CN102766504A - 一种抗微点蚀工业齿轮润滑油组合物 - Google Patents

一种抗微点蚀工业齿轮润滑油组合物 Download PDF

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CN102766504A
CN102766504A CN2011101165262A CN201110116526A CN102766504A CN 102766504 A CN102766504 A CN 102766504A CN 2011101165262 A CN2011101165262 A CN 2011101165262A CN 201110116526 A CN201110116526 A CN 201110116526A CN 102766504 A CN102766504 A CN 102766504A
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CN102766504B (zh
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伏喜胜
华秀菱
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China Petroleum and Natural Gas Co Ltd
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Priority to PCT/CN2012/000600 priority patent/WO2012152060A1/zh
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Abstract

本发明提供了一种抗微点蚀工业齿轮润滑油组合物，它包括(A)至少一种深精制矿物油，或合成油，或以上组分的任意组合物；(B)至少一种抗微点蚀添加剂；(C)至少一种抗磨添加剂；(D)至少一种金属钝化添加剂；(E)至少一种抗氧化添加剂。上述润滑油组合物具有优良的高、低温性能，可满足68、100、150、220、320、460、680工业齿轮油粘度级别要求；上述润滑油组合物具有优良的抗微点蚀性能、抗磨性能和抗氧化性能，通过了FVA 54抗微点蚀试验、FAG FE-8轴承磨损试验及SKF EMCOR轴承腐蚀试验，适用于许多大型工业传动机械和一些汽车传动机械，特别适用于风力发电齿轮传动系统。

Description

一种抗微点蚀工业齿轮润滑油组合物
(一)技术领域
本发明涉及一种润滑油组合物，尤其是一种用于风力发电齿轮传动系统润滑油组合物，属于润滑油技术领域。
(二)背景技术
点蚀及微点蚀是一种典型的接触疲劳破坏，是齿轮常见的失效形式。微点蚀是细微的滚动接触疲劳和磨损，它经常发生在磨削、硬质钢的表面硬化齿轮齿面上，通常在滚动和滑动接触、油膜较薄的条件下出现。
近十年来，微点蚀作为一种新型的齿面疲劳磨损而受到关注，它通常发生在凸轮、齿轮和滚动轴承等受交变负荷的机械零件中。由于微点蚀问题导致许多大型工业传动机械和一些汽车传动机械失效。微点蚀问题在风力发电等工业应用中显得尤为重要。微点蚀会影响齿牙的准确性，导致噪音增加和引起振动，从而减少齿轮的使用寿命。据不完全统计，全国每年对抗微点蚀工业齿轮油的需求量大约在3000吨左右，此需求还在不断增长中。
新一代齿轮油要求油品具有更宽的使用温度、更长的使用寿命；更优异的极压抗磨性、更好减摩节能特性；这是因为随着齿轮工业的高速发展，工业齿轮油已被作为齿轮设计的一个重要零部件，原因之一：设备润滑工况发生了变化，工业齿轮箱朝着更大的动力、更大的载荷和较小的体积方向发展，并且工作环境潮湿。其中载荷的增大，增加了齿面接触压力和金属与金属之间磨损和点蚀，齿轮箱体积的变小导致油品温度的升高，潮湿的工作条件导致轴承腐蚀加剧。其二：齿轮油在润滑齿轮的同时也要确保轴承的润滑。这些变化对工业齿轮油抗磨性能、承载能力、抗微点蚀性能和热稳定性以及抗腐蚀性能提出了更高的要求。体现这些变化的规格主要以德国标准DIN51517和OEM的Flender规格(工业齿轮箱制造商)最具代表性，规格中增加了FVA 54抗微点蚀试验以及FAG FE-8轴承磨损试验。
目前国外齿轮OEM对工业齿轮油的需求不仅仅停留在现有CKD重负荷工业齿轮油的基础上，而是在现有工业齿轮油相关标准的基础上都增添了抗微点蚀的试验。越来越多的齿轮生产厂家，在其研制的设备上要求使用抗微点蚀的工业齿轮油，该类油品目前仅有一家国外公司有相应的产品，但对抗微点蚀的工业齿轮油的配方组成严格保密，通过国内外专利查询，未发现与本发明提供的抗微点蚀的工业齿轮油的配方组成相同的专利。本发明提供的抗微点蚀工业齿轮润滑油组合物可满足风力发电齿轮传动系统的润滑，是一种性能优良、技术难度大、针对性强的工业齿轮润滑油组合物，而且与国外同类产品相比具有更好的抗磨性、抗腐蚀性、抗氧化性和抗微点蚀性能。
(三)发明内容
本发明的目的是：提供一种抗微点蚀工业齿轮润滑油组合物，具有优良的高低温性能、抗微点蚀性能、抗磨性能、抗腐蚀性能及抗氧化性能，可满足风力发电齿轮传动系统的润滑，突出的特点是优异的抗微点蚀性能。
本发明为实现上述目的，对润滑油组合物中的各基础油组分、添加剂组分进行精心选择，并对各组分油、各组分功能添加剂以及基础油与添加剂间的相互作用关系进行了全面系统的研究，把润滑油组合物的抗微点蚀性能、抗磨性能和抗氧化性能作为研究的重点，以期达到本发明的润滑油组合物满足风力发电齿轮传动系统的润滑。
本发明调配的齿轮油组合物，具有优良的高低温性能、抗微点蚀性能、抗磨性能、抗腐蚀性能和抗氧化性能，产品满足68、100、150、220、320、460、680工业齿轮油粘度级别要求，很好地通过了FVA 54抗微点蚀试验、FAGFE-8轴承磨损试验及SKF EMCOR轴承腐蚀试验，可满足风力发电齿轮传动系统的润滑。该产品生产成本低，抗微点蚀性能突出，应用于风力发电领域可产生很好的经济效益与社会效益。该润滑油组合物调配方便，性能优良，有广阔的推广应用前景。
本发明的抗微点蚀工业齿轮润滑油组合物，它含有：(A)至少一种深精制矿物油，或合成油，或以上组分的任意组合物；和(B)至少一种抗微点蚀添加剂；(C)至少一种抗磨添加剂；(D)至少一种金属钝化添加剂；(E)至少一种抗氧化添加剂。所说的(A)为深精制矿物油，或合成油，或以上组分的任意组合物，所说的润滑油组合物含(A)组分88.00～98.79wt％；所说的(B)为二烷基二硫代磷酸酯，或烷基磷酸酯胺盐，或间二膦酸酯，或它们任意组合的混合物，所说的润滑油组合物含(B)组分0.2～5.0wt％；所说的(C)为磷酸三烷基酯，或磷酸三芳基酯，或三烷基硫代磷酸酯，或三芳基硫代磷酸酯，或它们任意组合的混合物，所说的润滑油组合物含(C)组分0.5～3.0wt％；所说的(D)为苯三唑二烷基胺甲醛缩合物，或噻二唑烷基硫醇过氧化氢缩合物，或它们任意组合的混合物，所说的润滑油组合物含(D)组分0.01～1.0wt％；所说的(E)为2、6-二叔丁基对甲酚，或N-苯基-α-萘胺和二烷基二苯胺缩合物，或二烷基二硫代氨基甲酸酯，或它们任意组合的混合物，所说的润滑油组合物含(E)组分0.5～3.0wt％。
更进一步，本发明的抗微点蚀工业齿轮润滑油组合物，它含有：(A)至少一种深精制矿物油，或合成油，或以上组分的任意组合物；和(B)至少一种抗微点蚀添加剂；(C)至少一种抗磨添加剂；(D)至少一种金属钝化添加剂；(E)至少一种抗氧化添加剂。
其中所说的(A)是溶剂深精制矿物油，或异构脱蜡加氢深精制矿物油，或聚a-烯烃合成油，或酯类合成油，或以上组分的任意组合物，所说的润滑油组合物，含(A)组分的适宜含量为88.00～98.48wt％；
(B)组分较适宜的是二异丙基二硫代磷酸酯，或异丙基异辛基二硫代磷酸酯，或二异已基二硫代磷酸酯，或二异辛基二硫代磷酸酯，或二异丙基磷酸酯十八胺盐，或异丙基异辛基磷酸酯十八胺盐，或二异已基磷酸酯十八胺盐，或二异辛基磷酸酯十八胺盐，或间二膦酸二异丙酯，或间二膦酸异丙异辛酯，或间二膦酸二异已酯，或间二膦酸二异辛酯，或它们任意组合的混合物，组分(B)在润滑油组合物中的适宜含量为0.3～5.0wt％；
(C)组分较适宜的是磷酸三甲酚酯，或硫代磷酸三苯酯，或磷酸三丁酯，或硫代磷酸三丁酯，或磷酸三辛酯，或硫代磷酸三辛酯，或磷酸三(十二)烷基酯，或硫代磷酸三(十二)烷基酯，或它们任意组合的混合物，组分(C)在润滑油组合物中的适宜含量为0.6～3.0wt％；
(D)组分较适宜的是苯三唑二正丁胺甲醛缩合物，或苯三唑二辛胺甲醛缩合物，或噻二唑十二烷基硫醇过氧化氢缩合物，或噻二唑十八烷基硫醇过氧化氢缩合物，或它们任意组合的混合物，组分(D)在润滑油组合物中的适宜含量为0.02～1.0wt％；
(E)组分较适宜的是2、6-二叔丁基对甲酚，或N-苯基-α-萘胺和二正丁基二苯胺缩合物，或N-苯基-α-萘胺和丁基辛基二苯胺缩合物，或N-苯基-α-萘胺和丁基壬基二苯胺缩合物，或N-苯基-α-萘胺和二辛基二苯胺缩合物，或N-苯基-α-萘胺和二壬基二苯胺缩合物，或二正丁基二硫代氨基甲酸酯，或二正辛基二硫代氨基甲酸酯，或二正十二烷基二硫代氨基甲酸酯，或它们任意组合的混合物，组分(E)在润滑油组合物中的适宜含量为0.6～3.0wt％。
制法：上述抗微点蚀工业齿轮润滑油组合物的制备方法是：先将按比例所需量的组分油(A)加入带搅拌器的不锈钢调合釜内，其次将按比例所需量的抗微点蚀添加剂(B)、抗磨添加剂(C)、金属钝化添加剂(D)、抗氧化添加剂(E)加入到调合釜中，升温至50～60℃下搅拌4小时，至混合物均匀透明。
为了筛选添加剂组分和润滑油组合物，本发明在实验室主要用MPR微点蚀模拟试验进行模拟评定。MPR微点蚀模拟试验机是专门用来在特定的模拟试验条件下产生微点蚀或者点蚀的试验机，尤其适合于模拟齿轮、滚动轴承运动部件的接触情况。该试验机由于设计的要求，每小时可实现100万次的疲劳接触，从而大大缩短了试验时间，可以考察添加剂组成对点蚀、微点蚀的影响。模拟微点蚀试验分为4个阶段，从阶段1到阶段4载荷逐级增加，每个阶段运转1h，4h后评价试验辊子磨损情况，然后重复阶段4(1h)后再评价辊子的磨损情况。最后评价可采用三个方面：(1)失重，0h、4h、5h时对试验辊子称重，观察失重情况；(2)辊子宽度变化，新试验辊子的宽度为1mm，试验后由于微点蚀磨损造成宽度增加，观察0h、4h、5h时的辊子宽度变化情况；(3)显微镜照片，在显微镜下观察0h、4h、5h的辊子表面的微点蚀磨损情况。
为了评价润滑油组合物，采用了FZG微点蚀试验齿轮台架、FAG  FE-8轴承磨损试验台架、SKF EMCOR轴承腐蚀试验台架。FVA微点蚀试验台架是由德国慕尼黑技术大学FZG齿轮研究中心开发的试验设备，主要应用于润滑剂和材料的使用性能评价。微点蚀试验方法也是由FZG齿轮研究中心开发，该试验方法现属于德国机械制造商协会动力传动委员会(FVA)的标准，方法号为FVA54/I-IV。FE-8轴承磨损试验台架由德国FAG轴承公司开发，主要应用于润滑油、润滑脂及其添加剂对磨损性能的评价，也可以用于轴承材料的磨损性能的考察。该试验方法现属于德国国家标准，方法号为DIN 51819。SKF EMCOR试验台是由瑞典SKF公司开发的用于评价润滑脂、润滑油的抗锈蚀性能，根据润滑油脂应用环境不同，有蒸馏水或去离子水、合成海水、合成盐水三种试验液可供选择，试验在室温、没有负荷的条件下，低转速循环运转，总的试验时间164h，测定滚动轴承的抗腐蚀性能。
(四)附图说明
图1为组合物(IV)0h的辊子表面照片，图2为对比油0h的辊子表面照片，图3为组合物(IV)4h的辊子表面照片，图4为对比油4h的辊子表面照片，图5为组合物(IV)5h的辊子表面照片，图6为对比油5h的辊子表面照片。
(五)具体实施方式
本发明的效果通过下面的实施例进一步说明。但应明白，下面的实施例不是限制本发明的范围，任何不超出本发明构思和范围的改动，都在本发明的范围之内。
实施例1：
润滑油组合物(I)，它包括：93.78wt％的溶剂深精制矿物油HVIS 500SN(性质见表1)(组分A)；5.0wt％的二异已基二硫代磷酸酯(组分B)；0.60wt％磷酸三甲酚酯(组分C)；0.02wt％的苯三唑二辛胺甲醛缩合物(组分D)；0.60wt％的2、6-二叔丁基对甲酚(组分E)。润滑油组合物(II)除组分(B)5.0wt％的二异已基二硫代磷酸酯被5.0wt％的二异已基磷酸酯十八胺盐替代外，其余均同组合物(I)。润滑油组合物(III)除组份(B)5.0wt％的二异已基二硫代磷酸酯被5.0wt％的间二膦酸二异已酯替代外，其余均同组合物(I)。组合物(I)、(II)、(III)的主要性质、性能表2中。
表1HVIS 500SN主要性质
Figure BDA0000059618610000061
表2组合物主要性质、性能
Figure BDA0000059618610000062
Figure BDA0000059618610000071
从表中可以看出：抗微点蚀添加剂二异已基磷酸酯十八胺盐的抗点蚀性能好于二异已基二硫代磷酸酯和间二膦酸二异已酯。
实施例2：
润滑油组合物(IV)，它包括：82.875wt％的聚a-烯烃合成油PAO100(性质见表3)，14.625wt％的酯类合成油(性质见表4)(组分A)；0.5wt％的间二膦酸二异辛酯，0.1wt％二异辛基磷酸酯十八胺盐，0.4wt％异丙基异辛基二硫代磷酸酯(组分B)；0.5wt％硫代磷酸三苯酯(组分C)；0.05wt％的噻二唑十二烷基硫醇过氧化氢缩合物(组分D)；0.30wt％的2、6-二叔丁基对甲酚，0.40wt％N-苯基-α-萘胺和二壬基二苯胺缩合物，0.25wt％二正丁基二硫代氨基甲酸酯(组分E)。润滑油组合物(IV)评价结果见表5。
表3PA010、PA0100的主要性质
Figure BDA0000059618610000081
表4酯类油的主要性质
Figure BDA0000059618610000082
表5润滑油组合物(IV)评价结果
Figure BDA0000059618610000083
表5和图1、2、3、4、5、6MPR模拟微点蚀试验结果表明，失重：4h、5h试验后两个辊子失重组合物(IV)略低于对比油基本相当。宽度变化：组合物(IV)试验后的辊子宽度变化略低于对比油。显微镜下观察：0h组合物(IV)与对比油辊子表面一样(图1、图2)，从4h试验后的显微镜照片(图3、图4)看，辊子的微点蚀面积基本相当，但对比油表面有划痕。从5h试验后的显微镜照片(图5、图6)看，组合物(IV)的微点蚀面积与对比油的微点蚀面积大小基本一致。
结合以上三方面的分析，组合物(IV)的抗微点蚀性能与对比油的抗微点蚀性能接近。
实施例3：
润滑油组合物(V)，它包括：97.5wt％的聚a-烯烃合成油PA010(性质见表3)(性质见表4)(组分A)；0.5wt％的间二膦酸二异辛酯，0.1wt％二异辛基磷酸酯十八胺盐，0.4wt％异丙基异辛基二硫代磷酸酯(组分B)；0.5wt％硫代磷酸三苯酯(组分C)；0.05wt％的噻二唑十二烷基硫醇过氧化氢缩合物(组分D)；0.30wt％的2、6-二叔丁基对甲酚，0.40wt％N-苯基-α-萘胺和二壬基二苯胺缩合物，0.25wt％二正丁基二硫代氨基甲酸酯(组分E)。润滑油组合物(V)评价结果见表6。
表6润滑油组合物(V)评价结果
Figure BDA0000059618610000091
表6试验结果表明，本发明的产品很好地通过了FVA 54抗微点蚀试验、FAG FE-8轴承磨损试验及SKF EMCOR轴承腐蚀试验，可满足风力发电齿轮传动系统的润滑。

Claims (6)

1.一种抗微点蚀工业齿轮润滑油组合物，其特征在于它含有：
(A)至少一种深精制矿物油，或合成油，或以上组分的任意组合物，组合物含组分(A)88.00～98.79wt％，
(B)至少一种抗微点蚀添加剂，为二烷基二硫代磷酸酯，或烷基磷酸酯胺盐，或间二膦酸酯，或它们任意组合的混合物，组合物含组分(B)0.2～5.0wt％，
(C)至少一种抗磨添加剂，为磷酸三烷基酯，或磷酸三芳基酯，或三烷基硫代磷酸酯，或三芳基硫代磷酸酯，或它们任意组合的混合物，组合物含组分(C)0.5～3.0wt％，
(D)至少一种金属钝化添加剂，为苯三唑二烷基胺甲醛缩合物，或噻二唑烷基硫醇过氧化氢缩合物，或它们任意组合的混合物，组合物含组分(D)0.01～1.0wt％，
(E)至少一种抗氧化添加剂，为2、6-二叔丁基对甲酚，或N-苯基-α-萘胺和二烷基二苯胺缩合物，或二烷基二硫代氨基甲酸酯，或它们任意组合的混合物，组合物含组分(E)0.5～3.0wt％。
2.根据权利要求1所述的抗微点蚀工业齿轮润滑油组合物，其特征在于(A)组分为溶剂深精制矿物油，或异构脱蜡加氢深精制矿物油，或聚a-烯烃合成油，或酯类合成油，或以上组分的任意组合物，含量为88.00～98.48wt％。
3.根据权利要求1所述的抗微点蚀工业齿轮润滑油组合物，其特征在于(B)组分为二异丙基二硫代磷酸酯，或异丙基异辛基二硫代磷酸酯，或二异已基二硫代磷酸酯，或二异辛基二硫代磷酸酯，或二异丙基磷酸酯十八胺盐，或异丙基异辛基磷酸酯十八胺盐，或二异已基磷酸酯十八胺盐，或二异辛基磷酸酯十八胺盐，或间二膦酸二异丙酯，或间二膦酸异丙异辛酯，或间二膦酸二异已酯，或间二膦酸二异辛酯，或它们任意组合的混合物，含量为0.3～5.0wt％。
4.根据权利要求1所述的抗微点蚀工业齿轮润滑油组合物，其特征在于(C)组分为磷酸三甲酚酯，或硫代磷酸三苯酯，或磷酸三丁酯，或硫代磷酸三丁酯，或磷酸三辛酯，或硫代磷酸三辛酯，或磷酸三(十二)烷基酯，或硫代磷酸三(十二)烷基酯，或它们任意组合的混合物，含量为0.6～3.0wt％。
5.根据权利要求1所述的抗微点蚀工业齿轮润滑油组合物，其特征在于(D)组分为苯三唑二正丁胺甲醛缩合物，或苯三唑二辛胺甲醛缩合物，或噻二唑十二烷基硫醇过氧化氢缩合物，或噻二唑十八烷基硫醇过氧化氢缩合物，或它们任意组合的混合物，含量为0.02～1.0wt％。
6.根据权利要求1所述的抗微点蚀工业齿轮润滑油组合物，其特征在于(E)组分为2、6-二叔丁基对甲酚，或N-苯基-α-萘胺和二正丁基二苯胺缩合物，或N-苯基-α-萘胺和丁基辛基二苯胺缩合物，或N-苯基-α-萘胺和丁基壬基二苯胺缩合物，或N-苯基-α-萘胺和二辛基二苯胺缩合物，或N-苯基-α-萘胺和二壬基二苯胺缩合物，或二正丁基二硫代氨基甲酸酯，或二正辛基二硫代氨基甲酸酯，或二正十二烷基二硫代氨基甲酸酯，或它们任意组合的混合物，含量为0.6～3.0wt％。
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