CN114958454B - 离子液体组合物及其制备方法 - Google Patents

离子液体组合物及其制备方法 Download PDF

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CN114958454B
CN114958454B CN202210590157.9A CN202210590157A CN114958454B CN 114958454 B CN114958454 B CN 114958454B CN 202210590157 A CN202210590157 A CN 202210590157A CN 114958454 B CN114958454 B CN 114958454B
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ionic liquid
liquid composition
hydraulic oil
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phosphate
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CN114958454A (zh
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徐聪
杨开乔
王晓琳
李忆晨
张红敏
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Meishan Jinhong Electronic Materials Co ltd
Jinhong Gas Co ltd
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Abstract

本发明公开了一种离子液体组合物及其制备方法,所述离子液体组合物,按重量百分比计,包括80%‑90%离子液体A以及10%‑20%离子液体B。本发明的离子液体组合物及其制备方法,通过离子液体A和离子液体B的复配,使离子液体组合物满足作为液压油工质的条件,需要向离子液体组合物中加入其他添加剂,即可避免因为液压油挥发的VOCs导致的污染。

Description

离子液体组合物及其制备方法
技术领域
本发明是关于液压油技术领域,特别是关于一种离子液体组合物及其制备方法。
背景技术
离子液体(ILs)是一种热稳定性好、难燃的极性液体。由于其具有挥发性小,传热性能有两、熔点低、液体范围宽、与有机溶剂的相容性好等特点,被认为可以用作新一代的液压油及压缩机工质。
但是目前液压油为适应多种工况和机器状况,会向油品中加入多种添加剂,以应对诸如氧化、高温、摩擦等状况,而这些液压油添加剂往往存在蒸气压偏低的情况,即会在于气体接触的过程中将添加剂本身分子释放出来,导致气体分子被污染,影响气体品质。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
本发明的目的在于提供一种离子液体组合物及其制备方法,其具有降低气体分子被污染的可能性的优点。
为实现上述目的,本发明的实施方式提供了一种离子液体组合物,按重量百分比计,包括80%-90%离子液体A以及10%-20%离子液体B,
所述离子液体A的结构式为:其中:R1和R2相同或不同,分别选自C1~4的饱和烷基,X为碳原子或氮原子;
所述离子液体B的结构式为:其中:R3和R4相同或不同,分别选自C1~5的烃基、醛基、羧基以及酯基。
在本发明的一个或多个实施方式中,所述[R22-PO4]-为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子。
在本发明的一个或多个实施方式中,所述[R42-PO4]-为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子。
在本发明的一个或多个实施方式中,所述烃基为饱和烃基或不饱和烃基。
本发明的实施方式还提供了一种离子液体组合物的制备方法,包括以下步骤:制备离子液体A;制备离子液体B;将所述离子液体A和离子液体B混合均匀,即得到所述离子液体组合物。
在本发明的一个或多个实施方式中,制备离子液体A的步骤包括:在保护气氛围下,在容器内加入氮杂五元环衍生物,然后向所述容器内滴加磷酸酯,控制反应温度并搅拌,反应终止分离、干燥,即得到所述离子液体A。
在本发明的一个或多个实施方式中,制备离子液体A的步骤还包括:所述杂五元环衍生物与磷酸酯的反应温度为160~180℃,反应时间为12~16h。
在本发明的一个或多个实施方式中,制备离子液体B的步骤包括:在保护气氛围下,在容器内加入咪唑环衍生物,然后向所述容器内滴加磷酸酯,控制反应温度并搅拌,反应终止分离、干燥,即得到所述离子液体B。
在本发明的一个或多个实施方式中,制备离子液体B的步骤还包括:所述咪唑环衍生物与磷酸酯的反应温度为160~180℃,反应时间为12~16h。
在本发明的一个或多个实施方式中,所述保护气为惰性气体,所述惰性气体为氩气或氮气。
与现有技术相比,根据本发明实施方式的离子液体组合物及其制备方法,通过离子液体A和离子液体B的复配,使离子液体组合物满足作为液压油工质的条件,需要向离子液体组合物中加入其他添加剂,即可避免因为液压油挥发的VOCs导致的污染。
具体实施方式
下面对本发明的具体实施方式进行详细描述,但应当理解本发明的保护范围并不受具体实施方式的限制。
根据本发明优选实施方式的离子液体组合物,按重量百分比计,包括80%-90%离子液体A以及10%-20%离子液体B,
所述离子液体A的结构式为:其中:R1和R2相同或不同,分别选自C1~4的饱和烷基,X为碳原子或氮原子;
所述离子液体B的结构式为:其中:R3和R4相同或不同,分别选自C1~5的烃基、醛基、羧基以及酯基。
由于离子液体本身即具有较好的摩擦学性能,国外已有将离子液体作为润滑油或者液压油添加剂的实例。使用含有磷的离子液体将有利于提高热稳定性以及抗磨减摩性,并且咪唑基团本身的碱性可与磷酸酯的酸性发生中和,有效减低磷酸酯配阴离子的腐蚀性。此外,本发明中涉及的离子液体的热分解温度均大于200℃,故采用磷酸根作为咪唑型离子液体的配阴离子可作为抗磨剂及热稳定剂。
[(R2)2-PO4]-可以为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子。
[(R4)2-PO4]-为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子,烃基为饱和烃基或不饱和烃基。
根据本发明优选实施方式的离子液体组合物的制备方法,包括以下步骤:
S1、制备离子液体A。
上述步骤可以包括:在保护气氛围下,在容器内加入氮杂五元环衍生物,然后向所述容器内滴加磷酸酯,反应温度为160~180℃,在搅拌的状态下反应12~16h,反应终止分离、干燥,即得到所述离子液体A。
S2、制备离子液体B。
上述步骤可以包括:在保护气氛围下,在容器内加入咪唑环衍生物,然后向所述容器内滴加磷酸酯,反应温度160~180℃,在搅拌的状态下反应12~16h,反应终止分离、干燥,即得到所述离子液体B。
S1和S2的顺序可以颠倒,且在S1和S2中的保护气可以为惰性气体,惰性气体可以为氩气或氮气。
S3、将所述离子液体A和离子液体B混合均匀,即得到所述离子液体组合物。
下面将结合具体的实施例,详细介绍本发明的离子液体组合物及其制备方法。
实施例1
在N2保护下,向100mL烧瓶中加入41g,1-甲基吡唑,在磁力搅拌下逐滴滴加70g磷酸三甲酯至上述物质中,在160℃下搅拌反应约12h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸三甲酯及氮杂五元环衍生物,即得到离子液体A,其结构式为:
在N2保护下,向250mL三口烧瓶中加入41g,1-甲基咪唑,在磁力搅拌下,逐滴滴加70g磷酸三甲酯至上述物质中,在160℃下搅拌反应约12h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及咪唑环衍生物,即得到离子液体B,其结构式为:
称取90g的离子液体A和10g的离子液体B,即得到离子液体组合物。
实施例2
在N2保护下,向150mL烧瓶中加入16.42g,1-甲基吡唑,在磁力搅拌下,逐滴滴加37g磷酸三乙酯至上述物质中,在160℃下搅拌反应约12h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及氮杂五元环衍生物,即得到离子液体A,其反应方程及结构式为:
在N2保护下,向250mL三口烧瓶中加入50g1-甲基咪唑,在磁力搅拌情况下,逐滴滴加110g磷酸三乙酯至上述物质中,在180℃下搅拌反应约16h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及咪唑环衍生物,即得到离子液体B,其反应方程及结构式为:
称取90g的离子液体A和10g的离子液体B,即得到离子液体组合物。
实施例3
在N2保护下,向250mL烧瓶中加入41g,1-乙基-1,2,4-三氮唑唑,在磁力搅拌的情况下,逐滴滴加56g磷酸三甲酯至上述物质中,在160℃下搅拌反应约12h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及氮杂五元环衍生物,即得到离子液体A,其反应方程及结构式为:
在N2保护下,向100mL三口烧瓶中依次加入25g,1-甲基咪唑,在磁力搅拌的情况下,逐滴滴加42g磷酸三甲酯至上述物质中,在160℃下搅拌反应约14h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及咪唑环衍生物,即得到离子液体B,其反应方程及结构式为:
称取90g的离子液体A和10g的离子液体B,即得到离子液体组合物。
实施例4
在N2保护下,向250mL烧瓶中加入41g,1-甲基吡唑,在磁力搅拌下逐滴滴加70g磷酸三甲酯至上述物质中,在170℃下搅拌反应约16h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸三甲酯及氮杂五元环衍生物,即得到离子液体A,其结构式为:
在N2保护下,向100mL三口烧瓶中依次加入14g,1-乙氧甲酰咪唑,在磁力搅拌下,逐滴滴加14g磷酸三甲酯至上述物质中,在170℃下搅拌反应约16h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及咪唑环衍生物,即得到离子液体B,其结构式为:
称取80g的离子液体A和20g的离子液体B,即得到离子液体组合物。
实施例5:
在N2保护下,向100mL烧瓶中加入40g,1-乙基吡唑,在磁力搅拌的情况下,逐滴滴加75g磷酸三乙酯至上述物质中,在180℃下搅拌反应约13h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及氮杂五元环衍生物,即得到离子液体A,其反应方程及结构式为:
在N2保护下,向100mL三口烧瓶中依次加入22g,N-乙酰基咪唑,在磁力搅拌的情况下,逐滴滴加30g磷酸三甲酯至上述混合液中,在160℃下搅拌反应约12h;反应结束后,将混合物上层的有机相倒出,下层的离子液体相旋蒸,真空干燥除去未反应的原料磷酸酯及咪唑环衍生物,即得到离子液体B,其反应方程及结构式为:
称取85g的离子液体A和15g的离子液体B,即得到离子液体组合物。
下面对实施例1~5中得到的离子液体组合物进行如下性能测试:
1)粘度测试:将配置好的离子液体搅拌2h后静置30分钟,使用数字粘度计进行粘度测试;
2)热重分析:将配置好的离子液体搅拌2h后静置30分钟,然后使用热重分析仪进行综合热分析;
3)失重分析:将配置好的离子液体搅拌2h后静置30分钟,然后称取固定重量(10g)离子液体混合物放入小烧杯中称重(烧杯+离子液体重量),然后保持搅拌的情况下加热至100℃,搅拌持续时间24h。24h后,再次对烧杯进行称重,计算二者差值,并计算单一小时失重量。
得到如下表数据:
从上表的数据可以得知实施例1~5的离子液体组合物具有较好的热分解温度,并且恒定温度和时间下失重,24h失重量<0.1g,说明其在100℃的工作环境下,不会分解,且可在120~560mm/s2的粘度范围内可调,具有良好的可调节性,可针对不同工况进行调整。
综上所述,本发明的离子液体组合物及其制备方法的有益效果为:通过两种离子液体的组合物作为液压油工质,不仅具备了良好的粘度可调节性能,并且在200℃的热条件下不会产生分解还无需添加其他添加剂,从而避免了液压油挥发的VOCs导致气体的污染。
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式,并且很显然,根据上述教导,可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用,从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。

Claims (10)

1.一种用于液压油的离子液体组合物,其特征在于,按重量百分比计,包括80%-90%离子液体A以及10%-20%离子液体B,
所述离子液体A的结构式为:其中:R1和R2相同或不同,分别选自C1~4的饱和烷基,X为碳原子或氮原子;
所述离子液体B的结构式为:其中:R3和R4相同或不同,分别选自C1~5的烃基、醛基、羧基以及酯基。
2.如权利要求1所述的用于液压油的离子液体组合物,其特征在于,所述[(R2)2-PO4]-为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子。
3.如权利要求1所述的用于液压油的离子液体组合物,其特征在于,所述[(R4)2-PO4]-为磷酸二甲酯阴离子、磷酸二乙酯阴离子或磷酸二丙酯阴离子。
4.如权利要求1所述的用于液压油的离子液体组合物,其特征在于,所述烃基为饱和烃基或不饱和烃基。
5.如权利要求1-4任一项所述的用于液压油的离子液体组合物的制备方法,其特征在于,包括以下步骤:制备离子液体A;制备离子液体B;将所述离子液体A和离子液体B混合均匀,即得到所述用于液压油的离子液体组合物。
6.如权利要求5所述的用于液压油的离子液体组合物的制备方法,其特征在于,制备离子液体A的步骤包括:在保护气氛围下,在容器内加入氮杂五元环衍生物,然后向所述容器内滴加磷酸酯,控制反应温度并搅拌,反应终止分离、干燥,即得到所述离子液体A。
7.如权利要求6所述的用于液压油的离子液体组合物的制备方法,其特征在于,制备离子液体A的步骤还包括:所述杂五元环衍生物与磷酸酯的反应温度为160~180℃,反应时间为12~16h。
8.如权利要求5所述的用于液压油的离子液体组合物的制备方法,其特征在于,制备离子液体B的步骤包括:在保护气氛围下,在容器内加入咪唑环衍生物,然后向所述容器内滴加磷酸酯,控制反应温度并搅拌,反应终止分离、干燥,即得到所述离子液体B。
9.如权利要求8所述的用于液压油的离子液体组合物的制备方法,其特征在于,制备离子液体B的步骤还包括:所述咪唑环衍生物与磷酸酯的反应温度为160~180℃,反应时间为12~16h。
10.如权利要求6~9任一项所述的用于液压油的离子液体组合物的制备方法,其特征在于,所述保护气为惰性气体,所述惰性气体为氩气或氮气。
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