CN114507556B - 一种噻二唑类润滑油抗磨添加剂及其制备方法 - Google Patents

一种噻二唑类润滑油抗磨添加剂及其制备方法 Download PDF

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CN114507556B
CN114507556B CN202210041299.XA CN202210041299A CN114507556B CN 114507556 B CN114507556 B CN 114507556B CN 202210041299 A CN202210041299 A CN 202210041299A CN 114507556 B CN114507556 B CN 114507556B
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thiadiazole
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董均阳
李维民
王晓波
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Qingdao Center Of Resource Chemistry & New Materials
Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
    • C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure

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  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

本发明属于润滑油添加剂技术领域，具体为一种2,2,2‑三((5‑甲基‑1,3,4‑噻二唑‑2‑基)硫代)乙醇润滑油抗磨添加剂，结构如式(1)所示。本发明的润滑油抗磨添加剂由5‑甲基‑2‑巯基噻二唑和2,2,2‑三氯乙醇反应得到；该润滑油添加剂加入PEG类润滑油中，可显著提高PEG类润滑油的极压抗磨性能。

Description

一种噻二唑类润滑油抗磨添加剂及其制备方法
技术领域
本发明属于润滑油添加剂技术领域，具体涉及一种2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇作为润滑油抗磨添加剂的制备及使用方法。
背景技术
二巯基噻二唑可以通过巯基的偶联，生成二聚体、三聚体等。二巯基噻二唑二聚体不仅是重要的化工中间体，而且具有噻二唑类衍生物的通性-对金属的络合、钝化作用，同时也表现出极强的极压抗磨性能和协同抗氧性能；可用作各类工业、机械润滑脂等的极压抗磨剂，也可用作抗磨剂，尤其在重负荷工况下表现出优异性能。
目前，二巯基噻二唑二聚体类化合物作为润滑添加剂，由于其油溶性较差的问题，导致二巯基噻二唑二聚体类润滑添加剂在工业、机械润滑脂中广泛使用，而在工业、机械润滑油中则难以有效广泛使用。
发明内容
为了解决上述问题，本发明提供了一种2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇润滑油抗磨添加剂，具体结构如式(1)所示：
Figure BDA0003470073730000011
本发明的2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇润滑油抗磨添加剂由5-甲基-2-巯基噻二唑和2,2,2-三氯乙醇反应得到，合成路线如下所示：
Figure BDA0003470073730000021
具体合成方法如下：向三颈烧瓶中加入一定量的5-甲基-2-巯基噻二唑，随后向体系中加入适量的氢氧化钠和蒸馏水，缓慢升温至60-75℃，维持温度搅拌反应0.5-1.0小时；待体系中固体全部溶解后，加入一定量的2,2,2-三氯乙醇，维持温度搅拌反应3-5小时；停止反应后，反应液用热水洗涤，除去水溶性杂质，用二氯甲烷萃取，收集有机层，减压蒸馏除去溶剂，得到浅黄色固体产物，为添加剂目标产物。
本发明的2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇作为添加剂加入PEG类润滑油中，提高PEG类润滑油的极压抗磨性能。
本发明的有益效果：
目前，二巯基噻二唑二聚体类润滑添加剂，由于其油溶性较差的问题，难以在工业、机械润滑油中广泛有效使用。2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇作为抗磨添加剂可以在PEG类润滑油中有效使用，能显著提高PEG类润滑油的极压抗磨性能，解决了巯基噻二唑二聚体类润滑添加剂油溶性差这一关键问题，拓宽了噻二唑类抗磨添加剂的有效使用范围。
附图说明
图1实施例1制备的2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇的核磁氢谱图。
具体实施方式
下面将结合本发明的具体实施例与附图对本发明的技术方案进行清楚、完整地描述，显然，所描述实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
向三颈烧瓶中加入0.3mol的5-甲基-2-巯基噻二唑，随后向体系中加入0.3mol的氢氧化钠和100mL蒸馏水，缓慢升温至70℃，维持温度搅拌反应1小时；待体系中固体全部溶解后，加入0.1mol的2,2,2-三氯乙醇，维持温度搅拌反应4小时；停止反应后，反应液用热水洗涤，除去水溶性杂质，用二氯甲烷萃取，收集有机层，减压蒸馏除去溶剂，得到浅黄色固体产物，为添加剂目标产物。
目标产物经核磁氢谱表征确定为2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇，核磁氢谱图见附图1。
实施例2
向三颈烧瓶中加入0.15mol的5-甲基-2-巯基噻二唑，随后向体系中加入0.15mol的氢氧化钠和50mL蒸馏水，缓慢升温至70℃，维持温度搅拌反应0.5小时；待体系中固体全部溶解后，加入0.05mol的2,2,2-三氯乙醇，维持温度搅拌反应3小时；停止反应后，反应液用热水洗涤，除去水溶性杂质，用二氯甲烷萃取，收集有机层，减压蒸馏除去溶剂，得到浅黄色固体产物，为添加剂目标产物。
目标产物经核磁氢谱表征确定为2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇。
实施例3
向三颈烧瓶中加入0.06mol的5-甲基-2-巯基噻二唑，随后向体系中加入0.06mol的氢氧化钠和20mL蒸馏水，缓慢升温至65℃，维持温度搅拌反应0.5小时；待体系中固体全部溶解后，加入0.02mol的2,2,2-三氯乙醇，维持温度搅拌反应3小时；停止反应后，反应液用热水洗涤，除去水溶性杂质，用二氯甲烷萃取，收集有机层，减压蒸馏除去溶剂，得到浅黄色固体产物，为添加剂目标产物。
目标产物经核磁氢谱表征确定为2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇。
摩擦学性能评价
实验例：将实施例1合成的2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇加入聚乙二醇(PEG200)基础油中得润滑剂，质量分数为1.0％。
对比例：聚乙二醇(PEG200)基础油
采用Optimol-SRV IV摩擦磨损试验机评价润滑剂的润滑性能，摩擦系数由试验机给出；采用MicroXAM-3D三维轮廓仪检测磨斑的表面形貌并利用软件计算出磨损体积。试验条件为：载荷100N、温度为100℃、振幅1mm、频率25Hz，试验时间30min；载荷200N、温度为100℃、振幅1mm、频率25Hz，试验时间30min；载荷400N、温度为100℃、振幅1mm、频率25Hz，试验时间30min。上试球和下试盘均为GCr15钢(SAE52100，硬度为59-61HRC)，上试球直径为10mm；下试盘直径为24mm，厚度为8.0mm。每次试验前在球盘接触部位滴加两到三滴润滑剂。
摩擦学性能SRV测试结果显示，随着载荷的增加，实验例的磨损体积比对比例的磨损体积明显减小。实验例与对比例相比，当测试载荷为100N时，摩擦系数0.15保持不变，磨损体积从28.91×105μm3减少至2.67×105μm3左右；当测试载荷为200N时，摩擦系数从0.15减少至0.14，磨损体积从65.92×105μm3减少至4.44×105μm3：当测试载荷为400N时，摩擦系数0.16保持不变，磨损体积从15.40×106μm3减少至2.16×106μm3。测试结果说明添加剂具有优异的抗磨性能。
在PEG类润滑油中的溶解性能评价
本发明实施例1制备的2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇和二巯基噻二唑二聚体类添加剂在PEG200中的溶解性测试，测试结果见表1。
从表1对比试验数据可以看出，二巯基噻二唑二聚体类润滑添加剂油溶性较差，限制了其在润滑油中的使用；2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇添加剂的油溶性较好，可以作为润滑添加剂在PEG类润滑油中使用。
表1 2,2,2-三((5-甲基-1,3,4-噻二唑-2-基)硫代)乙醇与二巯基噻二唑二聚体类添加剂的对比试验
Figure BDA0003470073730000051
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (4)

1.一种润滑油添加剂，其特征在于，具体结构如式(1)所示：
Figure FDA0003470073720000011
2.权利要求1所述润滑油添加剂的制备方法，其特征在于，该润滑油添加剂由5-甲基-2-巯基噻二唑和2,2,2-三氯乙醇反应得到，合成路线如下所示：
Figure FDA0003470073720000012
3.如权利要求2所述润滑油添加剂的制备方法，其特征在于，具体合成方法如下：向三颈烧瓶中加入一定量的5-甲基-2-巯基噻二唑，随后向体系中加入适量的氢氧化钠和蒸馏水，缓慢升温至60-75℃，维持温度搅拌反应0.5-1.0小时；待体系中固体全部溶解后，加入一定量的2,2,2-三氯乙醇，维持温度搅拌反应3-5小时；停止反应后，反应液用热水洗涤，除去水溶性杂质，用二氯甲烷萃取，收集有机层，减压蒸馏除去溶剂，得到浅黄色固体产物，为添加剂目标产物。
4.权利要求1所述润滑油添加剂的应用，其特征在于，该润滑油添加剂加入PEG类润滑油中，提高PEG类润滑油的极压抗磨性能。
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