CN105646239A - 一种无氟烷基羧酸离子液体及其制备方法和应用 - Google Patents
一种无氟烷基羧酸离子液体及其制备方法和应用 Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 71
- -1 alkyl carboxylic acid Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 58
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 9
- 239000010687 lubricating oil Substances 0.000 claims abstract description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 4
- 229930195729 fatty acid Natural products 0.000 claims abstract description 4
- 239000000194 fatty acid Substances 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- PRYHQDXTXKTHCH-UHFFFAOYSA-M octanoate;tributyl(methyl)azanium Chemical compound CCCCCCCC([O-])=O.CCCC[N+](C)(CCCC)CCCC PRYHQDXTXKTHCH-UHFFFAOYSA-M 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CXYFRCVURBIHGZ-UHFFFAOYSA-L octanedioate tetrabutylazanium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.C(CCCC(=O)[O-])CCC(=O)[O-] CXYFRCVURBIHGZ-UHFFFAOYSA-L 0.000 claims description 6
- AHEWKOFOKYWYAT-UHFFFAOYSA-M octanoate;tetrabutylazanium Chemical compound CCCCCCCC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC AHEWKOFOKYWYAT-UHFFFAOYSA-M 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 36
- 239000010959 steel Substances 0.000 abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
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- 238000005260 corrosion Methods 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- SDWYUQHONRZPMW-UHFFFAOYSA-L disodium;octanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCC([O-])=O SDWYUQHONRZPMW-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 2
- DHAWHVVWUNNONG-UHFFFAOYSA-M tributyl(methyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(CCCC)CCCC DHAWHVVWUNNONG-UHFFFAOYSA-M 0.000 description 2
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- HGCHUZIWRLBTGP-UHFFFAOYSA-N octanoic acid;sodium Chemical compound [Na].CCCCCCCC(O)=O HGCHUZIWRLBTGP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C07C53/126—Acids containing more than four carbon atoms
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- 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
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Abstract
本发明提供了一种无氟烷基羧酸离子液体，具有如下通式(I)所示结构，其中：R1-R4分别独立选自碳原子数为1-18的烷基，或者苄基；R5选自碳原子数为1-6的烷基，或者通式(II)所示的基团，n选自2-12之间的任意整数。本发明提供的无氟烷基羧酸离子液体由于所采用的原料为低毒、廉价的季铵盐和脂肪酸钠盐，因此合成成本低、毒性小；由于不含氟元素，因此水解稳定性高，避免对金属基底材料造成腐蚀，是一种绿色环保的液体润滑剂，可作为钢/钢、钢/铜和钢/铝摩擦副的润滑剂，具有优异的减摩抗磨性能。
Description
技术领域
本发明涉及一种离子液体，具体涉及一种可作为润滑剂的无氟烷基羧酸离子液体及其制备方法。
背景技术
随着工业的飞速发展，传统的石油基润滑剂已很难满足现代机械在苛刻条件，如低倾点、高粘度指数、高热氧化稳定性、耐燃、超高真空、耐射线等苛刻条件下的润滑与防护。发展具有更好的耐高低温、耐高真空、化学安定性、难燃性和抗辐射性的高性能合成润滑剂显得尤为重要，它对于发展空间技术、信息技术、电子工业，尤其是涉及国家安全的高新技术领域有着极其重要的意义。
离子液体作为一类新型绿色介质，近年来在电化学、有机合成与催化、分离提取等领域受到了广泛关注。其不易燃易爆、蒸气压低、挥发性低、呈液态的温区范围宽、和较高的热稳定性等特点与理想润滑剂所期望的性能极为吻合，是一类极具发展前途的新型润滑剂。2001年，刘维民研究小组在国际上首次报道了离子液体是一类性能优异的多用途润滑剂[Ye，C.；Liu，W.；Chen，Y.；Yu，L.Chem.Commun.2001，21，2244-2245]。自此，离子液体润滑材料引起了国内外众多研究人员的重视。研究结果表明，离子液体无论是直接作为润滑剂，还是作为润滑油添加剂都具有优异的减摩抗摩效果。目前，文献中所报道的离子液体润滑剂绝大多数为含氟阴离子的离子液体，如：BF4 -，PF6 -，(CF3SO2)2N-等。这些离子液体不但合成成本高，而且由于含有氟元素，在长期储存或摩擦过程中，容易吸收空气中的潮气，通过水解产生氟化氢从而对金属基底材料产生腐蚀，并对周围环境造成污染，因此很难将它们进行大队规模的工业化应用。设计和制备高性能、低成本、绿色环保的无氟离子液体润滑剂仍然是该领域的研究热点之一。
发明内容
为了解决上述问题，本发明提供了一种无氟烷基羧酸离子液体，具有通式(I)所示结构，
其中：R1-R4分别独立选自碳原子数为1-18的烷基，或者苄基；
R5选自碳原子数为1-6的烷基，或者通式(II)所示的基团，
n选自2-12之间的任意整数。
优选地，本发明提供的无氟烷基羧酸离子液体，具有通式(III)所示结构或通式(IV)所示结构：
其中：R1-R4中，至少有一个选自碳原子数为1-8的烷基或者苄基，其余选自碳原子数为1-18的烷基。
更优选地，通式(III)和通式(IV)中，R1-R4中至少有一个选自甲基、乙基、丙基、丁基、辛基或苄基中的一种，其余选自甲基、乙基、丙基、丁基、辛基、癸基、十二烷基、十六烷基或十八烷基中的一种。
优选地，本发明提供的无氟烷基羧酸离子液体，所述通式(III)所示离子液体选自四丁基铵辛酸盐或甲基三丁基铵辛酸盐；
所述通式(IV)所示离子液体选自四丁基铵辛二酸盐、甲基三丁基铵辛二酸盐或甲基三丁基铵癸二酸盐。
本发明还提供了一种如通式(I)所述的无氟烷基羧酸离子液体的制备方法，具体为，将一定摩尔比的通式(V)所示的烷基取代季铵盐和通式(VI)所示的脂肪酸钠盐溶于乙腈水溶液中，在室温下反应12-48小时，反应结束后，将乙腈蒸干，水层用溶剂萃取、水洗，再次蒸干溶剂即得目标产物，
通式(V)中，R1-R4分别独立选自碳原子数为1-18的烷基，或者苄基，X选自Cl或Br；通式(VI)中R5选自甲基、乙基，丙基，异丙基、叔丁基，戊基或己基，或者通式(II)所示的基团，
n选自2-12之间的任意整数。
优选地，上述制备方法中，所述乙腈水溶液由体积比为1∶1的乙腈和水混合而成；所述萃取溶剂为乙醚、乙酸乙酯、二氯甲烷、氯仿或甲苯。
本发明还提供了上述离子液体作为润滑剂的应用，所述离子液体润滑剂由通式(I)所示的至少一种离子液体组成，
优选地，所述离子液体润滑剂由质量比为0-100∶100-0的通式(III)所示离子液体和通式(IV)所示离子液体组成。
本发明提供的无氟烷基羧酸离子液体作为液体润滑剂与传统含氟离子液体润滑剂相比，由于所采用的原料为低毒、廉价的季铵盐和脂肪酸钠盐，因此合成成本低、毒性小；由于不含氟元素，因此水解稳定性高，不容易对金属基底材料造成腐蚀。无氟烷基羧酸离子液体润滑剂是一种绿色环保的液体润滑剂，可作为钢/钢、钢/铜和钢/铝摩擦副的润滑剂，具有优异的减摩抗磨性能。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案并能予以实施，下面结合具体实施例对本发明作进一步说明，但所举实施例不作为对本发明的限定。
为了评价本发明所提供的无氟烷基羧酸离子液体作为润滑剂的抗摩擦磨损效果，本发明采用德国Optimol油脂公司生产的SRV-⑤微振动摩擦磨损试验机对所制备的润滑剂的抗摩擦磨损性能进行评价，并与市售油聚-α-烯烃(PAO10)以及传统常用的离子液体1-甲基-3-丁基咪唑双三氟甲烷黄酰亚胺盐(L-F104)进行对比。
其中，SRV-⑤微振动摩擦磨损试验机的摩擦副接触方式为球-盘点接触，测试条件为：载荷100N，温度25℃，频率25Hz，振幅1mm，实验时间30min；试验上试球为Φ10mm的AISI52100钢球；钢/钢摩擦副中，下试样为Φ24mm、厚度7.9mm的AISI52100钢块，硬度为59-61HRC；钢/铜摩擦副中，下试样为Φ24mm、厚度7.9mm的铜合金块，硬度为130-160HV；钢/铝摩擦副中，下试样为Φ24mm、厚度7.9mm的铝合金块，硬度为140-170HV；下试样的磨损体积由BRUKER-NPFLEX三维光学轮廓仪测得。
实施例1
一种可作为润滑剂的无氟烷基羧酸离子液体，具体为离子液体四丁基铵辛酸盐，该离子液体的制备方法为：将0.05mol的四丁基氯化铵和0.05mol辛酸钠溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得四丁基铵辛酸盐。
上述离子液体可作为润滑剂，具体采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪对该离子液体润滑剂的摩擦磨损性能进行评价，其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.042和0.3145*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.035和9.7701*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.043和33.0808*105μm3。
实施例2：
一种可作为润滑剂的无氟烷基羧酸离子液体，具体为离子液体四丁基铵辛二酸盐，该离子液体的制备方法为：将0.1mol的四丁基氯化铵和0.05mol辛二酸二钠盐溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得四丁基铵辛二酸盐。
上述离子液体可作为润滑剂，采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪评价了该离子液体润滑剂的摩擦磨损性能，其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.037和0.1280*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.045和12.5039*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.033和9.6217*105μm3。
实施例3：
由实施例1所制得的离子液体四丁基铵辛酸盐和实施例2所制得的离子液体四丁基铵辛二酸盐以质量比为10∶90的比例混合，室温下搅拌直至充分混合，得到由两种离子液体组成的组合型离子液体润滑剂。采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪评价了润滑剂的摩擦磨损性能，其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.037和0.2091*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.034和11.4402*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.033和10.1024*105μm3。
实施例4：
由离子液体甲基三丁基铵辛酸盐和离子液体甲基三丁基铵辛二酸盐以质量比为10∶90的比例混合，室温下搅拌直至充分混合，得到由上述两种离子液体组成的组合型离子液体润滑剂。
具体的，甲基三丁基铵辛酸盐的制备方法为：将0.05mol的甲基三丁基溴化铵和0.05mol辛酸钠溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得甲基三丁基铵辛酸盐。
甲基三丁基铵辛二酸盐的制备方法为：该离子液体的制备方法为，将0.1mol的甲基三丁基溴化铵和0.05mol辛二酸二钠盐溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得甲基三丁基铵辛二酸盐。
采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪对本实施例所制得的组合离子液体润滑剂的摩擦磨损性能进行评价，其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.039和0.3006*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.036和12.2789*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.036和12.2454*105μm3。
实施例5：
由实施例1所制得的四丁基铵辛酸盐和实施例2所制得的四丁基铵辛二酸盐以质量比为50∶50的比例混合，室温下搅拌直至充分混合，得到组合型的离子液体润滑剂。
采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪对本实施例所制得的组合离子液体润滑剂的摩擦磨损性能进行评价，其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.032和0.2778*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.030和11.0786*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.035和10.2044*105μm3。
实施例6：
由甲基三丁基铵辛酸盐和甲基三丁基铵癸二酸盐以质量比为10∶90的比例混合，室温下搅拌直至充分混合，得到由两种离子液体组成的组合型的离子液体润滑剂。
具体的，甲基三丁基铵辛酸盐的制备方法为：将0.05mol的甲基三丁基氯化铵和0.05mol辛酸钠溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得甲基三丁基铵辛酸盐。
甲基三丁基铵癸二酸盐的制备方法为：将0.1mol的甲基三丁基氯化铵和0.05mol癸二酸二钠盐溶于100mL体积比为1∶1的乙腈和水的混合液中，在室温下反应48小时，反应结束后将乙腈蒸干，水层用二氯甲烷萃取、水洗，再次蒸干溶剂即得甲基三丁基铵癸二酸盐。
采用SRV-⑤微振动摩擦磨损试验机和BRUKER-NPFLEX三维光学轮廓仪评价了润滑剂的摩擦磨损性能，其在100N，25℃条件下的平均摩擦系数和磨损体积分别为：其在100N，25℃条件下作为钢/钢摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.040和0.1918*105μm3；作为钢/铜摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.033和8.1204*105μm3；作为钢/铝摩擦副润滑剂的平均摩擦系数和磨损体积分别为：0.033和9.2904*105μm3。
对比市售油PAO10、传统离子液体L-F104以及本发明实施例1-6所提供的润滑剂在100N，25℃条件下的平均摩擦系数和磨损体积的数据具体如表1所示。
表1：各润滑剂的测试性能对比表
由表1摩擦磨损实验结果可见，本发明实施例1-6所提供的烷基羧酸离子液体润滑剂作为钢/钢、钢/铜和钢/铝三种机械设备中最常用的摩擦副的润滑剂，与市售油PAO10相比，具有非常低且平稳的摩擦系数和优异的抗磨性能，其抗摩擦磨损性能甚至比传统含氟离子液体润滑剂L-F104更优异。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，其保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内，本发明的保护范围以权利要求书为准。
Claims (9)
1.一种无氟烷基羧酸离子液体，其特征在于，具有通式(I)所示结构，
其中：R1-R4分别独立选自碳原子数为1-18的烷基，或者苄基；
R5选自碳原子数为1-6的烷基，或者通式(II)所示的基团，
n选自2-12之间的任意整数。
2.根据权利要求1所述的无氟烷基羧酸离子液体，其特征在于，具有通式(III)所示结构或通式(IV)所示结构：
其中：所述R1-R4中，至少有一个选自碳原子数为1-8的烷基或者苄基，其余选自碳原子数为1-18的烷基。
3.根据权利要求2所述的无氟烷基羧酸离子液体，其特征在于，
所述R1-R4中，至少有一个选自甲基、乙基、丙基、丁基、辛基或苄基，其余选自甲基、乙基、丙基、丁基、辛基、癸基、十二烷基、十六烷基或十八烷基。
4.根据权利要求3所述的无氟烷基羧酸离子液体，其特征在于，
所述通式(III)所示离子液体选自四丁基铵辛酸盐或甲基三丁基铵辛酸盐；
所述通式(IV)所示离子液体选自四丁基铵辛二酸盐、甲基三丁基铵辛二酸盐或甲基三丁基铵癸二酸盐。
5.根据权利要求1所述的无氟烷基羧酸离子液体的制备方法，其特征在于，将一定摩尔比的通式(V)所示的烷基取代季铵盐和通式(VI)所示的脂肪酸钠盐溶于乙腈水溶液中，在室温下反应12-48小时，反应结束后，蒸干，用溶剂萃取、水洗，再次蒸干溶剂即得通式(I)所示离子液体，
通式(V)中，R1-R4分别独立选自碳原子数为1-18的烷基，或者苄基，X选自Cl或Br；通式(VI)中R5选自碳原子数为1-6的烷基，或者通式(II)所示的基团，
n选自2-12之间的任意整数。
6.根据权利要求5所述的无氟烷基羧酸离子液体的制备方法，其特征在于，所述萃取溶剂为乙醚、乙酸乙酯、二氯甲烷、氯仿或甲苯。
7.根据权利要求5所述的无氟烷基羧酸离子液体的制备方法，其特征在于，所述乙腈水溶液由体积比为1∶1的乙腈和水混合而成。
8.一种润滑剂，其特征在于，由通式(I)所示的至少一种离子液体组成，
9.根据权利要求8所述的液体润滑剂，其特征在于，由质量比为0-100∶100-0的通式(III)所示离子液体和通式(IV)所示离子液体组成，
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