CN1017156B - 酯类化合物润滑剂 - Google Patents
酯类化合物润滑剂Info
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Abstract
用通式1的酯类化合物作润滑剂,特别是用作牵引传动装置的润滑剂,式中R1、R2、R3、Cb、m和n的定义如说明书所述。
Description
本方法涉及使用某些酯类化合物作为润滑剂,特别是它们在牵引传动装置中的应用。
这些润滑剂能用于各种工程技术,在牵引传动装置中有特殊价值。广义上讲,牵引的定义是物体在其运动表面上的粘着摩擦。牵引传动装置是一种借助于接触部件之间的牵引,通过滚动作用所特有的所谓点或线接触使转矩从输入部件传递到输出部件的装置。通常说到牵引部件接触时,一般公认在其间存在着一种流体膜。几乎所有的牵引传动装置都需要流体以散热、防止接触面的磨损及润滑轴承和其他与传动有关的运动部件。因此,有一层流体膜被引入接触区域并介入金属部件之间,代替了金属与金属之间的滚动接触。这种流体的性质在很大程度上决定着传动效能的限度和传动能力。大多数牵引传动装置在设计中都采用牵引流体,该流体的牵引系数最好约在0.06以上,在40℃~-20℃温度范围内的粘度约为4~20,000毫帕斯卡秒,并有很好的耐热性及抗氧化性。该流体还应对普通结构材料无腐蚀作用,并具有很好的承载性能及低磨损率。
矿物(基)油对于牵引传动装置来说是相当差的润滑剂,因为一般它们的牵引(摩擦)系数很低,这就是说,对于施加在齿轮传动装置上的任何给定负荷来说,被摩擦轮传递的最大切向力是很低的。
现已发现,某些酯类化合物是极好的润滑剂和牵引流体。因此,本发明提供下面的通式Ⅰ的酯类化合物作润滑剂,特别是用作牵引流体:
式中Cb是羧基,它可以是如式-O-CO-或-CO-O-的单羧基(MCb),或是如式-O-CO-R4-CO-O-或-CO-O-R4-O-CO-的二羧基(DiCb),也可以是如式-O-CO-R5-CO-O-R6-O-CO-R5-CO-O-的四羧基(TCb);R4代表任意取代的亚烷基或亚烯基、C5-10亚环烷基、双(C5-10亚环烷基)或C5-10亚环烯基;R5代表亚烷基,最好是1,2-亚乙基,R6代表亚环烷基,特别是亚环己基;每个R3各代表C1-6烷基、C2-6烯基、C3-20单-或多环烷基、或者最好是氢原子;m和n各为0或1;R1代表任意取代的C4-10叔烷基(最好是叔丁基)或是任意取代的C3-8环烷基或C6-14双环或三环烷基;R2和R1相同,或代表任意取代的烷基、烯基、单-或多环烷基,单-或多环烯基;但假如m和n都是0,且Cb是MCb或DiCb时(其中的R是亚环己基),那么R1和R2不能都是环己基。
双环烷基和多环烷基是指任何含两个或两个以上环烷基的基团。多环烯基与多环烷基相似,但至少有一个不饱和碳-碳键。它们包括含稠环的基团,例如十氢化萘基、双环〔2,2,2〕辛基及金刚烷基。其它合适的稠环体系是基或冰片基。当R1和/或R2代表(双)环烷基时,它们最好是环己基、环戊基或十氢化萘基。
R1和R2可以含取代基。合适的取代基包括烷基,烯基,炔基,环烷基,环烯基,多环烷基,多环烯基,羟基,桥氧基,烷氧基,酰基,烷
氧羰基,环烷基烷氧羰基,环烷氧羰基,多环烷氧羰基,烷酰基氧基,环烷酰氧基,环烷基烷酰氧基,多环烷酰氧基及多环烷基烷酰氧基。当环烷基作为取代基时,环烷基部分可以含一个或一个以上的C烷基,特别是甲基。上述烷基、烯基、炔基及烷氧取代基宜含1~10个碳原子,最好含1~6个碳原子。环烷取代基最好是环己基或环戊基。多环烷基最好是十氢化萘基或是带有环烷基的环己基;酰基包括C1-6烷酰基。
R3基团最好是比较简单的部分,如甲基或氢原子,从而提供更易得到的、因此也是较便宜的产品。当m和n都是0时,牵引流体通常具有较高的牵引系数,因之有较好的效能。
当Cb指MCb、且R1代表叔烷基或(双)环烷基时,R2宜从任意取代的C1-10烷基、C2-20烯基及十氢化萘基中选择。这类化合物中较好的是其中R1是环己基、R2是C1-4烷基或被环己基酰氧基取代的C17烷基,或者R1及R2两者都代表环戊基的那些化合物。
分子式中含一个以上酯基的化合物即Cb是指DiCb或TCb的那些化合物,具有优良的牵引性能。特别有用的二羧基化合物是通式Ⅱ的
其中m和n两者都是0或1,R1和R2是相同的,各代表可以有C1-4烷基取代基的环戊基或环己基、十氢化萘基或叔丁基;R4的定义如上述,最好选自至多有3个碳原子把羧基隔开的基团。式Ⅱ的化合物中尤以式中R和R2都是环己基、R4是亚环己基、亚甲基、1,2-亚乙基,1,2-亚乙烯基或1,3-亚丙基的那些化合物为佳,这些基团可以含有一个或一个以上的C1-10烷基取代基和/或被环己基氧羰基、环己基甲氧羰基、新戊氧羰基或甲氧羰基取代的C1-20烷基或烯基部分。
较为可取的个别化合物是丙二酸、丁二酸或戊二酸的双环己酯,其中环己基部分或丙二酸酯基、丁二酸酯基或戊二酸酯基可以含一个或一个以上甲基取代基,因为这些化合物有很高的牵引系数。
已发现上述酯类化合物的粘度特性很适合用于摩擦轮齿轮传动装置(牵引传动装置),在这种应用中,它们可以和普通的油脂增稠剂混合。这种增稠剂可以是通常用于增稠矿物油使其达到润滑粘度的任何物质,包括有机的及无机的组分,例如金属皂、合成聚合物、有机硅氧烷、粘土、膨润土及胶态硅。用于牵引传动装置的化合物的粘度性质要适合于在-30到150℃之间操作。为此,本发明的润滑剂中的酯类化合物在40℃时的粘度至多为1000毫米2/秒,最好为250毫米2/秒,100℃时的粘度至少为1毫米2/秒,最好为3毫米2/秒。
这些化合物能在各种工程技术中作为润滑剂使用。因为上述酯类化合物在牵引传动装置中显示了优异的润滑效能,所以本发明还特别使用这些酯类化合物作为牵引流体,并用于把这些酯类作为牵引流体的牵引传动装置的操作。
本发明的酯类化合物本身能作为润滑剂使用。它们并能和其他润滑剂如矿物油或合成油混合,也可以在此种酯类化合物中加入各种添加剂,如Ⅵ改进剂,倾点下降剂、分散剂、去污剂及抗氧化剂等。
本发明所采用的某些酯类化合物是新型化合物。因此,本发明还提供了如上面的式Ⅰ那样的酯类化合物,但其附带条件是,当m和n都是0且Cb是DiCb时,R4不是-CH2-,-CH(CH3),-CH2CH2-或-CH2CH(CH3)-。
对于用作润滑剂的酯类化合物的所有优先选用情况对于新型酯类化合物本身也是适用的。
这些酯类化合物最好通过加热如下式的化合物
和如下式的醇
来制备。其中X是H或甲基,n、m、R1、R2及R3的定义如上。反应在强酸,例如对-甲苯磺酸、硫酸或盐酸存在下便于进行。反应宜在升温情况下进行,例如从50℃到200℃,最好是回流温度。当酯基转移作用是在与水或甲醇形成共沸物的共沸剂中进行时,酯化反应生成的水(或当X是甲基时生成的是甲醇)能用共沸方法除去。合适的共沸剂包括液体烃类,特别是苯,甲苯,二甲苯及其混合物。
当其中一个取代基是环己基环时,该化合物可由相应的含苯基化合物经加氢而得。进行加氢反应时可使用各种催化剂,如镍、铂、铑或钯。催化剂最好是载于如碳、二氧化硅、氧化铝、硅-铝等载体上使用。氢气在1~15巴的压力下,于50~250℃下通入含苯基的化合物中。可将含苯基的化合物溶于溶剂中,但也可不用溶剂。合适的溶剂包括甲酸及乙酸。
现用以下各实施例阐明本发明,其中,某些化合物的特点是其在546.1毫微米波长下测定的折射指数(RI)。
实施例:
制备了下列化合物:
(a)通式为
化合物 n Rx R2沸点
编号 (℃/mmHg)
(No)
1 0 - 甲基 183/758
2 1 - 甲基 201/750
3 0 - 乙基 194-196/759
4 0 2-甲基 乙基 203-204/753
5 1 - 乙基 95-97/11
6 0 - 环己基 105-110/1.5
7 1 - 环己基甲基 122-126/1.0
(b)通式为
化合物编号 m R1沸点(℃/mmHg)
(No) 或RI
8 0 甲基 172-173/760
9 0 乙基 RI1.4408
10 0 正丁基 RI1.4435
11 0 异丁基 RI1.4415
12 0 1-(11-环己基酰) 232-234/0.1
氧基)十七烷基
(c)通式为
化合物编号 n n′ R9沸点
(No) (℃/mmHg)
13 0 0 1,2-亚乙基 159-162/1,6-2.0
14 0 0 1-辛基-2-(7-甲氧 206-208/0.1
基羰基庚基)亚乙基
(d)通式为
的化合物
化合物 m m′ R10Ry Ry′ 沸点(℃/mmHg)
编号 或RI
(No)
15 0 0 亚甲基 - - 164/2.5
16 0 0 二甲基亚甲基 - - RI1.4659
17 0 0 1,2-亚乙基 - - 152-156/0.9
18 0 0 甲基亚乙基 - - RI1.4716
19 0 0 1,1-二甲基亚 - - RI1.4704
乙基
20 0 0 1,2-亚乙基 2-甲基 2-甲基 168-176/1.6-2.4
21 0 0 1,2-亚乙基 4-甲基 4-甲基 172-176/1.5-2.0
22 0 0 1,3-亚丙基 - - 177/186/2.2-3.8
23 0 0 1-〔1-(环己氧 - - >240/0.2
羰基)-十七烷-
10-基〕亚乙基
化合物 m m′ R10Ry Ry′ 沸点(℃/mmHg)
编号 或RI
(No)
24 1 1 1-〔1-(环己基 - - 286-310/0.2-0.3
甲氧羰基)十七
烷-10-基〕亚乙基
25 1 1 1-〔1-(环己基 - - 29.2-29.4/0.2
甲氧羰基)十七-
8碳烯-10-基〕
亚乙基
26 0 0 1,2-亚环己基 - - RI1.4909
27 0 0 1,2-亚环己基 甲基 甲基 RI1.4849
28 0 0 1,3-(1,2,2- 5-甲基- 5-甲基- RI1.4765
三甲基)-亚环 2-异丙 2-异丙
戊基 基 基
34 0 0 CH2CH25-甲基- 5-甲基- RI1.4712
2-异丙基2-异丙基 m.pt35℃
35 0 0 对-4,4′-亚 - - m.pt69℃
环己基
36 0 0 1,5-亚癸基 - - m.pt48℃
(e)通式为
化合物编号 R11沸点
(No) (℃/mmHg)
29 1,2-亚乙基 128-134/5-7
30 1〔1-(新戊氧羰基)-十七-8-碳烯238-255/0.15
-10-基〕亚乙烯基
(f)通式为
化合物编号 R12RI
(No)
31 1-〔1-(环戊基甲氧羰基)-十七-8-碳 RI1.4771
烯-10-基〕亚乙烯基
(g)通式为
化合物编号(No) R13沸点(℃/mmHg)
32 环戊基 70-72/0.8-1.0
(h)通式为
化合物编号(No) R14RI
33 2-异丙基-5-甲基环己基 1.4879
化合物编号(No)37:-
通式为
的化合物
化合物编号(No) X 物理性质
38 1,2-亚环己基 RI1.4851
39 1,3-亚环己基 RI1.4858
40 1,4-亚环己基 m.pt60℃
制备方法:
化合物1-11用标准方法制备:可在少量酸(如对甲苯磺酸)存在下(但不是必需的),将酸加入到适当的醇中,然后将混合物回流一段时间,用蒸馏方法把酯从醇中分离出来。
化合物12制备方法如下:
将环己醇(50毫升)和12-羟基硬脂酸及对甲苯磺酸(1克)在甲苯(200毫升)中回流,用共沸方法除去水,直到再也收集不到水时为止。将
溶液用碳酸氢钠及水洗涤,然后于旋转蒸发器中除去溶剂,产品是12-羟基硬脂酸环己酯。
将12-羟基硬脂酸环己酯(100克)溶于甲苯(250毫升)及吡啶(21克)中。将该溶液搅拌并加热至50℃。滴加环己烷羧酸酰氯(38.5克),使混合物温度升至70℃。滴加完毕后再使反应混合物于80℃下维持2小时。冷却后先用碳酸氢钠洗涤,再用水洗至中性。在旋转蒸发器中除去溶剂,并将残余物蒸馏,在232-234℃/0.1mmHg下收集的产品为12-环己酰氧基硬脂酸环己酯。
化合物13的制备方法如下:
在对甲苯磺酸(18.0克)存在下,把乙二醇(436克,7.0摩尔)和环己烷羧酸(1.83公斤,14.3摩尔)在甲苯(1升)中一起回流。所生成的水收集于迪安-斯达克榻分水器中(Dean and Start trap),并使反应继续进行到不再产生水时为止(14小时)。将溶液冷却,先用饱和碳酸氢钠溶液洗涤,再用饱和氯化钠溶液洗涤。
反应得到的双环己烷羧酸乙二醇酯(1.92公斤含量87.7%w/w,85.0%产率)是浅棕色油状物。
把粗产品进行减压蒸馏,于159-162℃/1.6-2.0mmHg下得到反应产物双环己烷羧酸乙二醇酯,为浅黄色油状物。(1.5升,气液色谱分析含量97.3%w/w)。
化合物14制备方法如下:
把9,10-二羟基硬脂酸(253克mp:91-92℃)置于含有对甲苯磺酸(1.3克)的甲醇(1500毫升)中回流10小时。5小时后加入浓硫酸(5克)。过滤反应混合物,并用旋转蒸发器除去溶剂。产物溶于二氯甲烷中,该溶液用碳酸氢钠溶液洗涤以除去残留的酸。除去溶剂后产品用石油溶剂由(b.p60-80℃)重结晶,过滤后用石油溶剂油洗涤并晾干。产量为210克,熔
点为70-71℃。
把9,10-二羟基硬脂酸甲酯(55.5克)溶于甲苯(200毫升)及吡啶(28克)中的溶液加热至50℃,在搅拌下滴加环己烷羧酸酰氯(50克),此时产生白色沉淀。滴加完毕后把反应混合物加热至80℃,并在此温度下搅拌2小时。冷却后用碳酸氢钠溶液洗涤,再用水洗至中性。用硫酸镁干燥,并除去溶剂。将残余物进行减压蒸馏,于355-258℃/0.08mmHg下收集产物。
化合物15-22的制备方法如下:
于对甲苯磺酸存在下,将酸和适当的醇在甲苯混合物中回流,酸与醇的摩尔比为1∶2,制备和操作程序如制备化合物13所述。
化合物25的制备方法如下:
于氮气保护下,将油酸甲酯(0.5摩尔)和马来酸酐(1.0摩尔)一起回流并搅拌。每隔一小时取样用气液色谱进行分析。8~10小时后的检验结果表明,90%以上的反应物在180℃到230℃之间发生了变化。冷却后,将产物溶于***中,再用水洗(20×50毫升),直至洗出液的pH从1升到4为止。将醚溶液在除去溶剂前用无水硫酸钠干燥,得到暗棕色粘稠液体产物。
将所得到的油酸甲酯/马来酸酐加成物溶于三倍体积的甲醇中,在浓硫酸(1%体积比)存在下回流6~8小时。在旋转蒸发器中除去甲醇,并加入***。将醚溶液用水、5%碳酸钠溶液及水洗涤,直至洗出液呈中性为止。将溶液干燥后在旋转蒸发器中除去溶剂,并将残余物进行蒸馏。
于沸点232-236°/0.8-1.0mmHg下收集到所需要的三甲酯,它是浅黄色油状物。
将用甲醇酯化油酸甲酯/马来酸酐加成物得到的产物溶于5倍体积的甲苯中,并在对甲苯磺酸存在下(酯重量的1%)与环己醇(过量50%摩
尔)一起回流。反应过程中不断把甲醇、甲苯和未反应的醇的混合物除去,但每隔一段时间又补充更多的甲苯及所需要的醇。如制备化合物13所述制得反应产物。粗产品于硅胶上用石油醚作洗脱剂进行洗脱以便离析产物。于旋转蒸发器中除去洗脱剂后即得到化合物25。
化合物23系通过化合物22的加氢得到,如“有机化学杂志(J.Org.Chem)1966,31,3989所述(G.A.Brown和H.C.Brown)。反应结束后,过滤反应混合物以除去催化剂,然后在旋转蒸发器中除去乙醇。将残余物溶于二氯甲烷中,用水及碳酸钠溶液洗涤,然后再用水洗至中性。将溶液干燥后在旋转蒸发器中除去溶剂得到化合物23。
化合物24用类似制备化合物23的方法制备,但用环己基甲醇代替环己醇。
化合物26的制备方法如下:升温将邻苯二甲酸二环己酯(1.0公斤,3.03摩尔)溶于冰醋酸(2.0升)中。溶液于90℃,6个大气压的氢气压力下,用载于碳(50克)上的5%铑进行加氢。48小时后停止反应,将催化剂过滤出,然后溶液再用载于碳(25克)上的5%的新鲜铑进行加氢反应(6小时),直至加氢反应完全。滤出催化剂将溶液在高真空下蒸发至60℃。将所得到的油状物溶于二氯甲烷(1升)中并依次用饱和碳酸氢钠溶液(1升)及水(1升)洗涤。用硫酸钠干燥后将有机溶液于高真空下蒸发至75℃,得到1,2-环己烷二羧酸双环己酯(914.4克,含量99.3%w/w,产率98.2%),是无色的油状物。
化合物27用类似制备化合物23的方法制备,但原料用邻苯二甲酸双-甲基环己基酯。
化合物28用5-甲基-2-异丙基环己醇酯化1,2,2-三甲基环戊烷-1,3-二羧酸来制备,方法类似于制备化合物15-22。
化合物29和30分别使用类似于制备化合物17和25的方法制备,用新戊
醇代替环己醇。
化合物31的制备方法同化合物25,但使用环戊烷甲醇。
化合物32的制备方法同化合物1-11,但使用环戊醇。
化合物33用5-甲基-2-异丙基环己醇和樟脑-3-羧酸制备,加工过程类似于制备化合物1。
摩擦系数的测定
所有的摩擦系数的测定均在一个双圆盘机上完成。硬质钢的圆盘被固定在两个轴的顶端,使彼此成切向接触。施加径向力使圆盘压在一起,负荷为0~200千克力(Kgf)。每个盘均用马达驱动。两个盘的转速不同,以便产生转差率。
在马达和携带检测试样的较低的轴之间装一指示传动摩擦转矩的测量装置。测量装置是一个摆式齿轮测力计,当有力传递时,摆就离开其竖直的平衡位置,其倾斜角的正弦即是转矩的大小。转矩的测量通过仪器设计及仪器尺寸预先标定。摩擦系数的定义为所测出的转矩除以径向力和较低圆盘的半径的乘积。
所用的两个圆盘直径都是50.0毫米,上盘厚3毫米,下盘厚10毫米。轴的最大转速为606转/分,平均切向(表面的)速度是1.48米/秒,所施加的转差率是9.1%。
所有测定均在环境温度(21℃±2℃)下进行。摩擦系数在负荷为50,100,150和200千克力下测定,这些负荷分别相当于赫兹应力(Hertzian Stresses)0.69、0.97、1.19及1.38吉帕斯卡(GPa)。
化合物的摩擦系数列于下表。
表中还列出了化合物的运动粘度。
从这些结果可以看出,特别是化合物15~22和26~28有很高的摩擦系数和极好的转递能力。
Claims (2)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8626510 | 1986-11-06 | ||
GB868626510A GB8626510D0 (en) | 1986-11-06 | 1986-11-06 | Ester compounds as lubricants |
Publications (2)
Publication Number | Publication Date |
---|---|
CN87107642A CN87107642A (zh) | 1988-05-18 |
CN1017156B true CN1017156B (zh) | 1992-06-24 |
Family
ID=10606881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN87107642A Expired CN1017156B (zh) | 1986-11-06 | 1987-11-04 | 酯类化合物润滑剂 |
Country Status (16)
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---|---|
US (1) | US4786427A (zh) |
EP (1) | EP0266848B1 (zh) |
JP (1) | JPS63139150A (zh) |
KR (1) | KR950014392B1 (zh) |
CN (1) | CN1017156B (zh) |
AT (1) | ATE60876T1 (zh) |
AU (1) | AU598315B2 (zh) |
BR (1) | BR8705936A (zh) |
CA (1) | CA1291984C (zh) |
DE (1) | DE3768024D1 (zh) |
ES (1) | ES2021021B3 (zh) |
FI (1) | FI91881C (zh) |
GB (1) | GB8626510D0 (zh) |
GR (1) | GR3001748T3 (zh) |
PT (1) | PT86073B (zh) |
ZA (1) | ZA878273B (zh) |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2618271B2 (ja) * | 1989-04-26 | 1997-06-11 | 日本化薬株式会社 | モノp―ニトロベンジルマロネートマグネシウム塩の結晶変態及びその製法 |
AU3321093A (en) * | 1991-12-19 | 1993-07-19 | Exxon Research And Engineering Company | Refrigeration working fluid |
US5306851A (en) * | 1992-11-23 | 1994-04-26 | Mobil Oil Corporation | High viscosity index lubricant fluid |
US5318711A (en) * | 1993-01-21 | 1994-06-07 | Quaker Chemical Corporation | Method for lubricating metal-metal contact systems in metalworking operations with cyclohexyl esters |
US5397488A (en) * | 1993-12-09 | 1995-03-14 | Mobil Oil Corporation | Oxidatively stable esters derived from diamondoids totally hydroxylated at the bridgeheads |
CN1037275C (zh) * | 1994-11-11 | 1998-02-04 | 西安近代化学研究所 | 聚氯乙烯用外润滑剂 |
WO1997021792A1 (fr) * | 1995-12-12 | 1997-06-19 | New Japan Chemical Co., Ltd. | Huile lubrifiante |
US6068918A (en) * | 1996-10-15 | 2000-05-30 | N.V. Bekhaert S.A. | Steel cord treated with a corrosion inhibiting composition |
US5998340A (en) * | 1997-03-07 | 1999-12-07 | Hitachi Maxell, Ltd. | Lubricant and magnetic recording medium using the same |
EP0949319A3 (en) * | 1998-04-08 | 2001-03-21 | Nippon Mitsubishi Oil Corporation | Traction drive fluid |
US6797680B2 (en) * | 2003-02-05 | 2004-09-28 | General Motors Corporation | Traction fluid with di-acid ester bridged dimer |
US6828283B2 (en) | 2003-02-05 | 2004-12-07 | Genberal Motors Corporation | Traction fluid with alkane bridged dimer |
DE10343623A1 (de) * | 2003-09-20 | 2005-04-28 | Celanese Chem Europe Gmbh | Carbonsäureester auf Basis von Limonanalkohol [3-(4'-Methylcyclohexyl)butanol] mit niedrigem Stockpunkt |
JP4938250B2 (ja) * | 2005-04-28 | 2012-05-23 | 出光興産株式会社 | 動力伝達用潤滑剤 |
US8586519B2 (en) * | 2007-02-12 | 2013-11-19 | Chevron U.S.A. Inc. | Multi-grade engine oil formulations comprising a bio-derived ester component |
US20110009300A1 (en) | 2009-07-07 | 2011-01-13 | Chevron U.S.A. Inc. | Synthesis of biolubricant esters from unsaturated fatty acid derivatives |
CN104058965B (zh) * | 2014-04-16 | 2015-09-16 | 上海通快实业有限公司 | 二聚酸聚酯及其制备方法和用该聚酯制备可降解微量切削油 |
JP6274326B2 (ja) * | 2014-12-08 | 2018-02-07 | 新日本理化株式会社 | トラクションドライブ用潤滑油基油 |
JP7242635B2 (ja) * | 2018-03-27 | 2023-03-20 | 出光興産株式会社 | 潤滑油基油、該潤滑油基油を含有する潤滑油組成物、及び該潤滑油組成物を用いた無段変速機 |
WO2021112946A1 (en) * | 2019-12-04 | 2021-06-10 | The Lubrizol Corporation | Use of ester base stocks to improve viscosity index and efficiency in driveline and industrial gear lubricating fluids |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417281A (en) * | 1944-11-10 | 1947-03-11 | Standard Oil Dev Co | Instrument lubricant |
US2817673A (en) * | 1952-08-01 | 1957-12-24 | Ruhrchemie Ag | Tricyclodecane esters |
US2824065A (en) * | 1955-05-20 | 1958-02-18 | Sun Oil Co | Lithium greases containing naphthenyl diesters |
US2849399A (en) * | 1956-04-09 | 1958-08-26 | Exxon Research Engineering Co | Improved lubricating composition |
US3296065A (en) * | 1963-10-07 | 1967-01-03 | Monsanto Co | Paper products containing carboxylic acid esters and process for preparing such products |
US3440894A (en) * | 1966-10-13 | 1969-04-29 | Monsanto Co | Tractants and method of use |
FR2041647A5 (zh) * | 1969-05-14 | 1971-01-29 | Inst Francais Du Petrole | |
US3835050A (en) * | 1971-05-13 | 1974-09-10 | Monsanto Co | Grease compositions having high tractive coefficients |
US3793203A (en) * | 1971-05-17 | 1974-02-19 | Sun Oil Co | Lubricant comprising gem-structured organo compound |
DE2713440A1 (de) * | 1977-03-26 | 1978-09-28 | Bayer Ag | Carbonsaeureester, deren herstellung und verwendung als basisschmieroel |
IT1123575B (it) * | 1979-09-10 | 1986-04-30 | Snia Viscosa | Esteri di alcoli polivalenti,procedimento per la loro preparazione e loro impiego quali oli lubrificanti |
DE3151938A1 (de) * | 1981-12-30 | 1983-07-07 | Optimol Oelwerke Gmbh | Traktionsfluessigkeit |
JPH0631366B2 (ja) * | 1986-01-31 | 1994-04-27 | 東燃株式会社 | トラクシヨンフル−ド |
JPS62177099A (ja) * | 1987-07-30 | 1987-08-03 | Toa Nenryo Kogyo Kk | トラクシヨン用フル−ド |
-
1986
- 1986-11-06 GB GB868626510A patent/GB8626510D0/en active Pending
-
1987
- 1987-10-22 CA CA000549970A patent/CA1291984C/en not_active Expired - Fee Related
- 1987-10-22 US US07/111,479 patent/US4786427A/en not_active Expired - Fee Related
- 1987-11-04 ZA ZA878273A patent/ZA878273B/xx unknown
- 1987-11-04 AU AU80672/87A patent/AU598315B2/en not_active Ceased
- 1987-11-04 JP JP62279015A patent/JPS63139150A/ja active Pending
- 1987-11-04 EP EP87202149A patent/EP0266848B1/en not_active Expired - Lifetime
- 1987-11-04 FI FI874871A patent/FI91881C/fi not_active IP Right Cessation
- 1987-11-04 BR BR8705936A patent/BR8705936A/pt not_active IP Right Cessation
- 1987-11-04 KR KR1019870012346A patent/KR950014392B1/ko not_active IP Right Cessation
- 1987-11-04 AT AT87202149T patent/ATE60876T1/de not_active IP Right Cessation
- 1987-11-04 PT PT86073A patent/PT86073B/pt not_active IP Right Cessation
- 1987-11-04 DE DE8787202149T patent/DE3768024D1/de not_active Expired - Lifetime
- 1987-11-04 ES ES87202149T patent/ES2021021B3/es not_active Expired - Lifetime
- 1987-11-04 CN CN87107642A patent/CN1017156B/zh not_active Expired
-
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Also Published As
Publication number | Publication date |
---|---|
CA1291984C (en) | 1991-11-12 |
ES2021021B3 (es) | 1991-10-16 |
AU598315B2 (en) | 1990-06-21 |
FI874871A (fi) | 1988-05-07 |
ZA878273B (en) | 1988-05-03 |
JPS63139150A (ja) | 1988-06-10 |
DE3768024D1 (de) | 1991-03-21 |
ATE60876T1 (de) | 1991-02-15 |
GB8626510D0 (en) | 1986-12-10 |
FI91881B (fi) | 1994-05-13 |
EP0266848A2 (en) | 1988-05-11 |
KR880006349A (ko) | 1988-07-22 |
EP0266848A3 (en) | 1988-10-05 |
FI874871A0 (fi) | 1987-11-04 |
PT86073B (pt) | 1990-11-07 |
KR950014392B1 (ko) | 1995-11-27 |
PT86073A (en) | 1987-12-01 |
US4786427A (en) | 1988-11-22 |
CN87107642A (zh) | 1988-05-18 |
BR8705936A (pt) | 1988-06-14 |
EP0266848B1 (en) | 1991-02-13 |
FI91881C (fi) | 1994-08-25 |
GR3001748T3 (en) | 1992-11-23 |
AU8067287A (en) | 1988-08-04 |
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