CN110951517B - 无卤胆碱螯合硼离子液体润滑添加剂及应用 - Google Patents

无卤胆碱螯合硼离子液体润滑添加剂及应用 Download PDF

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CN110951517B
CN110951517B CN201911255672.6A CN201911255672A CN110951517B CN 110951517 B CN110951517 B CN 110951517B CN 201911255672 A CN201911255672 A CN 201911255672A CN 110951517 B CN110951517 B CN 110951517B
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王晓波
柳军明
赵改青
赵勤
李维民
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明提供无卤胆碱螯合硼离子液体润滑添加剂及应用,所述无卤胆碱螯合硼离子液体润滑添加剂以甘油单油酸酯、硼酸和氢氧化胆碱为原材料,通过络合反应和酸碱反应两步制备而成。其中甘油单油酸酯是市售的分析纯级。本发明的离子液体润滑添加剂具有优异的抗腐蚀性和高温下的减摩抗磨性能,对环境友好。

Description

无卤胆碱螯合硼离子液体润滑添加剂及应用
技术领域
本发明提供无卤胆碱螯合硼离子液体润滑添加剂及应用,涉及离子液体与工业润滑技术领域。
背景技术
离子液体是一种由阳离子和阴离子组成的室温下的熔融盐,其熔点一般低于100℃。离子液体具有热稳定性好、溶解性好、低蒸汽压、结构可设计、性能可调控的特点,在催化合成、材料制备、萃取分离、摩擦学等领域应用广泛。离子液体合成方法大体分为直接合成法和两步合成法,直接合成法包括酸碱中和季胺化反应,操作经济简便、没有副产物、产品易纯化。近年来,环境友好型含螯合硼酸阴离子的离子液体获得了大量的研究,这种离子液体被视为BF4 -,PF6 -和其他含有卤素或硫、磷元素的离子液体的替代者。专利ZL02808687.2中报道了氢-双(螯合)硼酸化合物和碱金属-双(螯合)硼酸盐的制备方法,该专利中双(螯合)硼酸化合物是硼酸或三氧化二硼与二羧酸有机化合物反应制备的。专利CN103113242B中报道了功能化氯化胆碱离子液体、其制备方法及其在电化学储能器件中的应用,其阴离子主要是Cl-、Br-、BF4 -等,该离子液体应用于锂离子电池和电容器领域。王向中等(王向中,王毓民.氯化胆碱作为润滑剂研究[J].河南科学.2001.29(5):538-540)研究了氯化胆碱在钢-钢摩擦副表面上不同速度不同载荷条件下的润滑特性,结果表明,用氯化胆碱作为润滑剂,钢-钢摩擦副之间能出现低的摩擦系数,但在摩擦一段时间之后,润滑剂会失去,摩擦系数上升。
聚乙二醇作为润滑基础油在工业生产中逐步获得了更多的青睐,其优异的润滑性能不仅可以为设备的正常运转提供有力的保障同时可生物降解对环境无害。因此,本发明利用环境友好型的甘油单油酸酯、硼酸与胆碱经过络合反应和酸碱反应两步制备了一种无卤胆碱螯合硼离子液体润滑添加剂,为聚乙二醇基础油在工业润滑领域中提供了一种抗腐蚀性优异、高温条件下减摩抗磨优异的绿色润滑添加剂。
发明内容
本发明的目的在于提供无卤胆碱螯合硼离子液体润滑添加剂及应用。
本发明是这样实现的,该添加剂以氢氧化胆碱为阳离子,以双甘油单油酸酯螯合硼为阴离子,该添加剂的化学结构式为式(1),
Figure GDA0002679682390000021
作为一种优选的实施方案,所述阴离子为甘油单油酸酯和硼酸经过络合反应制备而成。
无卤胆碱螯合硼离子液体润滑添加剂的应用,该添加剂用作聚乙二醇基础油的润滑添加剂,其用量是0.25wt.%~1wt.%。
本发明的有益效果:本发明提供的无卤胆碱螯合硼离子液体润滑添加剂在高温条件下具有优异的减摩抗磨性,具有优异的抗腐蚀性,对环境友好,无污染。
附图说明
图1为实施例1制备的离子液体和甘油单油酸酯的热失重曲线;
图2为实施例1制备的离子液体和甘油单油酸酯的热失重曲线的一阶积分曲线;
图3为实施例1制备的离子液体在聚乙二醇200中添加百分含量为0wt%、0.25wt%、0.5wt%、1wt%的摩擦系数曲线;
图4为实施例1制备的离子液体在聚乙二醇200中添加百分含量为0wt%、0.25wt%、0.5wt%、1wt%的磨损体积图表。
具体实施方式
下面通过具体的实施例与附图对本发明做进一步的阐述和说明。
实施例1
无卤胆碱螯合硼离子液体润滑添加剂的制备方法,包括如下步骤:
(1)称取1.236g(0.02mol)的硼酸加入到14.2616g(0.04mol)的甘油单油酸酯中,在80℃条件下,持续搅拌反应3h,混合物由无色转变为淡黄色。
(2)向步骤(1)所得的混合物添加5.2683g(0.02mol)氢氧化胆碱水溶液,120℃条件下持续搅拌反应3h,随着反应的进行水分被不断的蒸发,混合物由淡黄色逐渐转变为深棕色,然后70℃真空干燥48h,最后得到深棕色粘稠液体产物[cho][GMOB],[cho][GMOB]以氢氧化胆碱为阳离子,以双甘油单油酸酯螯合硼为阴离子,化学结构式如式(2)所示,
Figure GDA0002679682390000031
氢氧化胆碱水溶液与双甘油单油酸酯螯合硼的摩尔比为1:1。
DSC(NETZSCH)热重仪测试实施例1制备的离子液体[cho][GMOB]的热稳定性,同时与甘油单油酸酯GMO进行对比。称取20±0.5mg样品置于样品池中,测试条件为25℃-800℃,升温速率10℃/min,气氛为氮气。结果参见表1、附图1和附图2。
表1甘油单油酸酯GMO和制备离子液体[cho][GMOB]的热稳定分析数据
Figure GDA0002679682390000032
由表1可见,实施例1制备的离子液体润滑添加剂质量损失1%,5%,10%时对应温度分别为196.8℃,210.4℃,228.5℃,说明实施例1制备的离子液体润滑添加剂具备较高的耐热性能;实施例1制备的离子液体润滑添加剂的残炭率为4.28%,明显大于甘油单油酸酯的残碳率0.9%,可见实施例1制备的离子液体润滑添加剂中含有硼,残炭率主要是硼的氧化物。由图2可见,实施例1制备的离子液体润滑添加剂的DTG曲线中出现两个明显的吸热峰,第一个吸热峰表明胆碱的存在,说明目标离子液体制备成功。
腐蚀性能测试
按照国标GB/T 5096-2017《石油产品铜片腐蚀试验法》,测试实施例1制备的离子液体[cho][GMOB]对铜片的腐蚀性能。将实施例1制备所得离子液体[cho][GMOB]按照0.25wt.%、0.5wt.%、1wt.%的比例分别加入聚乙二醇200基础油中。将打磨光亮的三个标准尺寸的铜片依次放入添加剂添加量为0.25wt%、0.5wt%、1wt%的30ml润滑油品中,然后置于100℃浴中测试3h,然后取出铜片清洗干净,并与比色卡对比。试验结果显示三个铜片腐蚀程度均为1a,说明实施例1制备所得离子液体[cho][GMOB]具有优异的抗腐蚀性能。
摩擦学性能测试
将实施例1制备所得离子液体[cho][GMOB]按照0.25wt%、0.5wt%、1wt%的比例分别加入聚乙二醇200基础油中。然后对离子液体[cho][GMOB]含量为0wt.%和0.25wt.%、0.5wt.%、1wt.%的聚乙二醇200润滑油均进行摩擦系数表征与磨损表征。
使用德国Optimol油脂公司的SRV-IV微动摩擦磨损试验机,在温度为150℃,频率为25Hz,振幅为1mm,载荷为200N,时间为30min的条件下对离子液体[cho][GMOB]含量为0wt.%和0.25wt.%、0.5wt.%、1wt.%的聚乙二醇200润滑油进行摩擦系数评价。试验所用钢球为直径10mm的GCr15轴承钢,下试样所用块体为直径24mm、高7.9±0.1mm的GCr15钢块,结果参见附图3和表2。
表2制备离子液体[cho][GMOB]和基础油PEG200的摩擦系数分析
Figure GDA0002679682390000041
参阅图3及表2中摩擦系数结果可知随着制备离子液体[cho][GMOB]添加量的增加,与未添加离子液体[cho][GMOB]的基础油相比,900秒摩擦系数、1800秒摩擦系数及平均摩擦系数均有不同程度减小,且实施例1制备所得离子液体[cho][GMOB]添加量为1wt.%时摩擦系数降低最明显。
使用MicroXAM 3D非接触式三维表面轮廓仪对经过SRV摩擦系数评价后的离子液体[cho][GMOB]含量为0wt.%和0.25wt.%、0.5wt.%、1wt.%的聚乙二醇200润滑油的下试样钢块的磨痕进行磨损表征。结果参阅附图4,试验结果表明随着制备离子液体[cho][GMOB]添加量的增加,与基础油相比,磨损体积均有不同程度的减小,且制备离子液体[cho][GMOB]添加量为1wt.%时磨损降低最明显。
本发明的有益效果:本发明提供的无卤胆碱螯合硼离子液体润滑添加剂在高温条件下具有优异的减摩抗磨性,具有优异的抗腐蚀性,对环境友好,无污染。

Claims (3)

1.无卤胆碱螯合硼离子液体润滑添加剂,其特征在于,该添加剂以氢氧化胆碱为阳离子,以双甘油单油酸酯螯合硼为阴离子,该添加剂的化学结构式为式(1)。
Figure FDA0002679682380000011
2.根据权利要求1所述的无卤胆碱螯合硼离子液体润滑添加剂,其特征在于,所述阴离子为甘油单油酸酯和硼酸经过络合反应制备而成。
3.根据权利要求1所述的无卤胆碱螯合硼离子液体润滑添加剂的应用,其特征在于,该添加剂用作聚乙二醇基础油的润滑添加剂,其用量是0.25wt.%~1wt.%。
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