CN113365972A - 由糖醇酯合成的润滑基础油 - Google Patents
由糖醇酯合成的润滑基础油 Download PDFInfo
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- CN113365972A CN113365972A CN202080011474.XA CN202080011474A CN113365972A CN 113365972 A CN113365972 A CN 113365972A CN 202080011474 A CN202080011474 A CN 202080011474A CN 113365972 A CN113365972 A CN 113365972A
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- Prior art keywords
- acid
- fatty acids
- esters
- oil
- ester
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/33—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with hydroxy compounds having more than three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/40—Esters containing free hydroxy or carboxyl groups
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
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Abstract
本发明涉及至少一种糖多元醇和至少一种直链C6‑C11脂肪酸的酯,其中糖多元醇是赤藓糖醇。
Description
技术领域
本发明涉及由糖醇、特别是糖多元醇形成的酯,和其作为润滑剂基础物(base,基料,基础)的用途以及其制造方法。
背景技术
目前,润滑剂基础物市场由石油来源的矿物油主导。2008年,润滑剂的欧洲生产量为450万吨/年。这些润滑剂基础物用在各种行业中作为发动机油、用于链锯链(chainsawchain)的切削油、用于近海石油钻探(offshore oil drilling)的油、用于重型设备和农业机械的液压油等。
这些矿物油一旦使用并不总是被再循环,并且由于排放到地面上、下水道中、湖泊和河流中而造成环境污染。鉴于这些润滑油对环境的潜在影响,开发生态和可生物降解的润滑剂基础物是必要的,特别是对于润滑剂容易泄漏到环境中的应用。
已知其作为润滑剂的用途几年的植物油和动物油可满足这种对环境保护的关注,因为它们具有环境友好的优势。然而,这些油与矿物油相比具有低热稳定性以及低抗氧化性,并且在水的存在下易于水解。
由脂肪酸与醇连接形成的多元醇酯具有良好的氧化稳定性、良好的水解稳定性、相对高的可生物降解性和良好的低温性能。专利申请EP 1 533 360中描述了包含多元醇(例如新戊二醇或三羟甲基丙烷)和衍生自棕榈油的产物的衍生自棕榈油的多元醇酯的可生物降解的润滑剂组合物。然而,这样的组合物仅适合于范围为15℃至40℃的温度。
在这种情况下,因此仍然有必要开发替代的多元醇酯,其结构可完全衍生自可再生来源的成分,具有优异的润滑性质并且对人类和环境无害。
发明内容
在本发明的上下文中,已经观察到糖醇、特别是糖多元醇和C6-C11直链脂肪酸的酯具有对于在润滑剂中的应用而言优异的性质。
本发明得自发明人预料不到的发现(证实):糖醇、特别是糖多元醇、尤其是赤藓糖醇和C6-C11直链脂肪酸的酯具有对于在润滑剂中的应用而言优异的性质。
因此,本发明涉及至少一种糖醇、特别是糖多元醇和至少一种C6-C11直链脂肪酸的酯,其中糖醇、特别是糖多元醇是赤藓糖醇。
本发明还涉及如上所定义的至少一种糖醇、特别是糖多元醇和至少一种C6-C11直链脂肪酸的酯作为润滑剂基础物的用途。
本发明还涉及润滑剂基础组合物,其包含如上所定义的至少一种糖醇、特别是糖多元醇和至少一种C6-C11直链脂肪酸的酯。
本发明还涉及制备酯的方法,所述方法包括至少一种C6-C11直链脂肪酸与至少一种糖醇、特别是糖多元醇的酯化反应,优选地,所述方法包括除去过量酸的步骤,并且不存在以下步骤中的至少一个:
·通过添加添加剂进行的下游处理;
·添加催化剂;
·添加有机溶剂。
本发明还涉及通过如上所定义的方法获得的至少一种糖醇、特别是糖多元醇和至少一种C6-C11直链脂肪酸的酯。
具体实施方式
在没有添加催化剂和没有通过添加添加剂进行的下游处理的情况下由至少一种多元醇和可再生来源的脂肪酸(例如赤藓糖醇和正庚酸(例如来自Arkema的C7))的酯合成的根据本发明的润滑剂基础组合物使得可实现在热稳定性方面的性质,这些性质高于其中醇不是基于生物的、例如为三羟甲基丙烷的通常酯,如在以下实例(实施例)中详细描述的。
因此,本发明提供可再生来源的润滑剂基础组合物,其具有良好的氧化稳定性、良好的热稳定性和非常好的润滑性质。
此外,由于组合物在低温下具有良好的流动性,所以它特别适合于在低温(即典型地等于或小于0℃)下使用。
术语“可生物降解的”在本文中用于表示由如下的分子形成的化合物:所述分子可例如通过自然环境中的活微生物例如细菌、真菌和藻类转化成更小的、污染更少的分子。该降解的最终结果通常由水、二氧化碳或甲烷组成。
“衍生自可再生资源”或“基于生物”的材料或化合物或成分理解为意指可再生的天然材料或化合物或成分,其存料(stock,原料)可在人类时间尺度上的短时间段内重构。这些特别是动物来源或植物来源的原材料。术语“可再生来源的原材料”或“基于生物的原材料”意指包含基于生物的碳或可再生来源的碳的材料。具体地,与衍生自化石材料的材料不同,包含(composed of)可再生原材料的材料含有碳14(14C)。“可再生来源的碳的含量”或“基于生物的碳的含量”通过应用标准ASTM D 6866(ASTM D 6866-06)和ASTM D 7026(ASTMD 7026-04)来确定。
流体的粘度意指其在流动时抵抗其分子的内部滑动的阻力。粘度是针对参考温度给出的。以m/s2表示的运动粘度使用以下式计算:υ=η/ρ,其中
η是以Pa.s表示的动态粘度;并且
ρ是以kg/m3表示的流体的密度。
运动粘度也以斯托克(St)或厘斯托克(cSt)表示。
运动粘度根据标准ISO 3104测量。
氧化稳定性可通过两种测量来确定:氧诱导时间和氧诱导温度。氧诱导时间和氧诱导温度可根据标准ISO 11357-6:2018在差示扫描量热仪(DSC)中测量。
产品的倾点是产品仍然流动的最低温度。倾点根据标准ISO 3016测量。
粘度指数(VI)(无单位)指示油的粘度在给定温度范围内、通常在40℃和100℃之间的变化率。粘度指数可定义为材料在40℃和100℃之间的运动粘度梯度。当粘度指数低(小于100)时,流体显示出粘度随温度相对大的变化。当粘度指数高(大于150)时,流体具有粘度随温度相对小的变化。在各种应用中,高或非常高的粘度指数是优选的。根据标准ASTMD 2270中描述的测试方法测量粘度指数。
酯
醇理解为意指具有至少一个羟基(-OH)基团的分子。多元醇理解为意指具有至少两个羟基(-OH)基团的分子。
优选地,根据本发明的多元醇是含有多个羟基基团的有机化合物。优选地,多元醇不指含有除羟基之外的官能团的化合物。更优选地,根据本发明的多元醇是对应于化学通式CnH2n+2On并且具有至少两个羟基的化合物。
根据本发明的酯由至少一种糖醇、特别是糖多元醇和至少一种C6-C11脂肪酸形成。
根据一个实施方案,根据本发明的酯可为单酯、二酯、三酯和四酯。
根据本发明的糖醇、特别是糖多元醇优选从可再生资源获得。根据本发明的糖醇、特别是糖多元醇优选为可生物降解的。
优选地,根据本发明的糖醇、特别是糖多元醇选自单糖、二糖、三糖和其混合物。
优选地,根据本发明的单糖选自赤藓糖醇、木糖、阿拉伯糖、核糖、山梨糖醇、脱水山梨糖醇、葡萄糖、山梨糖、果糖、木糖醇和其混合物,更优选地选自木糖、阿拉伯糖、核糖、葡萄糖、山梨糖、果糖和其混合物。
优选地,根据本发明的二糖选自麦芽糖、乳糖、蔗糖和其混合物。
根据本发明的三糖优选选自棉子糖、麦芽三糖、氢化淀粉水解物和其混合物。
更优选地,根据本发明的糖醇、特别是糖多元醇是赤藓糖醇。
根据一个实施方案,根据本发明的糖多元醇通过糖的氢化获得。
根据本发明的脂肪酸优选衍生自可再生资源。根据本发明的脂肪酸优选为直链或支链的,饱和或不饱和的,植物或动物来源的。
根据本发明的脂肪酸优选通过研磨植物、特别是含油植物的种子、核仁(stone)或果实获得,例如亚麻籽油、菜籽油、葵花籽油、大豆油、橄榄油、棕榈油、蓖麻油、木油、玉米油、南瓜油、葡萄籽油、荷荷巴油、芝麻油、核桃油、榛子油、扁桃仁油、乳木果油、澳洲坚果油、棉籽油、苜蓿油、黑麦油、红花油、花生油、椰干油、妥尔油和摩洛哥坚果油(argan oil)或来自动物脂肪,例如牛脂(tallow fat)。
根据本发明的脂肪酸优选选自以下物质的脂肪酸:蓖麻油、椰子油、棉籽油、脱水蓖麻油、大豆油、妥尔油、菜籽油、葵花油、亚麻籽油、棕榈油、桐油、奥蒂树油、红花油、橄榄油、木油、玉米油、南瓜油、葡萄籽油、荷荷巴油、芝麻油、核桃油、榛子油、扁桃仁油、乳木果油、澳洲坚果油、苜蓿油、黑麦油、花生油、椰干油和摩洛哥坚果油。
根据本发明的脂肪酸包含6至11个碳原子。
优选地,根据本发明的脂肪酸选自己酸、庚酸、辛酸、壬酸、癸酸、呋喃二甲酸、四氢呋喃-2,5-二甲酸、四氢呋喃-3,5-二甲酸、壬二酸、癸二酸、10-十一碳烯酸、十一碳二酸和十二碳二酸。
优选地,根据本发明的脂肪酸是直链脂肪酸。
优选地,直链脂肪酸使得可增加所合成的润滑剂基础物的粘度指数,以改进其热稳定性,并且比主要衍生自石油工业的支链酸更容易可生物降解。
优选地,根据本发明的脂肪酸衍生自蓖麻油。
衍生自蓖麻油的脂肪酸应理解为意指在油中存在的脂肪酸和/或可在化学转化结束时(末端处)获得的脂肪酸。例如,庚酸和/或10-十一碳烯酸可从蓖麻油获得,其典型地通过使蓖麻油酸甲酯(其源自蓖麻油的酯交换)热裂解的步骤。根据本发明的脂肪酸优选为正庚酸。还优选地,根据本发明的脂肪酸为正庚酸(Arkema)。
优选地,正庚酸衍生自蓖麻油。
优选地,根据本发明的酯由根据本发明的糖醇、特别是由糖多元醇形成,其中至少3个醇基团、优选4个醇基团被根据本发明的脂肪酸酯化。
还优选地,根据本发明的脂肪酸对根据本发明的糖醇、特别是糖多元醇的重量比在4:1至10:1的范围内。更优选地,根据本发明的脂肪酸对根据本发明的糖醇、特别是糖多元醇的重量比为约5:1。
优选地,相对于酯的总重量计,至少50重量%、优选75重量%分数的酯衍生自可再生资源。
优选地,根据本发明的酯具有大于2小时的在差示扫描量热计中在150℃下测量的氧诱导时间。
优选地,根据本发明的酯具有大于200℃的在差示扫描量热计中测量的氧诱导温度。
根据本发明的酯优选包括低于-30℃、优选在-50℃和-30℃之间、更优选为约-42℃的倾点。
根据本发明的酯优选包括在40℃下在14和30mm2/s之间和/或在100℃下小于4.5mm2/s的运动粘度,其根据标准ISO 3104测量。
方法
根据本发明由糖醇、特别是糖多元醇和脂肪酸制备根据本发明的酯的方法可根据本领域技术人员熟知的通常酯化技术进行。
优选地,根据本发明的酯化方法包括,在有或没有催化剂的情况下,在过量的根据本发明的至少一种C6-C11直链脂肪酸的存在下使至少一种根据本发明的糖醇、特别是糖多元醇酯化的步骤。
根据本发明的酯化步骤优选在140℃和250℃之间的温度下进行0.5至12小时、优选1至10小时、更优选2至9小时的时间段。
根据本发明的酯化步骤优选在惰性气氛下进行。
优选地,根据本发明的制备酯的方法在受控真空下进行以除去过量的酸。根据本发明的酯化方法可包括添加吸收剂例如氧化铝、硅胶、沸石、活性炭和粘土的步骤。
根据本发明的方法可进一步包括添加水和碱以同时中和残留的有机酸和无机酸和/或使催化剂水解的步骤。在这种情况下,根据本发明的方法可包括通过加热和置于真空下除去所使用的水的步骤。
根据本发明的方法还可包括过滤酯混合物固体的步骤,该酯混合物固体含有在酯化反应中使用的过量酸混合物的大部分。
根据本发明的方法可包括通过蒸汽提取或通过任何其他蒸馏方法除去过量酸和将酸在反应容器中再循环的步骤。
根据一个实施方案,本发明的方法包括除去过量的酸的步骤,优选通过真空蒸馏进行。
优选地,通过未反应的酸的减压蒸馏来纯化根据本发明的方法获得的化合物。蒸馏优选在真空下进行15分钟至2小时。蒸馏进一步优选在140℃和180℃之间的温度下进行。蒸馏步骤之后剩余的游离酸的量可通过用环氧酯处理、通过用任何合适的碱性材料(例如石灰、碱金属氢氧化物、碱金属碳酸盐或碱性氧化铝)中和来减少。当用环氧酯处理时,可进行第二次减压蒸馏以除去过量的环氧酯。当进行碱处理时,可进行用水洗涤以除去过量的未反应的碱性材料。
根据本发明的方法可包括从在最终过滤期间提取的酯除去任何残留固体材料的步骤。
优选地,相对于所使用的糖醇、特别是糖多元醇的量计,根据本发明的脂肪酸以约10至50mol%、优选10至30mol%的过量存在于形成根据本发明的酯的反应中。
根据本发明的方法可在催化剂的存在下进行。催化剂可为本领域技术人员熟知的用于酯化反应的任何催化剂。优选地,催化剂选自:氯化锡,硫酸,对甲苯磺酸,甲磺酸,磺基琥珀酸,盐酸,磷酸,基于锌、铜、锡、钛、锆或钨的催化剂;碱金属盐例如氢氧化钠或氢氧化钾、碳酸钠或碳酸钾、乙醇钠或乙醇钾、甲醇钠或甲醇钾,沸石和酸性离子交换剂,或其混合物。
优选地,在根据本发明的制备酯的方法期间不进行通过添加添加剂进行的下游处理步骤。
术语“通过添加添加剂进行的下游处理”应理解为意指典型地在如上所述的酯化步骤结束时进行的一个或多个步骤,即,添加吸收剂的步骤、添加水和碱的步骤、从酯的混合物过滤固体的步骤和/或除去过量的酸的步骤。
优选地,制备酯的方法在没有催化剂的情况下进行。
优选地,制备酯的方法在没有添加有机溶剂的情况下进行。
优选地,制备酯的方法在不存在以下步骤中的至少一个、优选至少两个、更优选全部的情况下进行:
·通过添加添加剂进行的下游处理;
·添加催化剂;
·添加有机溶剂。
优选地,反应进行足够的时间以获得相对于酯的总量计大于或等于80重量%的四酯含量。更优选地,反应进行足够的时间以获得相对于酯的总量计大于或等于93重量%的四酯含量。
用途
根据本发明的酯优选原样用作润滑剂基础物或润滑剂基础油。
根据本发明的酯也可作为与其他基础油的混合物使用,所述其他基础油例如矿物油、高度精炼的矿物油、聚α烯烃(PAO)、聚亚烷基二醇(PAG)、磷酸酯、硅油、二酯、聚异丁烯和多元醇酯。
特别地,根据本发明的酯可用于制备润滑剂基础组合物。根据本发明的润滑剂基础组合物可用于所有类型的行业,特别是作为汽车润滑剂、作为金属加工油、作为液压油、作为涡轮机油或作为飞机油。
优选地,相对于酯的总量计,根据本发明的组合物可包含大于或等于80重量%的四酯含量。更优选地,相对于酯的总量计,组合物可包含大于或等于93重量%的四酯含量。
除了根据本发明的酯之外,根据本发明的组合物还可包含一种或多种添加剂。优选地,添加剂选自抗氧化剂、热稳定性改进剂、腐蚀抑制剂、金属钝化剂、润滑剂添加剂、粘度指数改进剂、倾点下降剂、清洁剂、分散剂、消泡剂、抗磨剂和极压添加剂。
优选地,相对于润滑剂基础组合物的总重量计,根据本发明的组合物中的添加剂的量不超过10重量%、优选8重量%、更优选5重量%。
优选地,相对于润滑剂基础组合物的总重量计,所使用的抗氧化剂的量在0.01%和5%之间。
优选地,相对于润滑剂基础组合物的总重量计,腐蚀抑制剂的量在0.01重量%和5重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,金属钝化剂的量在0.001重量%和0.5重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,润滑剂添加剂的量在0.5重量%和5重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,粘度指数改进剂的量在0.01重量%和2重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,倾点下降剂的量在0.01重量%和2重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,清洁剂的量在0.1重量%和5重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,分散剂的量在0.1重量%和5重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,消泡剂的量在0.01重量%和2重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,抗磨剂的量在0.01重量%和2重量%之间。
优选地,相对于润滑剂基础组合物的总重量计,极压添加剂的量在0.1重量%和2重量%之间。
抗氧化剂和热稳定性改进剂可选自本领域技术人员熟知的任何抗氧化剂和热稳定性改进剂。通过举例的方式,抗氧化剂和热稳定性改进剂可选自:
-二苯胺、二萘胺、苯基萘胺,其中苯基基团或萘基基团可被例如N,N'-二苯基苯二胺、对辛基二苯胺、p,p-二辛基二苯胺、N-苯基萘胺、N-苯基-2-萘胺、N-(对十二烷基)苯基-2-萘胺、二-1-萘胺和二-2-萘胺基团取代;
-吩噻嗪,例如N-烷基吩噻嗪;
-亚氨基二苄;和
-受阻酚例如6-(叔丁基)苯酚、2,6-二(叔丁基)苯酚、4-甲基-2,6-二(叔丁基)苯酚、4,4'-亚甲基双(2,6-二(叔丁基)苯酚)。
金属钝化剂可选自本领域技术人员熟知的任何金属钝化剂。通过举例的方式,金属钝化剂可选自咪唑、苯并咪唑、2-巯基苯并噻唑、2,5-二巯基噻二唑、水杨基-丙二胺、吡唑、苯并三唑、甲苯三唑、2-甲基苯并咪唑、3,5-二甲基吡唑和亚甲基双(苯并三唑)。金属钝化剂或腐蚀抑制剂的其他实例包括:
-有机酸和酯、其金属盐和酸酐,例如N-油基肌氨酸、脱水山梨糖醇单油酸酯、环烷酸铅、十二碳烯基琥珀酸及其偏酯和酰胺、以及4-壬基苯氧基乙酸;
-脂族和脂环族伯胺、仲胺和叔胺以及有机酸和无机酸的胺盐,例如油溶性羧酸烷基铵;
-含有氮的杂环化合物,例如噻二唑、取代咪唑啉和噁唑啉;
-喹啉、醌和蒽醌;
-没食子酸丙酯;
-二壬基萘磺酸钡;
-烯基琥珀酸酐或酸的酯和酰胺衍生物、二硫代氨基甲酸酯、二硫代磷酸酯;
-烷基酸式磷酸酯及其衍生物的胺盐。
润滑剂添加剂可选自本领域技术人员熟知的任何润滑剂添加剂。作为润滑剂添加剂的实例,可提及脂肪酸和天然油的长链衍生物,例如酯、胺、酰胺、咪唑啉和硼酸盐。
粘度指数改进剂可选自本领域技术人员熟知的任何粘度指数改进剂。作为粘度改进剂的实例,可提及聚甲基丙烯酸酯、乙烯基吡咯烷酮和甲基丙烯酸酯的共聚物、聚丁烯和苯乙烯-丙烯酸酯共聚物。
倾点下降剂可选自本领域技术人员熟知的任何倾点下降剂。作为倾点下降剂的实例,可提及:聚甲基丙烯酸酯例如甲基丙烯酸酯-乙烯-乙酸乙烯酯三元共聚物;烷基化萘衍生物;以及脲催化的与萘或酚的弗瑞德-克来福特(Friedel-Crafts)缩合的产物。
清洁剂和分散剂可选自本领域技术人员熟知的任何清洁剂和分散剂。作为清洁剂和分散剂的实例,可提及:聚丁烯基琥珀酸酰胺;聚丁烯基膦酸衍生物;被长链烷基取代的芳族磺酸及其盐;以及烷基硫化物、烷基酚及烷基酚和醛的缩合产物的金属盐。
消泡剂可选自本领域技术人员熟知的任何消泡剂。作为消泡剂的实例,可提及有机硅和某些丙烯酸酯的聚合物。
抗磨剂和极压添加剂可选自任何抗磨剂和极压添加剂。作为抗磨剂和极压添加剂的实例,可提及:
-硫化脂肪酸和脂肪酸酯例如硫化妥尔酸辛酯(octyl tallate);
-硫化萜烯;
-硫化烯烃;
-有机多硫化物;
-有机磷衍生物,包括磷酸胺、烷基酸式磷酸酯、二烷基磷酸酯、二硫代磷酸胺、三烷基和三芳基硫代磷酸酯、三烷基和三芳基膦、和二烷基亚磷酸酯例如磷酸单己酯的胺盐、二壬基萘磺酸的胺盐、三苯基磷酸酯、三萘基磷酸酯、二苯基甲苯基磷酸酯、和苯基苯基磷酸酯、萘基二苯基磷酸酯、三苯基硫代磷酸酯;
-二硫代氨基甲酸盐,例如二烷基二硫代氨基甲酸锑;
-氯化和/或氟化烃和黄原酸酯/盐。
将借助以下非限制性实施例进一步解释本发明。
实施例
本发明人研究了根据本发明的酯在润滑剂中的应用的性质。
1.酯的制备
制备了2个样品:
-赤藓糖醇和正庚酸的酯(根据本发明的酯);和
-三羟甲基丙烷和正庚酸的酯(对比实施例1)。
赤藓糖醇和正庚酸的酯(根据本发明的酯)的合成:
将赤藓糖醇(14.7g,0.12mol)和正庚酸(81.7g,0.62mol)装入到配备有搅拌器、温度计、冷凝器和氮气入口的250ml三颈烧瓶中。将反应混合物在氮气氛下在210℃下加热7h30min的时间段,直至收集到理论水量。然后将粗产物在180℃的温度下和最大真空下蒸馏1小时30min以除去过量的正庚酸以获得66.5g的具有0.1mgKOH/g的酸值的产物。
对产物的运动粘度、粘度指数(VI)和倾点进行评价并且报告在表2中。
产物的化学组成通过气相色谱确定如下:94.1%的赤藓糖醇和正庚酸的四酯,2.2%的赤藓糖醇和正庚酸的三酯和2.9%赤藓糖醇和正庚酸的脱水酯。
三羟甲基丙烷和正庚酸的酯(对比实施例1)的合成
将三羟甲基丙烷(53.8g,0.4mol)和正庚酸(181.5g,1.38mol)装入到配备有搅拌器、温度计、冷凝器和氮气入口的500ml三颈烧瓶中。将反应混合物在氮气氛下在185℃下加热3h的时间段,直至收集到理论水量。然后将四丁醇锆(1.5g,在丁醇中80%,0.5重量%/反应物的总重量)分批添加至反应器。使组装件在150℃下逐渐置于最大真空下达3小时30分钟以蒸馏出过量的未反应的酸并且得到187.4g的产物。对粗反应产物进行用活性碱性氧化铝的下游处理,并且得到具有0.1mgKOH/g的酸值的油。
对产物的运动粘度、粘度指数(VI)和倾点进行评价并且报告在表2中。
产物的化学组成通过气相色谱确定如下:98.8%三羟甲基丙烷三庚酸酯和0.03%三羟甲基丙烷二庚酸酯。
2.抗氧化性的测量
氧化稳定性通过两种测量来确定:氧诱导时间和氧诱导温度。氧诱导时间和氧诱导温度在差示扫描量热仪(DSC)中测量。
为了测量氧诱导时间,将样品加热至150℃,然后保持恒温。然后将其暴露于氧化气氛。与氧接触和氧化开始之间的时间是氧诱导时间。
为了测量氧诱导温度,在氧化气氛下以恒定加热速率加热样品直至反应开始。氧诱导温度是氧化反应开始时的温度。
结果示于以下表1中:
[表1]
表1:抗氧化性测量
测量显示两个样品在150℃下的氧诱导时间相似。根据本发明的酯具有比对比实施例的高的氧诱导温度。因此,根据本发明的酯具有比由非基于生物的醇合成的通常酯好的抗氧化性质。
4.运动粘度的测量
运动粘度根据标准ISO 3104在40℃和100℃下测量。
以mm2/s表示的结果示于以下表2中。
5.粘度指数的测量
根据标准ASTM D 2270中描述的测试方法测量粘度指数(无单位)。结果示于以下表2中:
6.倾点的测量
以℃表示的倾点根据标准ISO 3016测量。结果示于以下表2中:
[表2]
表2:运动粘度、粘度指数和倾点的测量。
这些结果显示,在没有添加催化剂和没有通过添加添加剂进行的下游处理的情况下仅由可再生来源的物质合成(与对比实施例不同)的根据本发明的酯具有接近于对比实施例的在40℃和100℃下的运动粘度。根据本发明的酯显示出更高的粘度指数,这意味着根据本发明的润滑剂基础物具有随着温度的变化更稳定的粘度。
本发明的润滑剂基础物显示出更高的倾点,这与赤藓糖醇的熔点(120℃)高于对比实施例的三羟甲基丙烷的熔点(60℃)有关,但该值仍然相对低并且有利于在润滑剂中的应用。
Claims (17)
1.至少一种糖多元醇和至少一种C6-C11直链脂肪酸的酯,其中糖多元醇是赤藓糖醇。
2.如权利要求1所述的酯,其中C6-C11直链脂肪酸是正庚酸。
3.如权利要求1或2所述的酯,其中C6-C11直链脂肪酸对糖多元醇的重量比为至少5:1。
4.如权利要求1至3中任一项所述的酯,其中C6-C11直链脂肪酸衍生自可再生资源。
5.如权利要求1至4中的一项所述的酯,其中C6-C11直链脂肪酸衍生自蓖麻油。
6.如权利要求1至5中的一项所定义的至少一种糖多元醇和至少一种C6-C11直链脂肪酸的酯作为润滑剂基础物的用途。
7.润滑剂基础组合物,其包含如权利要求1至5中的一项所定义的至少一种糖多元醇和至少一种C6-C11直链脂肪酸的酯。
8.制备酯的方法,所述方法包括在过量的至少一种C6-C11直链脂肪酸的存在下使至少一种糖多元醇酯化的步骤。
9.如权利要求8所述的方法,其中所述方法包括除去过量的酸的步骤,优选通过真空蒸馏进行。
10.如权利要求8和9中任一项所述的方法,其中所述方法在不存在以下步骤中的至少一个的情况下进行:
-通过添加添加剂进行的下游处理;
-添加催化剂;
-添加有机溶剂。
11.如权利要求8至10中的一项所述的方法,其中反应进行足够的时间以获得相对于酯的总量计大于或等于80重量%、优选大于或等于93重量%的四酯含量。
12.如权利要求8至11中任一项所述的方法,其中糖多元醇是赤藓糖醇。
13.如权利要求8至12中任一项所述的方法,其中C6-C11直链脂肪酸是正庚酸。
14.如权利要求8至13中任一项所述的方法,其中C6-C11直链脂肪酸衍生自可再生资源。
15.如权利要求13所述的方法,其中C6-C11直链脂肪酸衍生自蓖麻油。
16.如权利要求8至15中任一项所述的方法,其中C6-C11直链脂肪酸对糖多元醇的重量比为至少5:1。
17.通过如权利要求8至16中的一项所述的方法获得的至少一种糖多元醇和至少一种C6-C11直链脂肪酸的酯。
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CN103421605A (zh) * | 2012-05-25 | 2013-12-04 | 丰益(上海)生物技术研发中心有限公司 | 用赤藓糖醇脂肪酸酯分提油脂的方法及其应用 |
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US2760632A (en) * | 1951-01-02 | 1956-08-28 | Phillips Petroleum Co | Plasticization of sulfur vulcanizable materials, and related compositions |
JPS6156102A (ja) * | 1984-08-27 | 1986-03-20 | Mitsubishi Chem Ind Ltd | 種子の発芽防止剤 |
MY141241A (en) | 2003-11-20 | 2010-03-31 | Malaysia Palm Oil Board | Lubricant base from palm oil and its by-products |
EP1950218A1 (en) * | 2007-01-24 | 2008-07-30 | Centre National de la Recherche Scientifique | Sulfoglycolipid antigens, their process of preparation, and their use against tuberculosis |
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