200413517 政、發明說明： 【發明所屬之技術領域】 本發明係、關於包括具有增進氧化安定 潤滑劑組合物。 馮层添加劑之 【先前技術】 包含減磨添加劑之潤滑劑組合物已悉知數 等組合物用作為潤滑齒輪油、 刀，μ 夕m 自動傳動液、滑道潤滑劑及 夕用^引機液。該等組合物用於降低摩擦，使發動機完 成自靜態至動態的平穩變換，同時降低噪音 動扭矩。 ·、、、& 口 其後，隨著節約燃料成爲一 王琛性問趨，局降低基礎油 蝻耗，開始將減磨添加劑引入汽 /飞早曲釉相潤滑劑以提高燃 料效率。在美國，共同平均燁 j十巧燃枓經潸（cafe)法規也向原始 設備製造商（0EM，S)施加額外麼力促使其提高燃料效率。 隨著在全世界Μ車輛廢氣排放法規，對降低 摩擦的要求進-步增強。此是因爲吾人理解到發動機内燃 枓燃燒所産·生能量中20_25%消耗在摩擦上；其中大部分消 耗在活塞襯墊與活塞環的介面摩擦上，少部分消耗在軸承 與氣闕機構上。據預測，在將來的發動機中，活塞群所產 生的發動機摩擦將增至50%。 吾人認爲降低燃料消耗與排放的—種方法是選用適宜之 發動機潤滑劑組合物。發動機内幾個部件産生摩擦，該等 部件在不同負載、速度及溫度條件下工作。因此該等組合 物在發動機運行過程中可能經歷（黏彈性）流體動力、混合與 87883 邊界潤滑之不同組合。在 發動機摩擦。 α “、、狀況中，很多因素將影響 經過對該等因素之研究，基本確定主 降低摩擦及節約燃料。第—*可以 、、& 弟種方案爲當液體潤滑（（黏彈性） :軸 定因素時使用低黏度機油。該液體潤滑 粗別普遍。經過幾年逐步降低機油黏度，燃 :即、力效果顯著。第二種方案爲當邊界及/或混合潤滑爲決 疋口素4加人減磨劑。在氣閥機構與活塞群中該等因素爲 主要因素。在該情況下，添加劑系統的設計變得非常重要 。該種方案的重點爲對減磨添加劑的選擇與對添加劑/添 加劑以及添加劑/基液間相互作用的控制。 目所所應用之減磨添加劑在化學上主要界^爲三類，分 別爲有機、金屬有機及不溶於油之減磨添加劑。有機減磨 添加劑又進-步主要分成四類，其爲叛酸或其衍生物，其 包括以下一些實例：部分酯（partial ester);含氮化合物， 諸如醯胺、醯亞胺'胺及其衍生物；磷酸或次磷酸衍生物 ，及有機聚-合物。目前市售減磨添加劑之實例爲單油酸甘 油酯（glycerol monooleate)與油醯胺（oleyiamide)。 之 US 4,208,293揭示一種適於用作内燃機的曲轴箱潤滑劑 潤滑油’該潤滑油包括0·05至5 wt%之二乙醇胺之g旨或脂 肪酸醯胺（fatty acid amide)作爲減磨添加劑。較佳之脂肪酸 爲不飽和脂肪酸’尤以油酸爲最佳。 GB 2，0 3 8，3 5 6揭示於曲軸箱潤滑油中加入〇 ·2 5至2 wt%之 脂肪酸甘油S旨（fatty acid ester of glycerol)。較佳脂肪酸酉旨 87883 200413517 爲單油酸甘油酯與動物油甘油酯（glycerol tallowate)(牛脂 肪/油含有約40至45%之不飽和脂肪酸）。但其中並未揭示該 脂肪酸甘油醋所具有之經基值。 GB 2,097,813揭示於汽油與柴油機所用之潤滑油調配物 中加入0·05至0.2 wt%之C16-18脂肪酸之甘油部分醋 (glycerol partial ester)作爲燃料節約添加劑。其亦未揭示甘 油部分酯所具有之羥基值。該專利所述之實例中，製得該 酯之脂肪酸爲單油酸甘油酯或單油酸甘油酯與二油酸甘油 酯之混合物。 US 4,3 04,678揭示於内燃機所用之潤滑油組合物中添加 至4wt%(較佳爲2至4wt%)之燃料節約添加劑，該燃料節贫 添加劑選自下列以下之部分酷：單油酸甘油，、二油酸甘 油酯 '單油酸山梨糖醇酐s|、單月桂酸山梨糖醇野酿 _〇laur帅及完全醋化之頻果酸二異硬脂基酷 (diiS〇Stearyl㈣則與酒石酸二異硬脂基醋（dHSosteary丨 tartrate)對於所選用之大部分節約燃料添加劑（意 不專利中並未揭示每種添加劑所具有之經基值 μ “基醋與酒石酸二異硬脂基，不含有游離 二基;在。貫例中，當存在2%，與4%時， 百/比V-8發動機燃料效益。單油酸甘㈣加入量 局1 /〇日^又有對應的燃料效益。 在要求節約燃料的開始階 on)上，此階段爲滿足該要 /放在新鮮油（fresh 而現在則已開發出亦將解 ：：：業減磨添加劑’ ” +即、力哥命（i〇ngevity)問題 87883 200413517 之新機油規格。Sequence VI-Β測試即爲一有力實例，其是 爲ILSAC GF-3規格而開發之發動機測試。Sequence 包 括1 6至80小時之老化階段，以測定燃料節約度及燃料節約 壽命。該等老化階段與實施EPA(美國環保署）地鐵/公路節 油測試前所要求之累計行駛40〇〇-6〇〇〇公里等效（equivalent) 。EPA地鐵/公路節油測試用於決定車輛CAFE參數。 爲獲取具有最佳燃料節約壽命之機油調配物，將把需求 目私放在對基礎油的選擇及添加劑系統的設計上。該等目 標即爲儘量減小黏度的增大，從而使其在（黏彈性）流體動力 狀况下保持低摩擦係數，且在邊界與混合潤滑狀況下保持 低摩擦度。 藉由（根據黏度、氧化安定性及抗氧化劑敏感性）選用合適 的基礎油，及藉由選用抗氧劑及其處理程度（lad)可以降 低在（黏彈性）流體動力狀況下隨時間推移出現之黏度增大 或使其最小化。 爲在邊界與混合潤滑條件下達成低摩擦度，有必要應用 有^:的減磨j加劑。爲長時間保持較低邊界與混合摩擦度 、’/必須避免由於諸如氧化及熱分解等過程而引起的添加劑 消耗口此減磨添加劑之開發關鍵在於使其具有高熱/氧化 安定性’彳可以滿足長燃料節約壽命之新要求，且才能成 功地用於機油調配物中。 J研九1現，藉由對燃料本身添加減磨添加劑可以進 v ^约砧料。咸信燃料將減磨添加劑帶至已知摩擦很大 m衣k壁間介面’且用油量被控制在低水平。此外， 87883 200413517 已务現，隨著機油中燃料所攜帶之減磨添加劑的累積，油 潤滑部分之摩擦亦被減小。 已揭不‘油燃料中添加劑之存在將結合在現代發動機設 計之燃料系統中增大喷射壓力，來解決由於硫化合物的降 低及燃料的加氫處理而造成的燃料潤滑能力降低問題。 例如，US 5,993,498揭示一種多元醇酯燃料添加劑，該添 加劑用於在餾出燃料之應用中增強燃料潤滑能力，餾出燃 料選自下列各物組成之群：柴油、煤油、喷氣燃料及其混 β物夕元醇酯具有5至180(較佳爲5至140)之輕基值。多元 醇酯由多元醇與支鏈或線性飽和單羧酸反應而得，或多元 醉與多元酸及單醇（mon〇alc〇h〇1)反應而得。#乡元醇醋由 夕元醇與單羧酸反應製得時，線性單羧酸具有1 〇碳原 子爲較佳，支鏈單羧酸具有C5_cl〇碳原子爲較佳。 同時，EP 0680506 A1揭示於柴油燃料中加入具有2-5〇個 碳原子的羧酸與含有至少一個碳原子的醇形成之酯，來解 決由於柴油燃料中含硫量低而引起的燃料潤滑能力降低及 發動機磨損·問題。其被認為燃料中添加劑含量較低，例如 以重量計占單位燃料重量之1〇·2〇〇 ppm。所列舉之酯實例 舄甘油單及二酯。該專利沒有明確揭示酯類添加劑所含有 之基數。 EP 0859040 A1揭示於含有消泡添加劑及過鹼化 (—based)金屬清潔劑的柴油燃料中加入潤滑添加劑，以 此改吾含有該消泡添加劑及過鹼化金屬清潔劑之組合的柴 油之發泡性能。通常，該潤滑添加劑加入量爲1()至伽_ 87883 -10- 200413517 ，其中以20至100 ppm更佳。較佳之潤滑添加劑爲叛酸、羧 酸胺與叛酸西旨。尤以單萬麻酸甘油酿（glycerolmonoricinoleate) 爲最佳。 WO 98/11 1777 A1揭示於汽油燃料中加入部分醋化之多 元醇酯燃料添加劑’以增強對進氣閥與燃燒室沈積物的控 制’並降低燃料管路、燃燒室及活塞/氣缸總成中的磨損與 摩擦。部分自旨化之多元醇具有5至約18()之經基值。該發明 還提供了關於含有經基值為223之油酸甘油醋（_Γ〇1 oleate)混合物之酉旨的對照實 <列。該發明所述之西旨由至少一 種支鏈或線性餘和酸與多元醇反應製得爲較佳。對於此較 佳之醋而言，較佳之線性酸具有C2_ci〇碳原子，且較佳之 支鏈酸具有C5- C10碳原子。 目前市諸動機減磨添加髮不能很好地滿足上述對盆 在燃料節約度及燃料節約壽命兩方面的要求。吾人孰知單 油酸甘油_與油醯胺長時間應用容易被氧化分解。此外， 使用油醯胺的另一個缺毀曰 、 力1口缺點疋油醯胺與目前所使用的調配基 也由（基礎▲加上其他添加劑）相容性較差。 令吾人驚料是，已發現特㈣用之多S醇1旨既可以滿 足對減磨添加劑在4 + d在乳化女疋性方面的新要求，又不降低豆 =磨之性能。同時’該添加劑在發動機運行溫度下與調配 原油完全相容。 【發明内容】 本發明之潤滑劑組合物用於燃料、 要包括燃料或基礎油，及⑽之㈣之減磨添加劑。 87883 200413517 :減磨：加劑包括經基值至少達180之多元醇@旨，該多元醇 酉曰口由-經f基丙貌與碳鏈長度爲⑺至個碳原子之至少一 種單羧酸部分酯化而製得。 該至少—種單_以完全飽和酸爲較佳，亦可以含高達 训之不飽和度，例如，椰子油，其中含有至多12%之不飽 和^ ^至少一種單竣酸之碳鏈可以爲直鏈或支鏈，或包 3曰矢衣（aliphatic nng)。較佳之碳鏈長度爲12至22個碳原 子二更佳爲14至20個碳原子，且尤其爲以個碳原子。合適 之早竣酸貫例包括：椰子脂肪酸、月桂酸、肉豆謹酸、棕 櫚酸、硬脂酸、異硬脂酸、氯化⑶單體酸、d8單體酸、 十一烷酸、二十二烷酸（behenic acid)與二十四烷酸 (lign〇cenc acid)及其混合物。氫化ci8單體酸是油酸二聚之 =產物C18單體’其接著經氫化。⑶單體酸即爲副産物⑴ 單體本身’通常其不飽和度約爲20%。 潤滑劑組合物之基礎油可以選自下列所組成之群：礦物 油、聚α-浠烴、烧基苯、單醋、二_、多元醇醋、混合_ 、聚亞烧基-二醇及其混合物。較佳之基礎油包括礦物油或 聚-稀煙。 在调滑劑組合物中’根據本發明之減磨添加劑含量爲 至2重’車父佳爲〇」至18% ’更佳爲〇。至丄篇。 爲便於調配低黏度節能油，應對所用基礎油i 〇〇c>c下之運 動黏度（kinematic viscosity)加以選擇。1〇〇t下之基礎油運 動黏度較佳爲丨至]。，更佳爲3至8，最佳爲4至6“卜 減磨添加劑經基值至少達丨80，並較佳以25〇爲上限。特 87883 -12- 200413517 別較佳之範圍爲190至240，尤其爲2〇〇至24〇。 潤滑劑組合物還可以包括具有吾人熟知之官能度的其他 添加劑，该等添加劑占潤滑劑組合物總重量之1 〇至， K土爲12至18% ’尤佳爲14至16%。合適之添加劑包括：清 办Μ、分散劑、抗磨劑/極壓（extreme pressure)添加劑、黏 度改貝劑、抗腐蝕添加劑、消泡劑、傾點下降劑（p⑽r p〇int depressant)及其類似物。 、'、根據本發明之另一實施例，其係關於潤滑劑組合物在燃 ;斗枯1 ’由及/或傳動油中之應用，該潤滑劑組合物之主要組 份包括：燃料或基礎油，及〇.〇5至2〇重量％之減磨添加劑 =減磨添加劑包括㈣值至少達180之多元醇醋，該多元 醇-曰由一 L曱基丙少元與碳鏈長度爲10至24個碳原子之至少 一種單羧酸部分酯化反應而得。 、本發明所述之燃料指汽油與柴油燃料，所述之機油指汽 油舁木油（包括重型柴油）機油，傳動油指自動裝置、齒輪、 後軸與連續變速傳動油。200413517 Policy and invention description: [Technical field to which the invention belongs] The present invention relates to a lubricant composition having an improved oxidation stability. Feng layer additives [prior art] Lubricant compositions containing anti-friction additives have been known to be used as lubricating gear oils, knives, μxm automatic transmission fluids, slide lubricants, and engine fluids. . These compositions are used to reduce friction and allow the engine to perform a smooth transition from static to dynamic while reducing noise dynamic torque. · ,,, & Later, as fuel saving became a priority, Chen Chen reduced the consumption of base oil and began to introduce anti-friction additives into steam / fly early curve glaze phase lubricants to improve fuel efficiency. In the United States, the common average (ca) regulations also apply additional forces to original equipment manufacturers (OEMs, S) to improve fuel efficiency. With M vehicle exhaust emissions regulations worldwide, the demand for friction reduction has increased. This is because I understand that 20_25% of the energy produced by the internal combustion engine and the combustion of the engine is consumed in friction; most of it is consumed in the friction between the interface between the piston pad and the piston ring, and a small part is consumed in the bearing and the air valve mechanism. It is predicted that in future engines, the engine friction generated by the piston group will increase to 50%. I think one way to reduce fuel consumption and emissions is to choose a suitable engine lubricant composition. Friction occurs in several components within the engine, which work under different load, speed, and temperature conditions. Therefore these compositions may experience different combinations of (viscoelastic) hydrodynamics, mixing, and 87883 boundary lubrication during engine operation. Friction in the engine. α ", in the situation, many factors will affect the research on these factors, and basically determine the main reduction of friction and fuel savings. The first-* can ,, & the second solution is when the liquid lubrication ((viscoelastic): shaft Low viscosity engine oil is used for certain factors. This liquid is widely used for lubrication. After several years, the viscosity of the oil is gradually reduced, which means that the effect of force is significant. The second option is when the boundary and / or mixed lubrication is 4%. Human anti-wear agent. These factors are the main factors in the valve mechanism and piston group. In this case, the design of the additive system becomes very important. The focus of this solution is the choice of anti-wear additive and additive / Additives and control of additives / base fluid interactions. The antifriction additives used in the project are mainly divided into three categories in the chemical industry: organic, metal organic and oil-insoluble antifriction additives. Organic antifriction additives are The further steps are mainly divided into four categories, which are meta-acids or their derivatives, which include the following examples: partial esters; nitrogen-containing compounds, such as ammonium, ammonium'amine, and Derivatives; Phosphoric acid or hypophosphorous acid derivatives, and organic poly-complexes. Examples of currently available friction reducing additives are glycerol monooleate and oleyiamide. US 4,208,293 discloses a suitable Used as a crankcase lubricant lubricating oil for an internal combustion engine. The lubricating oil includes 0.05 to 5 wt% of diethanolamine or fatty acid amide as a friction reducing additive. A preferred fatty acid is an unsaturated fatty acid. Oleic acid is the best. GB 2,0 3 8, 3 5 6 reveals that 0.2 to 2 wt% fatty acid glycerol is added to the crankcase lubricant. Preferred fatty acids Purpose 87883 200413517 is glycerol monooleate and glycerol tallowate (tallow fat / oil contains about 40 to 45% unsaturated fatty acids). However, the base value of the fatty acid glycerol vinegar is not disclosed. GB 2,097,813 discloses the addition of 0.05 to 0.2 wt% of glycerol partial ester of C16-18 fatty acid as a fuel saving additive in the lubricant formulations used in gasoline and diesel engines. It is also undisclosed The glycerol partial ester has a hydroxyl value. In the example described in this patent, the fatty acid from which the ester is prepared is glyceryl monooleate or a mixture of glyceryl monooleate and glyceryl dioleate. US 4,3 04,678 discloses A fuel saving additive is added to the lubricating oil composition used in the internal combustion engine to 4 wt% (preferably 2 to 4 wt%). The fuel saving additive is selected from the following: cooler glycerol, glycerol dioleate Ester 'sorbitan monooleate | Sorbitol monolaurate berry_〇laur Shuai and fully vinegared diisostearyl dicarboxylic acid (diiS0Stearyl㈣ and diisostearyl tartrate Vinegar (dHSosteary 丨 tartrate) for most of the selected fuel-saving additives (the Italian patent does not disclose the base value of each additive μ "based vinegar and diisostearyl tartaric acid, does not contain free diyl; in. Conventionally, when 2% and 4% are present, the fuel efficiency of the V-8 engine is 100% / ratio. The amount of glycerol monooleate added to the board was 1/0 day ^ and there was corresponding fuel efficiency. At the beginning of the request for saving fuel, at this stage, in order to meet the requirements of / put in fresh oil (fresh and now it has been developed and will also solve the ::: industry anti-friction additives' ”+ namely, Lige Ming (i 〇ngevity) Issue 87883 200413517 for the new oil specification. The Sequence VI-B test is a powerful example, which is an engine test developed for the ILSAC GF-3 specification. The Sequence includes an aging period of 16 to 80 hours to determine fuel Conservation and fuel-saving life. These aging stages are equivalent to the cumulative travel of 40,000-66,000 kilometers required before the EPA (U.S. Environmental Protection Agency) subway / highway fuel economy test. EPA subway / highway The fuel-saving test is used to determine the vehicle CAFE parameters. In order to obtain the oil formulation with the best fuel-saving life, the demand will be privately focused on the selection of the base oil and the design of the additive system. These goals are to minimize The increase in viscosity allows it to maintain a low coefficient of friction under (viscoelastic) hydrodynamic conditions and low friction under boundary and mixed lubrication conditions. By (according to viscosity, oxidation Qualitative and antioxidant sensitivity) Use of suitable base oils, and the use of antioxidants and their degree of treatment (lad) can reduce or minimize the increase in viscosity that occurs over time under (viscoelastic) hydrodynamic conditions In order to achieve low friction under boundary and mixed lubrication conditions, it is necessary to apply the anti-friction additive of ^ :. In order to maintain low boundary and mixed friction for a long time, '/ must be avoided due to factors such as oxidation and thermal decomposition. Additive consumption caused by other processes The key to the development of this antifriction additive is to make it have high thermal / oxidative stability, which can meet the new requirements of long fuel saving life and can be successfully used in engine oil formulations. J 研 九1 Now, by adding anti-friction additives to the fuel itself, it can be used as a raw material. Xianxin Fuel will bring the anti-friction additives to the known interface with high friction, and the oil consumption is controlled at a low level. In addition, 87883 200413517 has been realized. With the accumulation of antifriction additives carried by fuel in engine oil, the friction of the oil lubricating part is also reduced. Increasing the injection pressure in a fuel system that will be incorporated in modern engine design to solve the problem of reduced fuel lubricating capacity due to the reduction of sulfur compounds and the hydroprocessing of the fuel. For example, US 5,993,498 discloses a polyol ester fuel additive, The additive is used to enhance the lubricating ability of the fuel in the application of distillate fuel. The distillate fuel is selected from the group consisting of diesel, kerosene, jet fuel and its mixed beta compounds. It is a light base value of 5 to 140). Polyol esters are obtained by reacting a polyol with a branched or linear saturated monocarboxylic acid, or by reacting a polyhydric alcohol with a polyacid and a monoalcohol (monoalcohol). . When #xiangyuan alcohol vinegar is prepared by reacting xiyuan alcohol with a monocarboxylic acid, it is preferable that the linear monocarboxylic acid has a carbon atom of 10, and the branched monocarboxylic acid has a carbon atom of C5_cl0. At the same time, EP 0680506 A1 discloses the addition of an ester of a carboxylic acid having 2 to 50 carbon atoms and an alcohol containing at least one carbon atom to a diesel fuel to solve the fuel lubricating ability caused by the low sulfur content in the diesel fuel. Reduction and engine wear and problems. It is considered to have a low content of additives in the fuel, such as 10.2 ppm by weight per unit fuel weight. Examples of listed esters 舄 Glycerol mono- and diesters. The patent does not explicitly disclose the number of bases contained in the ester additives. EP 0859040 A1 discloses the addition of a lubricating additive to a diesel fuel containing a defoaming additive and an overbased metal cleaner, thereby improving the development of diesel fuel containing a combination of the defoaming additive and an overbased metal cleaner. Bubble performance. Generally, the amount of the lubricating additive is 1 () to 87883-10-200413517, and more preferably 20 to 100 ppm. The preferred lubricating additives are meta-acid, carbamate, and meta-acid. Especially glycerol monoricinoleate is the best. WO 98/11 1777 A1 discloses the addition of partially acetated polyol ester fuel additives to gasoline fuel to 'enhance control of intake valve and combustion chamber deposits' and reduce fuel lines, combustion chamber and piston / cylinder assembly Wear and friction in Partially customized polyols have a base value of 5 to about 18 (). The invention also provides a comparative example < column for the purpose of containing a mixture of glycerol oleate (_Γ〇1 oleate) with a base value of 223. The purpose of the invention is preferably obtained by reacting at least one branched or linear co-acid and a polyhydric alcohol. For this better vinegar, the preferred linear acid has C2-Cio carbon atoms, and the preferred branched acid has C5-C10 carbon atoms. At present, the various motives in the city for friction reduction and addition cannot meet the above requirements of the basin in terms of fuel economy and fuel saving life. We do not know that glycerol monooleate and oleamide are prone to oxidative decomposition when used for a long time. In addition, another disadvantage of using oleamide is that it has a shortcoming. The oleamide has poor compatibility with the currently used formulations (basic ▲ plus other additives). To my surprise, it has been found that the use of special S alcohol 1 can meet the new requirements for emulsification of nucleus in 4 + d without reducing the performance of soybeans. At the same time, the additive is completely compatible with the blended crude oil at the operating temperature of the engine. [Summary of the Invention] The lubricant composition of the present invention is used for a fuel, which includes a fuel or a base oil, and a friction reducing additive. 87883 200413517: Anti-friction: Additives include polyols with a base value of at least 180 @ the purpose of the polyol is-at least one monocarboxylic acid with a f-based structure and a carbon chain length of ⑺ to 1 carbon atom. Partially esterified. The at least one kind of mono-saturated acid is preferably a fully saturated acid, and may also contain a high degree of unsaturation, for example, coconut oil, which contains up to 12% of unsaturation ^ ^ The carbon chain of at least one mono-acid may be straight Chain or branched chain, or package 3 (aliphatic nng). The preferred carbon chain length is 12 to 22 carbon atoms, more preferably 14 to 20 carbon atoms, and especially 1 carbon atom. Examples of suitable early completion acids include: coconut fatty acids, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, chlorinated CD monomer acid, d8 monomer acid, undecanoic acid, dicarboxylic acid Behenic acid and lignocenc acid and mixtures thereof. The hydrogenated ci8 monomer acid is the dimerization of oleic acid = product C18 monomer 'which is then hydrogenated. (3) The monomer acid is a by-product. The monomer itself 'usually has an unsaturation of about 20%. The base oil of the lubricant composition may be selected from the group consisting of mineral oil, poly-α-fluorene, benzene, benzene, vinegar, diacetate, polyhydric alcohol vinegar, mixed acetone, polyalkylene glycol, and Its mixture. Preferred base oils include mineral oil or poly-lean smoke. In the slip composition, the content of the "wear reduction additive according to the present invention is from 2 to 2", and "from 0 to 18%", more preferably from 0. To the article. In order to facilitate the deployment of low-viscosity energy-saving oils, the kinematic viscosity of the base oil i 〇c &c; c should be selected. The kinematic viscosity of the base oil at 100 t is preferably 丨 to]. , More preferably from 3 to 8, most preferably from 4 to 6 "The friction reducing additive has a base value of at least 丨 80, and preferably an upper limit of 25. Special 87883 -12- 200413517 A particularly preferred range is 190 to 240 , Especially from 200 to 24. The lubricant composition may also include other additives with functionalities that are well known to us, such additives account for 10 to 18% of the total weight of the lubricant composition, and K to 12 to 18%. Especially preferred is 14 to 16%. Suitable additives include: cleansing agent, dispersant, anti-wear agent / extreme pressure additive, viscosity modifier, anti-corrosive additive, defoamer, pour point depressant ( p⑽r p〇int depressant) and the like. According to another embodiment of the present invention, it relates to the application of a lubricant composition in a fuel; The main components of the composition include: fuel or base oil, and 0.05 to 20% by weight of anti-wear additive = anti-wear additive including polyol vinegar having a threshold value of at least 180, said polyol-said by one L Fluorenyl propionate and at least one monocarboxylic acid moiety having a carbon chain length of 10 to 24 carbon atoms Obtained reaction. The fuel of the present invention refers to a gasoline and diesel fuel, gasoline refers to the oil of the oil lift wood (including heavy duty diesel) engine oil, transmission oil refers to automatic devices, gear, continuously variable transmission oil and rear axle.
【實施方式J 將 >、考下文所列舉之實施例與圖式僅以實例之方式進一 乂七田述本發明。其中，圖1爲實例3所得結果之圖形表示， 且圖2爲實例5所得結果之圖形表示。 實例1 =用以下方法測試汽油機油中減磨添加劑之氧化安定性·· ’感應：間以分鐘計’感應時間即爲減磨添加劑開始發生 乳化之時間，不同減磨添加劑之感應時間採用差示掃描量 87883 -13- 200413517 熱法（DSC)^測，每種減磨添加劑中含〇·5重量％之抗氧化劑 (Clba專業化學品公司生産之Irgan〇x L1丨^以型），差示掃 ^里熱儀爲具Mettler TC 15 TA控制器之MeUler dSc27HP 型。量測條件爲·· 起始溫度：3 0。〇 加熱速度：50t:/分鐘直至170它之測試溫度 氣壓：40巴（bar) 氣流：50毫升/分鐘 樣品量：5+/-0.4毫克 坩堝：鋁質，40微升 量測結果如下表1所示： 表1 減磨添加劑 二沒甲基丙烧單-單體酉旨（trimethy〇lpr〇pane mono-monomerate) 感應時間(分鐘） 59 三羥甲基丙烷C12/C14酸酯 144 油醯胺（對照） 11 單油酸甘油醮（對照） 4 三羥曱基丙烷單-單體酯由莫耳濃度過量的三羥曱基丙 烷與氫化C18單體酸部分酯化而得，其羥基值爲186。該産 物爲酯之混合物，其中實際三羥甲基丙烷單_單體酯含量約 40% 〇 一沒甲基丙烧Cl 2/C14酸酯由三經甲基丙燒與1:1莫爾比 的月桂酸與肉豆蔻酸之混合物部分酯化而得，其經基值爲 87883 -14- 218。 218。200413517 表1中數據清楚說明，與所列市售減磨添加劑相比，本發 明減磨添加劑氧化安定性明顯更高。 實例2 含0.5重量％之減磨添加劑之潤滑劑組合物的摩擦係數採 用銷-環型（pin-on-ring)摩擦計量測，量測溫度範圍40至140 t。摩擦計環爲730毫米直徑之100Cr6不銹鋼環，且摩擦計 銷爲8毫米直徑之同材料製成的圓柱，銷具有可撓性端部， 因此各端可輕度彎曲，以便於與環完全對準。所施加之負 載爲100N，且旋轉速度爲0.03公尺/秒鐘，以確保系統在邊 界潤滑條件下運行。量測結果如表2所示，其中基於1 -癸烯 之氫化寡聚物之OW/30油為調配之基礎油（baseline oil)(機 油）〇 表2 調配之基礎油 0W/30 0W/30 0W/30 0W/30 減磨添加劑 未力σ 單油酸甘油酉旨 (對照） 油醯胺 (對照） 三羥甲基丙烧單-單體酯 (40%) 溫度 摩擦係數 摩擦係數 摩擦係數 摩擦係數 [°C] 40 0.1368 0.1066 0.1110 0.1139 50 0.1395 0.1063 0.1110 0.1166 60 0.1410 0.1098 0.1146 0.1180 70 0.1426 0.1140 0.1134 0.1190 80 0.1436 0.1154 0.1105 0.1194 90 0.1442 0.1164 0.1093 0.1190 87883 -15 - 200413517 100 0.1445 0.1164 0.1078 0.1187 110 0.1449 0.1173 0.1071 0.1182 120 0.1456 0.1195 0.1078 0.1179 130 0.1466 0.1227 0.1090 0.1174 140 0.1545 0.1302 0.1119 0.1172 表2中數據清楚說明，本發明之減磨添加劑與吾人熟知之 單油酸甘油酯及油醯胺相比具有相近之減磨能力。儘管與 吾人熟知之減磨添加劑相比，本發明之減磨添加劑具有更 強之氧化安定性（如實例1中所示），但其氧化安定性並未影 響其減磨性質。 實例3 針對二個具有不同羥基值之TMP C12/C14酸酯之樣品重 複實例2。量測中所使用之CEC RL 179/2調配之基礎油爲歐 洲燃料節約測試所用之5 W-30校準油。量測結果如表3及圖1 所示。 表3 調配之基 礎油 CECRL 179/2 CEC RL 179/2 CEC RL 179/2 減磨添加劑 未加 三羥甲基丙烷C12/C14 酸酯 (羥基值92)(對照） 三羥曱基丙烷C12/C14 酸酉旨 (羥基值218) 溫度 摩擦係數 摩擦係數 摩擦係數 [°C] 40 0.1077 0.1030 0.0995 50 0.1147 0.1076 0.1048 87883 -16- 200413517 __60 0.1177 0.1105 0.1070 70 -—---- 0.1185 0.1135 0.1083 80 --—---__ 0.1191 ------ 0.1161 0.1100 90 0.1199 0.1171 0.1121 100 --—-- 0.1221 0.1190 0.1145 110 0.1245 0.1211 0.1182 120 0.1273 0.1244 0.1241 130 —----- 0.1349 0.1293 0.1307 140 0.1353 0.1284 0.1353 圖1中最上面一條曲線代表未加入減磨添加劑，中間曲線 代表三經甲基丙烷C12/C14酸酯對照樣品，最下面之曲線代 表根據本發明之三羥甲基丙烷^^^斗酸酯。 表3與圖1清楚說明，羥基值至少達18〇之減磨添加劑舆具 有車乂低.基值之減磨添加劑相比摩擦係數減小。 實例4 〇·5重里％之二羥甲基單·單體酯減磨添加劑與調配 之基礎油之’谷性採用以下方法量測。將減磨添加劑加至 調配之基礎油中，並將曰 η I將所付化合物冷卻至-10°C。該混合物[Embodiment J] The present invention will be further described by way of example with reference to the examples and drawings enumerated below. Among them, FIG. 1 is a graphical representation of the results obtained in Example 3, and FIG. 2 is a graphical representation of the results obtained in Example 5. Example 1 = Test the oxidation stability of antifriction additives in gasoline engine oil by the following method: "Induction: in minutes" The induction time is the time when the antifriction additives begin to emulsify, and the induction time of different antifriction additives is different. Scanning amount 87883 -13- 200413517 thermal method (DSC) ^, each friction reducing additive contains 0.5% by weight of antioxidants (Irgan 0x L1 ^^ by Clba Professional Chemicals Co., Ltd.), differential The scanner is a MeUler dSc27HP model with Mettler TC 15 TA controller. The measurement conditions are: · Starting temperature: 30. 〇Heating rate: 50t: / min up to 170. Test temperature: 40 bar (bar) Air flow: 50ml / min Sample volume: 5 +/- 0.4mg Crucible: aluminum, 40μl The measurement results are shown in Table 1 Shown: Table 1 TrimethyOlprpane mono-monomerate, anti-wear additive Additive time (minutes) 59 Trimethylolpropane C12 / C14 acid ester 144 oleamide (Control) 11 Glycerol monooleate (control) 4 Trishydroxypropylpropane mono-monomer ester is obtained by partial esterification of an excess of trihydroxymethylpropane with hydrogenated C18 monomer acid, and its hydroxyl value is 186. The product is a mixture of esters, in which the actual trimethylolpropane mono-monomer ester content is about 40%. The monomethylpropane chloride Cl 2 / C14 acid ester is prepared by trimethylmethacrylate and 1: 1 molar ratio. The mixture of lauric acid and myristic acid is obtained by partial esterification, and its base value is 87883-14-218. 218.200413517 The data in Table 1 clearly show that the oxidation stability of the friction-reducing additives of the present invention is significantly higher than the listed commercially available friction-reducing additives. Example 2 The friction coefficient of a lubricant composition containing 0.5% by weight of a friction-reducing additive was measured using a pin-on-ring friction gauge, and the temperature range was 40 to 140 t. The tribometer ring is a 100Cr6 stainless steel ring with a diameter of 730 mm, and the tribometer pin is a cylinder made of the same material with a diameter of 8 mm. The pin has flexible ends, so each end can be slightly bent to facilitate complete alignment with the ring. quasi. The applied load is 100N and the rotation speed is 0.03 m / s to ensure that the system operates under marginal lubrication conditions. The measurement results are shown in Table 2. Among them, OW / 30 oil based on 1-decene hydrogenated oligomer is formulated base oil (machine oil). Table 2 Prepared base oil 0W / 30 0W / 30 0W / 30 0W / 30 Antifriction additives σ Glycerol monooleate (comparative) oleylamine (comparative) trimethylol propane mono-monomer (40%) temperature coefficient of friction friction coefficient friction coefficient friction Coefficient [° C] 40 0.1368 0.1066 0.1110 0.1139 50 0.1395 0.1063 0.1110 0.1166 60 0.1410 0.1098 0.1146 0.1180 70 0.1426 0.1140 0.1134 0.1190 80 0.1436 0.1154 0.1105 0.1194 90 0.1442 0.1164 0.1093 0.1190 87883 -15-200413517 100 0.1445 0.1164 0.1078 0.1187 110 0.1449 0.1173 0.1071 0.1182 120 0.1456 0.1195 0.1078 0.1179 130 0.1466 0.1227 0.1090 0.1174 140 0.1545 0.1302 0.1119 0.1172 The data in Table 2 clearly show that the antifriction additive of the present invention has similar antifriction ability compared to our well-known glyceryl monooleate and oleylamine. Although the friction reducing additive of the present invention has stronger oxidation stability (as shown in Example 1) compared with the friction reducing additive which is well known to us, its oxidation stability does not affect its friction reducing property. Example 3 Example 2 was repeated for two samples of TMP C12 / C14 acid esters with different hydroxyl values. The CEC RL 179/2 formulated base oil used in the measurement is a 5 W-30 calibration oil used in European fuel economy testing. The measurement results are shown in Table 3 and Figure 1. Table 3 Blended base oils CECRL 179/2 CEC RL 179/2 CEC RL 179/2 Antiwear additives without trimethylolpropane C12 / C14 acid ester (hydroxyl value 92) (control) Trihydroxymethylpropane C12 / C14 acid acid (hydroxyl value 218) temperature coefficient of friction coefficient of friction coefficient of friction [° C] 40 0.1077 0.1030 0.0995 50 0.1147 0.1076 0.1048 87883 -16- 200413517 __60 0.1177 0.1105 0.1070 70 --------- 0.1185 0.1135 0.1083 80- -----__ 0.1191 ------ 0.1161 0.1100 90 0.1199 0.1171 0.1121 100 ----- 0.1221 0.1190 0.1145 110 0.1245 0.1211 0.1182 120 0.1273 0.1244 0.1241 130 ------- 0.1349 0.1293 0.1307 140 0.1353 0.1284 0.1353 Figure The top curve in 1 represents that no antiwear additive was added, the middle curve represents the trimethylmethane C12 / C14 acid ester control sample, and the bottom curve represents the trimethylolpropane ^^ bucket acid ester according to the present invention. Table 3 and FIG. 1 clearly show that the friction reducing additives having a hydroxyl value of at least 180% have a lower car body. The friction coefficient of the friction reducing additives is lower than the base value. Example 4 The 'glutarity' of 0.5% by weight of dimethylol mono-monomer ester antifriction additive and formulated base oil was measured by the following method. Add the anti-wear additive to the formulated base oil and cool the compound to -10 ° C. The mixture
最長放置3個月，#中&旦、日丨# L ^ 疋期s測其相容性。所謂相容性指流體 ^政，热模糊、渾濁及沈殿現象出現。 量測中發現，在整 之其礎-、由相- 狀月内三羥甲基單-單體酯與調配 之基礎油相谷，而含有油醯 開始出現結晶及沈澱。 、，、?、樣品在開始量測3天後 由以上數據明顯可知，、， 乃之二羥甲基單-單體酯與調 87883 -17- 200413517 配之基礎油相容。 實例5 含1 · 0重量％之減磨添加劑之潤滑劑組合物的摩擦係數， 係使用微型牵引機（Mini Traction Machine)在溫度範圍40至 140°C間而測得。牽引機施加負載30N，轉速0.06公尺/秒鐘 。量測結果如表4及圖2所示，其中5W/30油爲調配之基礎油 (機油）。 表4 调配之基礎油 5W/30 5W/30 5W/30 減磨添加劑 未加 三羥甲基丙烷單體酯 (40%)(TMPMM) 三羥曱基丙烷單·單體酯 (70%)(TMPMM) 溫度 摩擦係數 摩擦係數 摩擦係數 [°C] 40 0.118 0.114 0.1139 50 0.122 0.117 0.1166 60 0.125 0.118 0.1180 70 0.128 0.120 0.1190 80 0.130 0.122 0.1194 90 0.131 0.123 0.1190 100 0.132 0.125 0.1187 110 0.132 0.125 0.1182 120 0.134 0.124 0.1179 130 0.134 0.124 0.1174 140 0.135 0.124 0.1172 87883 -18- 200413517 二羥甲基丙烷單-單體酯（70%)由莫耳濃度過量之三羥甲 基丙烷與氫化C18單體酸反應製得，並經分子蒸餾至純度達 7〇 （相較於未經額外分子蒸餾階段的純度為4〇%)。該産物 之羥基值爲2 1 2。 由表4與圖2數據明顯可知，本發明之減磨添加劑與吾人 热知之單油酸甘油酯減磨添加劑具有相近減磨能力。此外 ，k咼二羥甲基丙烷單-單體酯之羥基值可對應地降低摩 擦係數。 儘管與吾人熟知之減磨添加劑（如上實例1所述）相比，本 發明之減磨添加劑具有增加之氧化安定性，但其氧化安定 性並未影響其減磨性質。 87883 19-The longest period is 3 months, and the compatibility is measured in # 中 & 旦 、 日 丨 # L ^ period. The so-called compatibility refers to the presence of fluid, thermal blur, turbidity, and Shen Dian phenomenon. It was found in the measurement that during the whole period, the trimethylol mono-monomer ester and the base oil phase valley formulated in the phase-like month, and the crystals and precipitates contained in the oleic acid began to appear. It is clear from the above data that the sample is 3 days after the start of the measurement, and that the dimethylol mono-monomer ester is compatible with the base oil formulated with 87883 -17- 200413517. Example 5 The coefficient of friction of a lubricant composition containing 1.0% by weight of a friction reducing additive was measured using a Mini Traction Machine over a temperature range of 40 to 140 ° C. The tractor applies a load of 30N and rotates at a speed of 0.06 meters / second. The measurement results are shown in Table 4 and Figure 2. Among them, 5W / 30 oil is the blended base oil (motor oil). Table 4 Blended base oils 5W / 30 5W / 30 5W / 30 Antiwear additive without trimethylolpropane monomer ester (40%) (TMPMM) Trimethylolpropane monomer monomer (70%) ( TMPMM) Coefficient of temperature friction Coefficient of friction [° C] 40 0.118 0.114 0.1139 50 0.122 0.117 0.1166 60 0.125 0.118 0.1180 70 0.128 0.120 0.1190 80 0.130 0.122 0.1194 90 0.131 0.123 0.1190 100 0.132 0.125 0.1187 110 0.132 0.125 0.1182 120 0.134 0.124 0.1179 130 0.134 0.124 0.1174 140 0.135 0.124 0.1172 87883 -18- 200413517 Dimethylolpropane mono-monomer ester (70%) is prepared by reacting trimethylolpropane with a molar excess and hydrogenated C18 monomer acid, and the molecule Distilled to a purity of 70 (compared to 40% purity without the additional molecular distillation stage). The hydroxyl value of this product was 2 1 2. It is clear from the data in Table 4 and Figure 2 that the antifriction additive of the present invention has similar antifriction ability to the glyceryl monooleate antifriction additive that we know well. In addition, the hydroxyl value of k-dimethylolpropane mono-monomer ester can correspondingly reduce the friction coefficient. Although the anti-friction additive of the present invention has an increased oxidation stability compared to the anti-friction additive known to me (as described in Example 1 above), its anti-oxidation stability does not affect its anti-friction properties. 87883 19-