CN110724065B - 马尿酸盐类抗腐蚀性离子液体及其制备方法和应用 - Google Patents
马尿酸盐类抗腐蚀性离子液体及其制备方法和应用 Download PDFInfo
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- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 title abstract description 19
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 80
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Abstract
本发明提供马尿酸盐类抗腐蚀性离子液体及其制备方法和应用，涉及液体润滑剂技术领域。该离子液体为[CnMIM][Hip]、[CHO][Hip]和[PXXXY][Hip]中的任意一种，该离子液体可以作为润滑剂。本发明提供的离子液体引入马尿酸根阴离子，阴离子无卤素，对金属具有强吸附性，具有较好的抗腐蚀性与优异的摩擦学性能。
Description
技术领域
本发明涉及离子液体润滑剂技术领域，具体是马尿酸盐类抗腐蚀性离子液体及其制备方法和应用，该马尿酸盐类抗腐蚀性离子液体作为离子液体润滑剂，具有良好的抗腐蚀性与良好的摩擦学性能。
背景技术
离子液体作为一种在室温下或室温附近呈现液态的、完全由阴阳离子构成的熔盐体系。它一般具有难挥发、宽液程、高热稳定性和结构可设计性等一系列高性能液体润滑材料所必需的特殊性能，很有潜力作为新型高性能液体润滑剂在航空、航天及电子信息等高技术领域得到广泛的应用(Zhou F,Liang Y.M.,Liu W.M.Chem Soc Rev 2009；38:2590-2599；Zhang S.W.,Hu L.T.,Qiao D.,Tribol.Int.,2013；66:289-295.)。2001年，刘维民院士在国际上首次发现离子液体是一类性能优异的多用途润滑剂，并引起了相当多国内外科研人员的广泛重视(Ye C.F.,Liu W.M.,Chen Y.X.,Yu L.G.Chem.Commun.2001；21:2244-2245)。
随着研究的深入，研究人员发现常规离子液体虽然润滑性能优异，但也表现出一定的腐蚀性能，特别是在水存在的条件下，一些常规离子液体会对金属摩擦部件产生较为严重的腐蚀问题，强腐蚀性离子液体不仅会损坏金属运动机构及其相关部件，同时还会加剧金属摩擦部件的腐蚀磨损，严重影响运动机构长期运转的稳定性和可靠性(Li Y,ZhangS.W.,Ding Q,Feng D.P.,Qin B.F.,,Hu L.T.Tribol Int 2017；114:121-31)。因此，兼具抗腐蚀性和优异润滑性能的离子液体在润滑工程领域具有很大的应用潜力。
发明内容
本发明提供马尿酸盐类抗腐蚀性离子液体及其制备方法和应用，解决了现有技术中离子液体对金属具有强腐蚀性的技术问题。
本发明是这样实现的：所述马尿酸盐类抗腐蚀性离子液体为[CnMIM][Hip]、[CHO][Hip]和[PXXXY][Hip]中的任意一种，所述[CnMIM][Hip]的化学结构如式(1)所示，所述[CHO][Hip]的化学结构如式(2)所示，所述[PXXXY][Hip]的化学结构如式(3)所示，
其中，R1、R2和R3均为烷基，n为R1的碳原子数，X为R2的碳原子数，Y为R3的碳原子数。
作为一种优选的实施方案，所述R1为乙基、丁基或己基中的一种，所述n分别为2、4或6中的一个值。
作为一种优选的实施方案，R2为丁基或己基中的一种，所述X分别为4或6中的一个值。
作为一种优选的实施方案，R3为癸基或十四烷基中的一种，所述Y分别为10或14中的一个值。
马尿酸盐类抗腐蚀性离子液体的制备方法，包含如下步骤：将马尿酸钠和硝酸银分别溶解到蒸馏水中，配制质量分数为20％-50％的马尿酸钠水溶液和30％-60％的硝酸银水溶液，然后将所述硝酸银水溶液逐滴加入所述马尿酸钠水溶液中，室温下搅拌反应10-30min后过滤收集沉淀，用150ml乙醇水溶液洗涤沉淀3次，得到马尿酸银固体；
将氯化物溶解到蒸馏水中，然后向氯化物溶液中加入所述马尿酸银固体，室温下搅拌反应5-10h，过滤除去沉淀，滤液旋蒸之后经80-100℃真空干燥箱干燥12-36h，得到马尿酸盐类抗腐蚀性离子液体。
作为一种优选的实施方案，所述马尿酸钠与硝酸银的摩尔比为1:1～1.15。
作为一种优选的实施方案，所述乙醇水溶液中乙醇的质量分数为50％。
作为一种优选的实施方案，所述氯化物与马尿酸银的摩尔比为1:1.1～1.2。
作为一种优选的实施方案，所述氯化物为氯化甲基烷基咪唑、氯化胆碱和氯化四烷基季鏻盐中的一种。
马尿酸盐类抗腐蚀性离子液体的应用，将[CnMIM][Hip]、[CHO][Hip]和[PXXXY][Hip]作为离子液体润滑剂，所述[CnMIM][Hip]为[C2MIM][Hip]、[C4MIM][Hip]和[C6MIM][Hip]中的一种，所述[PXXXY][Hip]为[P44410][Hip]、[P44414][Hip]、[P66610][Hip]和[P66614][Hip]中的一种。
本发明的有益效果：本发明提供的马尿酸盐类抗腐蚀性离子液体具有良好的抗腐蚀性，用作离子液体润滑剂时具有优异的润滑性能。
附图说明
图1为含[BMIM][BF4]的水溶液以及含马尿酸盐类抗腐蚀性离子液体的水溶液对低碳钢腐蚀的电化学阻抗谱对比图；
图2为含[BMIM][BF4]的水溶液以及含马尿酸盐类抗腐蚀性离子液体的水溶液对低碳钢腐蚀的动电位极化曲线对比图；
图3为聚乙二醇基础油和马尿酸盐类抗腐蚀性离子液体作为钢/钢润滑剂的实时摩擦系数比较图；
图4为聚乙二醇基础油和马尿酸盐类抗腐蚀性离子液体作为钢/钢润滑剂的磨损体积比较图。
具体实施方式
下面将结合附图，阐述本发明的实施例，显然，所描述的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做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
将24.14g马尿酸钠和20.38g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.0，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将14.66g氯化甲基乙基咪唑离子液体溶解到蒸馏水中制备氯化物水溶液，其中氯化甲基乙基咪唑离子液体与马尿酸银的摩尔比为1:1.2，然后向氯化物溶液中加入马尿酸银固体，室温下搅拌反应5h，过滤除去沉淀得滤液，将滤液旋蒸之后经80℃真空干燥箱干燥12h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[C2MIM][Hip]，化学结构参见式(4)，
其中，R1为乙基。
实施例2
将24.14g马尿酸钠和20.38g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.0，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将17.47g氯化甲基丁基咪唑离子液体溶解到蒸馏水中制备成氯化物水溶液，氯化甲基丁基咪唑与马尿酸银的摩尔比为1:1.2，然后向氯化物水溶液中加入马尿酸银固体，室温下搅拌反应8h，过滤除去沉淀得滤液，将滤液旋蒸之后经80℃真空干燥箱干燥24h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[C4MIM][Hip]，化学结构式如式(5)所示。
其中，R1为丁基。
实施例3
将24.14g马尿酸钠和20.38g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.0，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将20.27g氯化甲基己基咪唑离子液体溶解到蒸馏水中得氯化物溶液，其中氯化甲基己基咪唑与马尿酸银的摩尔比为1:1.2，然后向氯化物溶液中加入马尿酸银，室温下搅拌反应10h，过滤除去沉淀得滤液，将滤液旋蒸之后经80℃真空干燥箱干燥36h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[C6MIM][Hip]，化学结构式参见式(6)。
其中，R1为己基。
实施例4
将24.14g马尿酸钠和22.42g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.1，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将15.23g氯化胆碱离子液体溶解到蒸馏水中得氯化物溶液，氯化胆碱与马尿酸银的摩尔比为1:1.1，然后向氯化物溶液中加入马尿酸银，室温下搅拌反应10h，过滤除去沉淀得滤液，将滤液旋蒸之后经80℃真空干燥箱干燥36h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[CHO][Hip]，化学结构式参见式(7)。
实施例5
将24.14g马尿酸钠和22.42g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.1，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将41.35g氯化三丁基癸基季鏻盐溶解到蒸馏水中得氯化物溶液，氯化三丁基癸基季鏻盐与马尿酸银的摩尔比为1:1.1，然后向氯化物溶液中加入马尿酸银固体，室温下搅拌反应8h，过滤除去沉淀得滤液，将滤液旋蒸之后经100℃真空干燥箱干燥12h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[P44410][Hip]，化学结构式参见式(8)，
其中R2为丁基，R3为癸基。
实施例6
将24.14g马尿酸钠和22.42g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.1，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将47.48g氯化三丁基十四烷基季鏻盐溶解到蒸馏水中(氯化物与马尿酸银的摩尔比为1:1.1)，然后向溶液中加入马尿酸银，室温下搅拌反应10h，过滤除去沉淀得滤液，将滤液旋蒸之后经100℃真空干燥箱干燥24h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[P44414][Hip]，化学结构式参见式(9)。
其中R2为丁基，R3为十四烷基。
实施例7
将24.14g马尿酸钠和30.57g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.5，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将48.33g氯化三己基癸基季鏻盐溶解到蒸馏水中制备氯化物水溶液，化三己基癸基季鏻盐与马尿酸银的摩尔比为1:1.15，然后向氯化物水溶液中加入马尿酸银，室温下搅拌反应8h，过滤除去沉淀得滤液，将滤液旋蒸之后经100℃真空干燥箱干燥24h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[P66610][Hip]，化学结构参见式(10)。
其中R2为己基，R3为癸基。
实施例8
将24.14g马尿酸钠和30.57g硝酸银分别溶解到50mL蒸馏水中制备马尿酸钠水溶液和硝酸银水溶液，马尿酸钠与硝酸银的摩尔比为1:1.5，然后利用恒压漏斗将硝酸银水溶液逐滴加入马尿酸钠水溶液中，室温下搅拌反应30min，然后过滤收集沉淀，并用150ml50％乙醇水溶液洗涤沉淀3次，得到马尿酸银固体。将51.93g氯化三己基十四烷基基季鏻盐溶解到蒸馏水中制备氯化物水溶液，氯化三己基十四烷基基季鏻盐与马尿酸银的摩尔比为1:1.15，然后向氯化物溶液中加入马尿酸银固体，室温下搅拌反应10h，过滤除去沉淀得滤液，将滤液旋蒸之后经100℃真空干燥箱干燥36h，即可得到马尿酸盐类抗腐蚀性离子液体，记作[P66614][Hip]，化学结构式见式(11)。
其中R2为己基，R3为十四烷基。
离子液体性能测试实验
抗腐蚀性能测试
制备含马尿酸盐类抗腐蚀性离子液体的水溶液：将马尿酸盐类抗腐蚀性离子液体：[C4MIM][Hip]、[CHO][Hip]和[P44414][Hip]均取1g分别溶于49g去离子水中，配制成含2.0％马尿酸盐类抗腐蚀性离子液体的水溶液。
制备含[BMIM][BF4]的水溶液：取常规离子液体1-甲基-3-丁基咪唑四氟硼酸盐([BMIM][BF4])1g溶于49g去离子水中，配制成含2.0％[BMIM][BF4]的水溶液，作为对照。
电化学测试：选取打磨好的低碳钢样块作为工作电极，铂电极作为辅助电极，饱和甘汞电极作为参比电极，电解液分别为质量分数2.0％的[BMIM][BF4]的水溶液、质量分数2.0％的马尿酸盐类抗腐蚀性离子液体的水溶液，在电化学工作站Gamry Reference 3000上进行电化学阻抗谱和极化曲线测试。电化学阻抗谱测试是在溶液的开路电位下进行，施加的正弦波幅值是5.0mV，扫描频率范围是105Hz到10-1Hz，动电位极化曲线扫描电位的范围为相对于工作电极开路电位的-350mV到350mV，扫描速率为0.5mV/s，工作电极的暴露面积是1.0cm2。
电化学测试结果：通过Gamry Echem.Analyst软件对电化学实验结果进行分析，得到相关的电化学参数，参见表1，对低碳钢腐蚀的电化学阻抗谱对比参见附图1，对低碳钢腐蚀的动电位极化曲线对比参见附图2。
表1四种电解液的腐蚀电位、腐蚀电流密度和溶液电荷转移电阻参数表
由表1可见，常规离子液体[BMIM][BF4]具有较强的腐蚀性，对低碳钢的腐蚀较为严重，本发明制备的马尿酸盐类离子液体腐蚀电流密度远远小于常规离子液体[BMIM][BF4]，阻抗远远大于[BMIM][BF4]，表现出良好的抗腐蚀性能。
润滑性能测试
在Optimol公司SRV-IV微振动摩擦磨损试验机上考察马尿酸盐类抗腐蚀性离子液体润滑剂的润滑性能，并与常规润滑油聚乙二醇200(PEG200)作对比。选定载荷100N，温度100℃，频率25Hz，振幅1mm，实验时间30min，实验上试球为AISI 52100钢球，下试样为AISI52100钢块。摩擦实验结束后，采用MicroXAM公司非接触式三维表面轮廓仪检测钢块的磨损情况，实验结果参见表2，聚乙二醇基础油和马尿酸盐类抗腐蚀性离子液体作为钢/钢润滑剂的实时摩擦系数对比参见附图3，磨损体积比较参见附图4。
表2不同润滑剂的平均摩擦系数表
| 润滑剂 | 平均摩擦系数 |
| PEG200 | 0.166 |
| [C<sub>4</sub>MIM][Hip] | 0.103 |
| [CHO][Hip] | 0.116 |
| [P<sub>44414</sub>][Hip] | 0.098 |
由表2和图3、图4可见，PEG200在该摩擦副上具有较高的摩擦系数和磨损量，而三种马尿酸盐类抗腐蚀性离子液体润滑剂均表现出较低且平稳的摩擦系数和较小的磨损量，具有优异的润滑性能。
发明的有益效果：本发明提供的马尿酸盐类抗腐蚀性离子液体具有良好的抗腐蚀性，用作离子液体润滑剂时具有优异的润滑性能。
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 (7)
1.马尿酸盐类抗腐蚀性离子液体，其特征在于，为 [CHO][Hip]，所述[CHO][Hip]的化学结构如式(2)所示：
2.如权利要求1所述的马尿酸盐类抗腐蚀性离子液体的制备方法，其特征在于，具体包含如下步骤：将马尿酸钠和硝酸银分别溶解到蒸馏水中，配制质量分数为20％-50％的马尿酸钠水溶液和30％-60％的硝酸银水溶液，然后将所述硝酸银水溶液逐滴加入所述马尿酸钠水溶液中，室温下搅拌反应10-30min后过滤收集沉淀，用150ml乙醇水溶液洗涤沉淀3次，得到马尿酸银固体；
将氯化物溶解到蒸馏水中，然后向氯化物溶液中加入所述马尿酸银固体，室温下搅拌反应5-10h，过滤除去沉淀，滤液旋蒸之后经80-100℃真空干燥箱干燥12-36h，得到马尿酸盐类抗腐蚀性离子液体。
3.根据权利要求2所述的制备方法，其特征在于，所述马尿酸钠与硝酸银的摩尔比为1:1～1 .15。
4.根据权利要求2所述的制备方法，其特征在于，所述乙醇水溶液中乙醇的质量分数为50％。
5.根据权利要求2所述的制备方法，其特征在于，所述氯化物与马尿酸银的摩尔比为1:1 .1～1 .2。
6.根据权利要求2至5任意一项所述的制备方法，其特征在于，所述氯化物为氯化胆碱。
7.如权利要求1所述的马尿酸盐类抗腐蚀性离子液体的应用，其特征在于，将[CHO][Hip]作为离子液体润滑剂。
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