) | 2015-09-09 |
TWI575065B (zh) | 2017-03-21 |
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