CN1190427A - 润滑组合物 - Google Patents
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- CN1190427A CN1190427A CN96195327A CN96195327A CN1190427A CN 1190427 A CN1190427 A CN 1190427A CN 96195327 A CN96195327 A CN 96195327A CN 96195327 A CN96195327 A CN 96195327A CN 1190427 A CN1190427 A CN 1190427A
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/042—Metal salts thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/061—Metal salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
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Abstract
一种润滑组合物,该组合物包括:(a)基础油;(b)式(Ⅰ)的磷酸酸酯,式中R1是含3~30碳原子的一价有机基,R2是氢或含3~30碳原子的一价有机基和(c)式(Ⅱ)的膦酸酯,式中R3和R4分别是含1~10碳原子的一价有机基,R5是含4~30碳原子的一价有机基,优选的是含10~24碳原子的一价有机基,(b)和(c)的含量足以提高其摩擦性。
Description
本发明涉及适于用作润滑油的组合物,特别是适于用作滑槽润滑油的组合物。
机床加工制品时常常要求达到非常小的公差,例如在加工凸轮轴时,其公差可能只有大约1微米。因此,机床必须精确定位。滑槽润滑油就是用来润滑机床安装面的润滑油,使机床容易达到要求的精确定位。
以前曾提出在滑槽润滑组合物中用磷酸酯来作摩擦缓和剂,例如曾描述过将磷酸单戊酯和磷酸双戊酯与脂类物质如硫化酯组合使用的情况。
以前,这些脂类物质的需用量很大,通常是润滑组合物的1%~5%(重量),磷酸酯的用量为润滑组合物的0.05~1%(重量)。人们都希望能够减少添加剂的用量,这不仅是经济原因,还因为添加剂会污染金属加工的流体。
本发明为此提供了一个解决方案,其方法是提供一种包含膦酸酯和磷酸酸酯的组合物,该组合物在添加剂的含量比以前低的情况下能达到所要求的低摩擦性。本发明提出了一种润滑组合物,该组合物包含:
(a)基础油
(b)下式的磷酸酸酯式中R1是含3~30碳原子,优选的是4~24碳原子的一价有机基,R2是氢或含3~30碳原子,优选的是4~24碳原子的一价有机基
基础油可以是任何一种润滑油,天然的或合成的均可。天然油包含链烷、环烷和芳族油或其混合物。合成油中有聚α-烯烃流体,聚乙二醇、聚缩醛、聚硅氧烷和酯。
上述酯是由多元醇和一元羧酸制成的,诸如由季戊四醇或新戊基甘醇及其同系物和含4~9碳原子的脂族一元羧酸制成的酯。还可以采用的酯是由二羧酸如癸二酸和一元醇如2-乙基己醇制成的酯。在上式酸酯中,R1和R2(当不是氢时)优选的是脂族基,例如,烷基或链烯基,优选的是直链基,并含5~20碳原子的基。R1与R2相同是合适的。
单酯和双酯两者都合适,而且还可以使用两者的混合物。特别合适的酯是近似等摩尔比的两种酯的混合物,如40∶60~60∶40的双正庚酸磷酸酯和单正庚酸磷酸酯的混合物。
上式膦酸酯中,优选的R3和R4均为脂族基,例如,含1~10碳原子的脂族基,更优选的是含1~6碳原子的脂族基。优选的R5是其碳原子数比R3或R4多,并也是一种脂族基,合适的是含12~24碳原子的脂族基,更优选的是含15~20碳原子的脂族基。
优选的R5是不含芳族取代基,而最佳是直链烷基。有一些支链是可以接受的,但膦酸酯中所含的支链物最好是不超过1%(重量)。
酸酯的优选含量是基础油(a)、磷酸酸酯(b)和膦酸酯(c)的总量的0.05%(重量)以上。除了需考虑溶解度以外,其含量没有上限,但一般来说,含量高于1%也不会带来更多的好处,因此,通常的含量不会高于此值。一般为0.1~0.6%(重量)。
优选的膦酸酯用量为0.1%以上。至于磷酸酯,其用量没有上限,但用量大于1%通常也不会有更多的好处。通常为0.25~0.7%(重量)。
酸酯与膦酸酯的摩尔比可以为1∶5~2∶1,优选的是1∶2~1.5∶1。本发明的组合物适于用作滑槽润滑油。当采用时,该组合物可含其它添加剂,那是一些通常加到滑槽润滑油中的添加剂,其添加量也是通常的用量。例如,抗氧剂如酚型抗氧剂,基添加量约为0.1%,抗磨剂如烷基或芳基亚磷酸酯,例如二丁基亚磷酸氢酯,其添加量高达约0.5%,破乳剂如环氧乙烷/环氧丙烷共聚物,其添加量约为0.002%,金属减活剂,其添加量约为0.05%和防沫剂,其添加量约为0.005%,所有百分比都是以全部组合物计的重量百分比。
本发明润滑组合物的静态摩擦系数优选的是小于0.110,更优选的是小于0.105,最优选的是小于0.100,其测定方法如下所述。
磷酸酸酯和膦酸酯在加进基础油之前可先混合以形成一种添加剂浓缩液或称“配套料”。本发明的另一内容提出了一种添加剂浓缩液,该浓缩液可用来与基础油掺和以制成润滑组合物,该添加剂浓缩液包含上述定义的磷酸酸酯和膦酸酯,酸酯与膦酸酯的摩尔比为1∶5~2∶1。
添加剂浓缩液可以含有上述任何一种或全部其它添加剂,诸如抗氧剂、抗磨剂、破乳剂、金属减活剂和防沫剂,其添加量要达到一定要求,即当浓缩液用基础油稀释时,所得到的润滑组合物应含有必要量的添加剂。
通过下面实施例对本发明进行说明。
实施例1
将基础油与(a)各种酸式磷酸酯,(b)各种膦酸酯和(c)酸式磷酸酯和膦酸酯两者进行掺和,以制备润滑组合物。制备组合物的方法是将磷酸酯和/或膦酸酯加到预热达40-50℃的基础油中并对混合物进行搅拌。
测定每一种组合物的摩擦系数。
各组份的含量和摩擦系数记录在下表中。测得的摩擦系数是边界润滑条件下的静态摩擦系数,是用Cameron Plint TE 77型高频摩擦仪测定的。该摩擦仪由一个油浴槽构成,槽中固定着一块铸铁板。将油注入浴槽中(按配方配制的油或非配方油均可)。将一块已知表面积,由铸铁或环氧树脂制成的活动滑块用既定的力放到因定板的顶上。顶部滑块在固定板上作往复移动、固定板附在一个能检测到微小移动的压电晶体上。移动量转换成电压,以虚拟方波的形式显示在示波器上,虚拟方波的振幅就表示静态摩擦系数。采用的方法曾由A G Plint和M A Plint在“国际磨损学”1985年8月18卷NO.4 P.247~249上描述过,该杂志由Butterworth出版有限公司出版。测试程序严格按照文献所述方法进行,只是(i)驱动头与移动试片之间不加弹性垫片,(ii)移动试片的表面积为30×20mm,而不是10×10mm,(iii)温度是20℃,而不是50℃,(iv)载荷是60N,而不是250N。
表试验号 组合物 摩擦系数1 基础油 0.2982 基础油+0.5%DMODP 0.196 3 基础油+0.5% DMODP+0.3% HAP 0.0934 基础油+0.25% AAP 0.1085 基础油+0.5% DMODP+0.25% AAP 0.1046 基础油+0.3% HAP 0.1127 基础油+0.35% NAP 0.2038 基础油+O.5% DM0DP+O.35% NAP O.1359 基础油+0.45% TDAP O.22310 基础油+0.45% TDAP+O.5% DM0DP O.16511 基础油+0.58% 0AP O.18812 基础油+O.5% DM0DP+0.58% 0AP O.12213 基础油+0.35% DBBP 0.28114 基础油+0.35% DBBP+0.25% AAP 0.11315 基础油+0.35% DBBP+O.3% HAP 0.12116 基础油+0.35% DBBP+0.35% NAP 0.18817 基础油+0.35% DBBP+0.45% TDAP 0.19718 基础油+0.35% DBBP+0.58% OAP 0.177
基础油是150溶剂中性润滑油的基本原料。
百分比是以基础油和磷酸酯和/或膦酸酯总重量计的重量百分比。DMODP和HAP的用量是经过选定的,然后对其它添加剂的用量进行计算,使每一次试验中组合物的磷酸酯和膦酸酯的摩尔数均相同。
采用的酸性磷酸酯都是单酯和双酯的1∶1混合物。每一种酯中的烷基都是直链的。
上表中所用的缩写词如下:DMODP 是二甲基正十八烷基膦酸酯DBBP 是二正丁基正丁基膦酸酯AAP 是正戊基酸性磷酸酯HAP 是正庚基酸性磷酸酯NAP 是正壬基酸性磷酸酯TDAP 是正十三烷基酸性磷酸酯OAP 是正油基酸性磷酸酯
第1,2,4,6,7,9,11和13次试验并不是按本发明方法做的试验,列在表中只是为了进行比较而已。
第2,3和6次试验对比结果表明,DMODP与HAP组合使用优于HAP或DMODP单独使用。第2,4和5次试验表明,DMODP与AAP组合使用优于AAP或DMODP单独使用。第2,7和8次试验表明,DMODP与NAP组合使用优于NAP或DMODP单独使用。第2,9和10次试验表明,DMODP与TDAP组合使用优于DMODP或TDAP单独使用。第2,11和12次试验表明,DMODP与OAP组合使用优于OAP或DMODP单独使用。
第1次和13次对比试验表明,单独使用DBBP(这里非优选的膦酸酯)对整个基础油稍有改善。第4次和14次试验表明,DBBP与AAP组合使用不如AAP单独使用有效。
此外,第6试验与第15次试验对比表明,DBBP与HAP组合使用不如HAP单独使用有效。
第7次试验与第16次试验对比表明,DBBP与NAP组合使用比NAP单独使用更有效。第17次和18次试验也表明,当DBBP与TDAP或OAP组合使用时比这些磷酸酯单独使用时有所改善。
Claims (10)
2.权利要求1的润滑组合物,其中R1和R2基是含4~24碳原子的脂族基。
3.权利要求1或2的润滑组合物,其中R3和R4是含1~6碳原子的烷基或链烯基。
4.前述任何一项权利要求的润滑组合物,其中R5基含12~24碳原子。
5.前述任何一项权利要求的润滑组合物,其中酸酯与膦酸酯的摩尔比为1∶5~2∶1。
6.前述任何一项权利要求的润滑组合物,其中磷酸酸酯的含量至少为基础油(a)磷酸酸酯(b)和膦酸酯(c)的总量的0.05%(重量)。
7.权利要求6的润滑组合物,其中磷酸酸酯的含量为0.1~0.6%(重量)。
8.前面任何一项权利要求的润滑组合物,其中膦酸酯的含量至少为基础油(a)磷酸酸酯(b)和膦酸酯(c)的总量的0.1%(重量)。
9.权利要求8的润滑组合物,其中膦酸酯的含量为0.25~0.7%(重量)。
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GB9510071.5 | 1995-05-18 | ||
GBGB9510071.5A GB9510071D0 (en) | 1995-05-18 | 1995-05-18 | Lubricating compositions |
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US (1) | US5824628A (zh) |
EP (1) | EP0826023A1 (zh) |
JP (1) | JPH11505283A (zh) |
KR (1) | KR19990014903A (zh) |
CN (1) | CN1190427A (zh) |
AU (1) | AU709312B2 (zh) |
BR (1) | BR9608766A (zh) |
CA (1) | CA2221309A1 (zh) |
GB (1) | GB9510071D0 (zh) |
NZ (1) | NZ308145A (zh) |
TR (1) | TR199701382T1 (zh) |
WO (1) | WO1996036682A1 (zh) |
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CN100500817C (zh) * | 2002-08-27 | 2009-06-17 | 新日本石油株式会社 | 润滑油组合物 |
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US20090318319A1 (en) * | 2008-06-23 | 2009-12-24 | Afton Chemical Corporation | Friction modifiers for slideway applications |
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US2174019A (en) * | 1936-11-27 | 1939-09-26 | Standard Oil Co | Lubricant |
GB1105965A (en) * | 1964-09-18 | 1968-03-13 | British Petroleum Co | Lubricating compositions |
GB1147508A (en) * | 1967-01-30 | 1969-04-02 | Mobil Oil Corp | Lubricant composition |
US4158633A (en) * | 1978-03-30 | 1979-06-19 | Edwin Cooper, Inc. | Lubricating oil |
US4356097A (en) * | 1978-03-30 | 1982-10-26 | Edwin Cooper, Inc. | Alkylphosphonate lubricating oil |
DE3585120D1 (de) * | 1984-10-03 | 1992-02-20 | Hitachi Ltd | Schmiermittel fuer die plastische verformung von metallen. |
JPH02269197A (ja) * | 1984-12-14 | 1990-11-02 | Idemitsu Kosan Co Ltd | 摺動兼金属加工用潤滑組成物 |
JPS61291687A (ja) * | 1985-06-19 | 1986-12-22 | Hitachi Ltd | アルミニウム冷間鍛造用潤滑剤 |
DE69121808T2 (de) * | 1990-06-29 | 1997-04-03 | Tonen Corp | Hydraulik-, Schmier- und Kupplungsmittelzusammensetzung, die einen Organopolysiloxan und einen Phosphor enthaltenden Additiv enthält. |
JP2614149B2 (ja) * | 1991-03-11 | 1997-05-28 | 富士写真フイルム株式会社 | 新規アルキルホスフェート |
EP0510633A1 (en) * | 1991-04-24 | 1992-10-28 | Japan Sun Oil Company, Ltd. | Lubricating oil composition and use thereof |
JPH05302093A (ja) * | 1992-04-28 | 1993-11-16 | Tonen Corp | 潤滑油組成物 |
-
1995
- 1995-05-18 GB GBGB9510071.5A patent/GB9510071D0/en active Pending
-
1996
- 1996-05-16 CA CA002221309A patent/CA2221309A1/en not_active Abandoned
- 1996-05-16 TR TR97/01382T patent/TR199701382T1/xx unknown
- 1996-05-16 NZ NZ308145A patent/NZ308145A/xx unknown
- 1996-05-16 US US08/945,887 patent/US5824628A/en not_active Expired - Fee Related
- 1996-05-16 EP EP96914288A patent/EP0826023A1/en not_active Withdrawn
- 1996-05-16 BR BR9608766A patent/BR9608766A/pt not_active Application Discontinuation
- 1996-05-16 KR KR1019970708248A patent/KR19990014903A/ko not_active Application Discontinuation
- 1996-05-16 WO PCT/GB1996/001173 patent/WO1996036682A1/en not_active Application Discontinuation
- 1996-05-16 CN CN96195327A patent/CN1190427A/zh active Pending
- 1996-05-16 AU AU57697/96A patent/AU709312B2/en not_active Ceased
- 1996-05-16 JP JP8534642A patent/JPH11505283A/ja active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100500817C (zh) * | 2002-08-27 | 2009-06-17 | 新日本石油株式会社 | 润滑油组合物 |
CN1329491C (zh) * | 2003-12-30 | 2007-08-01 | 中国科学院兰州化学物理研究所 | 含膦酸酯官能团的离子液体及其制备方法和用途 |
Also Published As
Publication number | Publication date |
---|---|
KR19990014903A (ko) | 1999-02-25 |
CA2221309A1 (en) | 1996-11-21 |
WO1996036682A1 (en) | 1996-11-21 |
JPH11505283A (ja) | 1999-05-18 |
AU709312B2 (en) | 1999-08-26 |
GB9510071D0 (en) | 1995-07-12 |
AU5769796A (en) | 1996-11-29 |
TR199701382T1 (en) | 1998-03-21 |
US5824628A (en) | 1998-10-20 |
NZ308145A (en) | 1999-08-30 |
BR9608766A (pt) | 1999-07-06 |
EP0826023A1 (en) | 1998-03-04 |
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