CN103068956B - 润滑油用极压剂和含有其的润滑油组合物 - Google Patents
润滑油用极压剂和含有其的润滑油组合物 Download PDFInfo
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Abstract
本发明的目的是提供一种在润滑的用途中具有与含金属元素等的已有极压剂相同的性能、且不含金属元素等的安全性高的极压剂。本发明的极压剂,其特征在于,由共聚物(A)构成,所述共聚物(A)含有用下述通式(1)表示的丙烯酸烷基酯(a)和用下述通式(2)表示的羟基烷基丙烯酸酯(b)作为必须的构成单体,(a)与(b)的反应比是(a)/(b)=50/50~80/20(摩尔比),且所述共聚物(A)的重均分子量为40000~150000。(1)(式中,R1表示碳原子数为10~18的烷基。)(2)(式中,R2表示碳原子数为2~4的亚烷基。)。
Description
技术领域
本发明涉及新的极压剂。更详细地说,涉及具有与含有金属元素、磷、硫等元素的已有极压剂相同的性能、且不含金属元素、磷、硫等元素的新极压剂。
背景技术
在润滑剂的用途中,包括金属加工油、机油、驱动系统油、液压油等各种用途,近年来,由于机械类的高性能化、大型化及追求节省燃料费用性能,正在开展润滑油的低粘度化等。由于这些影响,在需要润滑的接触面上施加有比目前高的压力的情况增多,作为其弊端,在接触面上产生磨损的问题也增加了。为了防止该磨损,通常使用极压剂(参见例如专利文献1~3)。
在专利文献1中,作为润滑油用的极压剂,记载了硫醚类、亚砜类、砜类、硫代磷酸酯类、硫代碳酸酯类、二硫碳化物类、烷基硫代氨基甲酰类、油脂、硫化油脂、硫化烯烃、磷酸酯、亚磷酸酯、磷酸酯胺盐、亚磷酸酯胺盐、氯代烃、氯代油脂、二硫代磷酸锌、硫代氨基甲酸盐等。
在专利文献2中,作为润滑油的极压剂,记载了萘酸铅、硫代脂肪酸酯、硫代鲸油、硫代萜烯、二苄基二硫化物、氯化石蜡、氯化石脑油磺酸盐(クロロナフサザンテート)、磷酸三甲酚酯、磷酸三丁酯、亚磷酸三甲酚酯、次磷酸正丁基二正辛基酯、磷酸二正丁基二己酯、磷酸二正丁基苯基酯、氨基磷酸二丁酯、氨基二丁基磷酸酯(アミンジブチルホスフェート)等。
在专利文献3中,作为润滑油的极压剂,记载了硫化油脂、烯烃多硫化物(オレフィンポリスルフィド)、二苄基硫醚、磷酸单辛酯、磷酸三丁酯、亚磷酸三苯酯、亚磷酸三丁酯、硫代磷酸酯、硫代磷酸金属盐、硫代氨基甲酸金属盐、酸性磷酸酯金属盐等。
然而,如上所述,这些已知的极压剂基本都含有硫、磷、铅、锌、氯等元素。对于极压剂而言,这些元素起到重要作用,但另一方面,存在这些元素会成为对润滑面腐蚀的原因的情况、这些元素对人体健康产生坏影响的情况、以及这些元素在废弃润滑油时会对环境产生坏影响的情况。近年来对环境问题的意识和对人体的安全性的意识得到提高,因此强烈希望避免使用含有这些元素的化合物,并强烈希望通过由碳、氢和氧这三种元素构成的化合物来获得效果。另一方面,公知的是油脂(参见专利文献1)、脂肪酸酯等不含金属元素等的化合物也具有作为极压剂的性能,但是这些化合物作为极压剂的性能较低,无法在苛刻的条件下使用。由此,期望具有与已有的含金属元素等的极压剂相同的性能、且不含所述金属元素等的安全性高的极压剂。
现有技术文献
专利文献
专利文献1:日本专利公开公报特开平1-287196号
专利文献2:日本专利公开公报特开2002-012881号
专利文献3:日本专利公开公报特开2005-325241号
发明内容
本发明要解决的技术问题
因此,本发明要解决的问题是提供一种在润滑的用途中具有与含金属元素等的已有的极压剂相同的性能、且不含金属元素等的安全性高的极压剂。
解决技术问题的技术方案
因此,本发明人进行了专心的研究,发现了不含金属元素等且能发挥高极压性的添加剂,从而完成了本发明。即,本发明提供一种润滑油用极压剂,其特征在于,所述润滑油用极压剂由共聚物(A)构成,所述共聚物(A)含有用下述通式(1)表示的丙烯酸烷基酯(a)和用下述通式(2)表示的羟基烷基丙烯酸酯(b)作为必须的构成单体,(a)与(b)的反应比是(a)/(b)=50/50~80/20(摩尔比),并且所述共聚物(A)的重均分子量为40000~150000。
[化学式1]
(式中,R1表示碳原子数为10~18的烷基。)
[化学式2]
(式中,R2表示碳原子数为2~4的亚烷基。)
本发明的效果
本发明的效果在于提供了一种在润滑剂的用途中具有与已有的含有金属元素等的极压剂相同的性能、且不含金属元素的安全性高的极压剂,具体地说,提供了一种由碳、氢和氧这三种元素构成的极压剂。
具体实施方式
本发明中能使用的丙烯酸烷基酯(a)是具有碳原子数为10~18的烷基的丙烯酸烷基酯,可以用下述通式(1)表示。
[化学式3]
(式中,R1表示碳原子数为10~18的烷基。)
作为所述通式(1)的R1,可以例举癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等直链烷基;支链癸基、支链十一烷基、支链十二烷基、支链十三烷基、支链十四烷基、支链十五烷基、支链十六烷基、支链十七烷基、支链十八烷基等支链烷基等。其中,从在润滑基油中的溶解性与极压性的平衡的观点出发,优选的是碳原子数为10~16的烷基,进一步优选的是碳原子数为10~14的烷基,更优选的是碳原子数为10~14的直链烷基。
本发明中能使用的羟基烷基丙烯酸酯(b)是具有碳原子数为2~4的亚烷基的羟基亚烷基丙烯酸酯,可以用下述通式(2)表示。
[化学式4]
(式中,R2表示碳原子数为2~4的亚烷基。)
作为所述通式(2)的R2,可以例举亚乙基、亚丙基、亚丁基、甲基亚乙基、甲基亚丙基、二甲基亚乙基等。其中,由于能以低价格制造,所以优选的是碳原子数为2~3的亚烷基,更优选的是亚乙基。
通过将所述单体(a)和(b)共聚,能获得共聚物(A)。对共聚物(A)的聚合方式没有特别的规定,可以是嵌段共聚、无规共聚、或嵌段无规共聚中的任一种。其中,由于聚合反应容易,优选的是无规共聚。单体(a)与单体(b)的反应比例对所得到的共聚物的极压性能和在基油中的溶解性有很大影响,因此(a)与(b)的反应比需要是(a)/(b)=50/50~80/20(摩尔比),优选的是(a)/(b)=50/50~70/30(摩尔比),更优选的是(a)/(b)=55/45~65/35(摩尔比)。单体(a)的比例如果大于(a)/(b)=80/20(摩尔比),则无法获得良好的极压性能,单体(b)的比例如果大于50/50(摩尔比),则在基油中的溶解性恶化,会产生沉淀及浑浊等问题。
通过将单体(a)和(b)共聚得到的共聚物(A)的重均分子量需要为40000~150000,如果考虑极压性和在基油中溶解性的平衡,则重均分子量优选的是50000~100000。重均分子量如果小于40000,则无法获得良好的极压性,如果超过150000,则在基油中的溶解性恶化,会产生沉淀和浑浊等问题,无法获得良好的极压性。另外,重均分子量是通过GPC(凝胶渗透色谱)进行测定,并用苯乙烯换算求出的。
本发明的润滑油用极压剂的合成方法没有特别的限定,只要是公知的方法就可以采用任意的方法进行合成。作为所述的方法,可以例举乳化聚合、悬浮聚合、溶液聚合等,由于本发明的润滑油用极压剂添加到矿物油或合成油等基油中使用,因此与如乳化聚合及悬浮聚合这样使用水作为溶剂的聚合方法相比,优选的是使用将能在基油中溶解的有机溶剂作为溶剂的溶液聚合。如果用乳化聚合或悬浮聚合合成,则在合成结束后,需要将水除去的工序,但是在溶液聚合的情况下,无需除去使用的溶剂,可以直接将溶解在溶剂中的本发明产品添加到基油中。此外,在溶液聚合的情况下,也可以向聚合结束后的体系中进一步加入溶剂来实现产品化,还可以将部分或全部溶剂除去来实现产品化。
作为溶液聚合的具体方法,例如在反应器中加入溶剂、单体(a)和单体(b),并使全部单体成分成为5~80质量%,升温至80~120℃左右,一次或分批添加相对于单体的总量为0.1~10摩尔%量的引发剂,搅拌1~20小时左右进行反应即可。
作为可以使用的溶剂,可以例举甲醇、乙醇、丙醇、丁醇等醇类;苯、甲苯、二甲苯、己烷等烃类;乙酸乙酯、乙酸丁酯、乙酸异丁酯等酯类;丙酮、甲乙酮、甲基异丁基酮等酮类;甲氧基丁醇、乙氧基丁醇、乙二醇单甲醚、乙二醇单丁醚、丙二醇单丁醚、二恶烷等醚类;石蜡系矿物油、环烷系矿物油、或将它们进行氢化精制、溶剂脱沥青、溶剂萃取、溶剂脱蜡、氢化脱蜡、接触脱蜡、氢化分解、碱蒸馏、硫酸洗涤、白土处理等精制后得到的精制矿物油等矿物油;聚-α-烯烃、乙烯-α-烯烃共聚物、聚丁烯、烷基苯、烷基萘、聚苯醚、烷基取代二苯基醚、多元醇酯、二元酸酯、受阻酯、单酯、GTL(天然气合成油)等合成油以及它们的混合物等。
作为能使用的引发剂,可以使用例如2,2’-偶氮二(2-甲基丙腈)、2,2’-偶氮二(2-脒基丙烷)二盐酸盐、2,2’-偶氮二-(N,N-二亚甲基异丁基脒)二盐酸盐、1,1’-偶氮二(环己基-1-腈)等偶氮系引发剂;过氧化氢、过氧化苯甲酰、叔丁基过氧化氢、枯烯过氧化氢、甲乙酮过氧化物、过苯甲酸等有机过氧化物;过硫酸钠、过硫酸钾、过硫酸铵等过硫酸盐;过氧化氢-Fe2+等氧化还原引发剂;其它已知的自由基引发剂等。另外,本发明的润滑油用极压剂必须是特定的分子量,在合成时,可以通过公知的方法对分子量进行控制,作为对分子量的控制可以例举控制反应温度、引发剂的量、单体的加入方法、溶剂的种类、链转移剂的使用等。
共聚物(A)除了单体(a)和(b)以外,在不妨害本发明效果的范围内,还可以共聚其它的单体。其它的单体的聚合方法没有特别的限定,可以在单体(a)与(b)聚合后,共聚其它的单体,也可以将其它的单体与单体(a)和(b)一起聚合。作为所述其它的单体,只要具有双键,就可以是任意的单体,可以例举苯乙烯、乙烯基甲苯、2,4-二甲基苯乙烯、4-乙烯基苯乙烯、2-乙烯基萘等芳香族系乙烯基单体;乙酸乙烯酯、丙酸乙烯酯、辛酸乙烯酯、甲基乙烯基醚、乙基乙烯基醚、2-乙基己基乙烯基醚等脂肪族系乙烯基单体;氯乙烯、溴乙烯、偏二氯乙烯、烯丙基氯、二氯苯乙烯等卤系乙烯基单体;丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬酯等丙烯酸酯;烯丙胺、丙烯酸氨基乙酯、丙烯酸氨基丙酯、丙烯酸氨基丁酯、丙烯酸甲基氨基乙酯、2-二苯基胺基丙烯酰胺(2-ジフェニルアミンアクリルアミド)、丙烯酸二甲基氨基甲酯、二甲基氨基甲基丙烯酰胺、N,N-二甲基氨基苯乙烯、4-乙烯基苯乙烯、N-乙烯基吡咯烷酮等含有氨基的单体等。作为与丙烯酸基类似的结构,包括甲基丙烯酸基,但如果使用具有甲基丙烯酸基的单体,则在基油中的溶解性有时会恶化。此外,在所得到的共聚物中,所述其它的单体含量如果较多,则有时无法发挥极压性能,在基油中的溶解性有时也会不佳,因此所得到的共聚物中的所述其它的单体的含量优选的是30质量%以下,进一步优选的是20质量%以下,更优选的是10质量%以下,最优选的是实质上不含所述其它的单体。另外,单体(a)和单体(b)具有丙烯酸基团,但该基团如果是甲基丙烯酸基,则无法获得本发明的效果,例如,使用甲基丙烯酸烷基酯和羟基亚烷基甲基丙烯酸酯制造出的共聚物无法获得高的极压性能。
本发明的润滑油组合物是在基油中添加了本发明的润滑油用极压剂的组合物。作为能使用的基油,可以例举石蜡系矿物油、环烷系矿物油或将它们进行氢化精制、溶剂脱沥青、溶剂萃取、溶剂脱蜡、氢化脱蜡、接触脱蜡、氢化分解、碱蒸馏、硫酸洗涤、白土处理等精制得到的精制矿物油等矿物油;聚-α-烯烃、乙烯-α-烯烃共聚物、聚丁烯、烷基苯、烷基萘、聚苯醚、烷基取代二苯基醚、多元醇酯、二元酸酯、受阻酯、单酯、GTL(天然气合成油)等合成油、或矿物油与合成油的混合物。
本发明的润滑油组合物中本发明的润滑油用极压剂的添加量虽然没有特别的规定,但是相对于润滑油组合物总量,优选的是添加0.1~50质量%,进一步优选的是添加1~30质量%,更优选的是添加3~20质量%。如果添加量不足0.1质量%,则有时无法获得极压性能,如果添加量超过50质量%,则有时无法完全在基油中溶解、且有时无法获得与添加量相符的效果。
此外,本发明的润滑油组合物可以添加公知的润滑油添加剂,根据使用目的,在不损害本发明效果的范围内,还可以添加防氧化剂、摩擦降低剂、油性提高剂、清洁剂、分散剂、粘度指数提高剂、降凝剂、防锈剂、防腐蚀剂、消泡剂等。
作为防氧化剂,可以例举2,6-二叔丁基苯酚、2,6-二叔丁基对甲酚、2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,4-二甲基-6-叔丁基苯酚、4,4’-亚甲基二(2,6-二叔丁基苯酚)、4,4’-二(2,6-二叔丁基苯酚)、4,4’-二(2-甲基-6-叔丁基苯酚)、2,2’-亚甲基二(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基二(4-乙基-6-叔丁基苯酚)、4,4’-亚丁基二(3-甲基-6-叔丁基苯酚)、4,4’-异亚丙基二(2,6-二叔丁基苯酚)、2,2’-亚甲基二(4-甲基-6-环己基苯酚)、2,2’-亚甲基二(4-甲基-6-壬基苯酚)、2,2’-异亚丁基二(4,6-二甲基苯酚)、2,6-二(2’-羟基-3’-叔丁基-5’-甲基苄基)-4-甲基苯酚、3-叔丁基-4-羟基茴香醚、2-叔丁基-4-羟基茴香醚、3-(4-羟基-3,5-二叔丁基苯基)丙酸辛酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸硬脂基酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸油基酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸十二烷基酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸癸酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸辛酯、四{3-(4-羟基-3,5-二叔丁基苯基)丙酰氧基甲基}甲烷、3-(4-羟基-3,5-二叔丁基苯基)丙酸甘油单酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸与甘油基单油基醚的酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸丁二醇二酯、3-(4-羟基-3,5-二叔丁基苯基)丙酸硫代二醇二酯、4,4’-硫代二(3-甲基-6-叔丁基苯酚)、4,4’-硫代二(2-甲基-6-叔丁基苯酚)、2,2’-硫代二(4-甲基-6-叔丁基苯酚)、2,6-二叔丁基-α-二甲基氨基对甲酚、2,6-二叔丁基-4-(N,N’-二甲基氨基甲基苯酚)、二(3,5-二叔丁基-4-羟基苄基)硫醚、三{(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基}异氰脲酸酯、三(3,5-二叔丁基-4-羟基苯基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、二{2-甲基-4-(3-正烷基硫代丙烯酰氧基)-5-叔丁基苯基}硫醚、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、四邻苯二甲酰基-二(2,6-二甲基-4-叔丁基-3-羟基苄基硫醚)、6-(4-羟基-3,5-二叔丁基苯胺基)-2,4-二(辛基硫基)-1,3,5-三嗪、2,2-硫代-{二乙基-二-3-(3,5-二叔丁基-4-羟基苯基)}丙酸酯、N,N’-六亚甲基二(3,5-二叔丁基-4-羟基-氢化氨基氰)、3,5-二叔丁基-4-羟基-苄基-磷酸二酯、二(3-甲基-4-羟基-5-叔丁基苄基)硫醚、3,9-二[1,1-二甲基-2-{β-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}乙基]-2,4,8,10-四氧杂螺[5,5]十一烷、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、二{3,3’-二-(4’-羟基-3’-叔丁基苯基)丁酸}二醇酯等苯酚系防氧化剂;1-萘胺、苯基-1-萘胺、对辛基苯基-1-萘胺、对壬基苯基-1-萘胺、对十二烷基苯基-1-萘胺、苯基-2-萘胺等萘胺系防氧化剂;N,N’-二异丙基对苯二胺、N,N’-二异丁基对苯二胺、N,N’-二苯基对苯二胺、N,N’-二-β-萘基对苯二胺、N-苯基-N’-异丙基对苯二胺、N-环己基-N’-苯基对苯二胺、N-1,3-二甲基丁基-N’-苯基对苯二胺、二辛基对苯二胺、苯基己基对苯二胺、苯基辛基对苯二胺等对苯二胺系防氧化剂;二吡啶胺、二苯胺、p,p’-二正丁基二苯胺、p,p’-二叔丁基二苯胺、p,p’-二叔戊基二苯胺、p,p’-二辛基二苯胺、p,p’-二壬基二苯胺、p,p’-二癸基二苯胺、p,p’-二(十二烷基)二苯胺、p,p’-二苯乙烯基二苯胺、p,p’-二甲氧基二苯胺、4,4’-二(4-α,α-二甲基苯甲酰基)二苯胺、对异丙氧基二苯胺、二吡啶胺等二苯胺系防氧化剂;吩噻嗪、N-甲基吩噻嗪、N-乙基吩噻嗪、3,7-二辛基吩噻嗪、吩噻嗪二羧酸酯、吩硒嗪等吩噻嗪系防氧化剂;二硫代磷酸锌等。这些防氧化剂的混合量,优选的是相对于基油为0.01~5质量%,更优选的是相对于基油为0.05~4质量%。
作为摩擦降低剂,可以例举二硫代氨基甲酸硫化氧化钼、二硫代磷酸硫化氧化钼等有机钼化合物。这些摩擦降低剂的混合量,以钼含量计,优选的是相对于基油为30~2000质量ppm,更优选的是相对于基油为50~1000质量ppm。
作为油性提高剂,可以例举油醇、硬脂醇等高级醇类;油酸、硬脂酸等脂肪酸类;油基甘油酯、硬脂基甘油酯、月桂基甘油酯等酯类;月桂酰胺、油酰胺、硬脂酰胺等酰胺类、月桂胺、油胺、硬脂胺等胺类;月桂基甘油醚、油基甘油醚等醚类。这些油性提高剂的混合量,优选的是相对于基油为0.1~5质量%,更优选的是相对于基油为0.2~3质量%。
作为清洁剂,可以例举钙、镁、钡等的磺酸盐、高铁酸盐、水杨酸盐、磷酸盐和它们的过碱性盐。其中,优选的是过碱性盐,在过碱性盐中,更优选的是TBN(总碱值)为30~500mgKOH/g的物质。此外,优选的是没有磷和硫原子的水杨酸系清洁剂。这些清洁剂的混合量,优选的是相对于基油为0.5~10质量%,更优选的是相对于基油为1~8质量%。
作为分散剂,可以例举加成了重均分子量约500~3000的烷基或烯基的琥珀酰亚胺、琥珀酸酯、苄胺或它们的硼改性物等。这些分散剂的混合量,优选的是相对于基油为0.5~10质量%,更优选的是相对于基油为1~8质量%。
作为粘度指数提高剂,可以例举聚(C1~C18)烷基(甲基)丙烯酸酯、(C1~C18)烷基丙烯酸酯/(C1~C18)烷基(甲基)丙烯酸酯共聚物、二乙基氨基乙基(甲基)丙烯酸酯/(C1~C18)烷基(甲基)丙烯酸酯共聚物、乙烯/(C1~C18)烷基(甲基)丙烯酸酯共聚物、聚异丁烯、聚烷基苯乙烯、乙烯/丙烯共聚物、苯乙烯/马来酸酯共聚物、苯乙烯/异丁烯氢化共聚物等。此外,还可以使用赋予分散性能的分散型或多功能型粘度指数提高剂。平均分子量为10000~1500000左右。所述粘度指数提高剂的混合量,优选的是相对于基油为0.1~20质量%,更优选的是相对于基油为0.3~15质量%。另外,粘度指数提高剂优选的是使用甲基丙烯酸酯系的聚合物。这是由于与丙烯酸酯系的聚合物相比,甲基丙烯酸酯系的聚合物作为粘度指数提高剂的性能特别优异。本发明的极压剂具有与特定的粘度指数提高剂近似的结构,但是由于是丙烯酸酯系的聚合物,因此几乎没有作为粘度指数提高剂的功能。
作为降凝剂,可以例举聚甲基丙烯酸烷基酯、聚丙烯酸烷基酯、聚烷基苯乙烯、聚乙酸乙烯酯等,重均分子量为1000~100000。所述降凝剂的混合量,优选的是相对于基油为0.005~3质量%,更优选的是相对于基油为0.01~2质量%。降凝剂与粘度指数提高剂相同,优选的是甲基丙烯酸酯系的聚合物,本发明的极压剂几乎没有降凝剂的功能。
作为防锈剂,可以例举亚硝酸钠、氧化石蜡钙盐、氧化石蜡镁盐、牛脂脂肪酸碱金属盐、碱土类金属盐或胺盐、烯基琥珀酸或烯基琥珀酸半酯(烯基的分子量为100~300左右)、脱水山梨糖醇单酯、壬基酚聚氧乙烯醚(ノニルフェノールエトキシレート)、羊毛脂脂肪酸钙盐等。所述防锈剂的混合量,优选的是相对于基油为0.01~3质量%,更优选的是相对于基油为0.02~2质量%。
作为防腐蚀剂,可以例举苯并三唑、苯并咪唑、苯并噻唑、苯并噻二唑、二硫化四烷基秋兰姆等。这些防腐蚀剂的的混合量,优选的是相对于基油为0.01~3质量%,更优选的是相对于基油为0.02~2质量%。
作为消泡剂,可以例举聚二甲基硅氧烷、三氟丙基甲基硅氧烷、胶体二氧化硅、聚丙烯酸烷基酯、聚甲基丙烯酸烷基酯、醇乙氧化物/丙氧化物、脂肪酸乙氧化物/丙氧化物、脱水山梨糖醇部分脂肪酸酯等。这些消泡剂的混合量,优选的是相对于基油为0.001~0.1质量%,更优选的相对于基油为0.001~0.01质量%。
本发明的润滑油组合物只要是润滑的用途就可以任意使用,例如,可以用于机油、齿轮油、透平油、液压油、阻燃性液压油、冷冻机油、压缩机油、真空泵油、轴承油、绝缘油、滑动面油、凿岩机油、金属加工油、塑性加工油、热处理油、润滑脂(グリース)等润滑油。其中,优选的是用于机油、齿轮油、轴承油、金属加工油、润滑脂。
实施例
下面通过实施例对本发明进行具体说明。
<试样1的合成>
在具有温度计、氮气导入管和搅拌器的容量1000ml的四口烧瓶中,加入作为单体(a)的240g(1mol)丙烯酸十二烷基酯(在通式(1)中,R1=十二烷基)、作为单体(b)的116g(1mol)2-羟基乙基丙烯酸酯(在通式(2)中,R2=亚乙基)、作为溶剂的178g甲醇和178g二恶烷。将烧瓶内用氮气置换,添加作为引发剂的3.3克2,2’-偶氮二(2-甲基丙腈),然后边搅拌边缓慢升温,在85~95℃的温度下边回流边反应5小时,得到了试样1。试样1的摩尔比是单体(a)/单体(b)=50/50(摩尔比),用GPC测定分子量的结果是:以苯乙烯换算,重均分子量为98000。
<其它试样的合成>
使用下述a-1~a-7和b-1~b-5这些单体,通过与试样1同样的方法,合成了试样2~试样18的聚合物。另外,试样16用178g异丙醇替代甲醇作为溶剂;试样17使引发剂的量为1.1g(试样1的聚合方法的1/3),控制分子量并进行了聚合反应。
a-1:丙烯酸癸酯(通式(1)中,R1=癸基)
a-2:丙烯酸十二烷基酯(通式(1)中,R1=十二烷基)
a-3:丙烯酸十八烷基酯(通式(1)中,R1=十八烷基)
a-4:丙烯酸丁酯(通式(1)中,R1=丁基)
a-5:丙烯酸2-乙基己酯(通式(1)中,R1=2-乙基己基)a-6:甲基丙烯酸十二烷基酯
a-7:甲基丙烯酸十六烷基酯
b-1:丙烯酸2-羟基乙酯(通式(2)中,R2=亚乙基)
b-2:丙烯酸2-羟基丙酯(通式(2)中,R2=亚丙基)
b-3:甲基丙烯酸2-羟基乙酯
b-4:N,N-二甲基氨基乙基丙烯酸酯
表1:本发明产品
表2:比较品
其它的比较品
试样18:磷酸三甲酚酯
试样19:氯化石蜡(氯含量40质量%)
试样20:甘油单油酸酯(グリセリンモノオレイルエステル)
试验方法
以使试样1~试样20成为1质量%的方式将所述试样1~试样20加热溶解在下述基油1和基油2中,在25℃下放置24小时后,研究了有无沉淀。将没有发现沉淀的作为试验试样,使用高速四球试验机,进行了极压性试验。另外,在溶解在溶剂中的状态下制造了试样1~试样17,但是将通过减压蒸馏除去溶剂后的产物作为添加试样(添加量以固体成分换算)使用。具体的试验方法是在转速为1760rpm、室温、10秒的条件下,改变施加在球上的负荷,进行了耐负荷试验,测定了各负荷下的球的磨斑直径(mm)。磨斑直径越小,越是极压性高的润滑油。另外,溶解稳定性试验按照下述标准进行了评价,极压性试验的磨斑直径刚超过1.0mm,未进行比造成磨斑直径刚超过1.0mm的负荷更高负荷的试验。基油1的试验结果在表3中示出,基油2的试验结果在表4中示出。
基油1:动力粘度4.24mm2/S(100℃)、19.65mm2/S(40℃)、粘度指数=126的矿物油
基油2:动力粘度4.0mm2/S(100℃)、18.4mm2/S(40℃)、粘度指数=119的合成油
溶解稳定性试验
○:未确认到沉淀的均匀的溶液
×:确认到有沉淀
表3:基油1的试验结果
*比较例14是仅有基油的试验结果
表4:基油2的试验结果
*比较例17是仅有基油的试验结果
根据所述结果可以判明:本发明的极压剂显示出与含有磷原子、氯原子的已有的极压剂(比较例11、12)相同或更好的极压性能。此外判明了:具有与本发明的极压剂近似结构的甲基丙烯酸系的聚合物与已有的极压剂相比性能都较差,并且与对应的本发明的极压剂(丙烯酸系聚合物)相比性能存在很大不同。
Claims (2)
1.一种润滑油用极压剂,其特征在于,所述润滑油用极压剂不含金属元素,其特征还在于,所述润滑油用极压剂由共聚物(A)构成,所述共聚物(A)含有用下述通式(1)表示的丙烯酸烷基酯(a)和用下述通式(2)表示的羟基烷基丙烯酸酯(b)作为必须的构成单体,(a)与(b)的反应摩尔比是(a)/(b)=50/50~80/20,并且所述共聚物(A)的重均分子量为55000~98000,
[化学式1]
在通式(1)中,R1表示十二烷基,
[化学式2]
在通式(2)中,R2表示亚乙基。
2.一种润滑油组合物,其特征在于,所述润滑油组合物含有基油和权利要求1所述的润滑油用极压剂,相对于润滑油组合物总量,含有0.1~50质量%的所述润滑油用极压剂。
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EP2607464B1 (en) | 2018-02-21 |
KR101820549B1 (ko) | 2018-01-19 |
KR20140017478A (ko) | 2014-02-11 |
CN103068956A (zh) | 2013-04-24 |
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US20130150274A1 (en) | 2013-06-13 |
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