CN110845417A - 一种氨基酸离子液体水基添加剂及其制备方法和应用 - Google Patents
一种氨基酸离子液体水基添加剂及其制备方法和应用 Download PDFInfo
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- CN110845417A CN110845417A CN201911180623.0A CN201911180623A CN110845417A CN 110845417 A CN110845417 A CN 110845417A CN 201911180623 A CN201911180623 A CN 201911180623A CN 110845417 A CN110845417 A CN 110845417A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 84
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 80
- 239000000654 additive Substances 0.000 title claims abstract description 78
- 230000000996 additive effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000001014 amino acid Nutrition 0.000 claims description 79
- 230000001050 lubricating effect Effects 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 14
- -1 isooctyl Chemical group 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 8
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 8
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 8
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 claims description 5
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 5
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 claims description 5
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 5
- 235000018417 cysteine Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 4
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004472 Lysine Substances 0.000 claims description 4
- 239000002173 cutting fluid Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229930182817 methionine Natural products 0.000 claims description 4
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001421 myristyl 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])[H] 0.000 claims description 3
- 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 3
- 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 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 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 3
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 3
- 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 40
- 239000010959 steel Substances 0.000 abstract description 40
- 239000000314 lubricant Substances 0.000 abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002894 organic compounds Chemical class 0.000 abstract description 4
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- 239000002904 solvent Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 22
- 238000005406 washing Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000002994 raw material Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 239000012074 organic phase Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 238000001819 mass spectrum Methods 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- DEZDKWLZZLEVST-UHFFFAOYSA-N tetrabutyl(hydroxy)-$l^{5}-phosphane Chemical compound CCCCP(O)(CCCC)(CCCC)CCCC DEZDKWLZZLEVST-UHFFFAOYSA-N 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HNRXDBMBQAOWFV-UHFFFAOYSA-M tetraoctadecylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCCCC[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC HNRXDBMBQAOWFV-UHFFFAOYSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- DFQPZDGUFQJANM-UHFFFAOYSA-M tetrabutylphosphanium;hydroxide Chemical compound [OH-].CCCC[P+](CCCC)(CCCC)CCCC DFQPZDGUFQJANM-UHFFFAOYSA-M 0.000 description 1
- NEUNMNDZSAVWGE-UHFFFAOYSA-N tetraethyl(hydroxy)-lambda5-phosphane Chemical compound CCP(O)(CC)(CC)CC NEUNMNDZSAVWGE-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- DCFYRBLFVWYBIJ-UHFFFAOYSA-M tetraoctylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC DCFYRBLFVWYBIJ-UHFFFAOYSA-M 0.000 description 1
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
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- C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
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- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
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- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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Abstract
本发明提供了一种氨基酸离子液体水基添加剂及其制备方法和应用,属于润滑油添加剂有机化合物技术领域。本发明提供的氨基酸离子液体水基添加剂,结构式如式1所示。本发明提供的氨基酸离子液体水基添加剂可以生物降解,对环境友好,无污染,并具有良好的溶解性。本发明制得的氨基酸离子液体水基添加剂亦能够充分溶解于不同极性的有机溶剂如氯仿、甲醇,和水中,作为钢/钢摩擦副的润滑剂时,具有优良的减摩抗磨性能以及高承载能力。
Description
技术领域
本发明属于润滑油添加剂有机化合物技术领域,尤其涉及一种氨基酸离子液体水基添加剂及其制备方法和应用。
背景技术
传统石油基润滑剂可以有效地提高减摩抗磨性能、降低摩擦副的磨损率,但传统石油基润滑剂成本高、导热系数低、易燃性高、闪点低、易造成环境污染,影响了它的大范围使用。与此相比,水性添加剂具有成本低、耐火和导热性能好、环保等优点。但是水性添加剂在使用过程中,水会引起金属表面严重腐蚀,同时水的粘度低,使得摩擦副之间难以形成弹性流体动力润滑膜,增大了摩擦副的磨损率。
离子液体是一种很好的润滑添加剂,具有低熔点,优异的热稳定性以及良好的有机化合物的相容性,大大改善了摩擦磨损的问题。把离子液作为添加剂可以有效改善水的摩擦学性能。但目前研究较多的离子液体液体多集中于含卤素阴离子的咪唑型离子液体,这类离子液的使用对环境造成一定的污染,对于设计一种环境友好型的低污染甚至无污染的离子液体成了当下亟待解决的问题。
发明内容
鉴于此,本发明的目的在于提供一种氨基酸离子液体水基添加剂及其制备方法和应用。本发明提供的氨基酸离子液体水基添加剂具有良好的溶解性、润滑性能和抗摩擦性能,对环境友好,无污染,是一种性能优异的水润滑添加剂。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种氨基酸离子液体水基添加剂,结构式如式1所示:
其中,X为P或N;
R1、R2、R3和R4独立地为C1~C18的烷基;
R包括式a~g中的一种:
优选地,所述R1、R2、R3和R4独立地包括甲基、乙基、丙基、丁基、异丁基、戊基、异戊基、辛基、异辛基、癸基、异癸基、十二烷基、十四烷基、十六烷基或十八烷基。
本发明还提供了上述技术方案所述氨基酸离子液体水基添加剂的制备方法,包括以下步骤:
将四烷基氢氧化物、氨基酸和水混合,进行酸碱中和反应后,得到所述氨基酸离子液体水基添加剂;
所述氨基酸包括色氨酸、半胱氨酸、赖氨酸、苯丙氨酸、丝氨酸、蛋氨酸或组氨酸;
所述四烷基氢氧化物中的烷基的碳个数独立地为1~18;
所述四烷基氢氧化物为四烷基氢氧化磷或四烷基氢氧化铵。
优选地,所述四烷基氢氧化物和氨基酸的摩尔比为1:1~1:1.4。
优选地,所述酸碱中和反应的温度为室温,时间为4~24h。
本发明还提供了上述技术方案所述的氨基酸离子液体水基添加剂或由本发明还提供了上述技术方案所述制备方法制得的氨基酸离子液体水基添加剂在水基润滑加工液或切削液的制备领域中的应用。
本发明提供了一种氨基酸离子液体水基添加剂,结构式如式1所示:
其中,X为P或N;
R1、R2、R3和R4独立地为C1~C18的烷基;
R包括式a~g中的一种:
本发明提供的氨基酸离子液体水基添加剂以季磷盐离子或季铵盐离子作为离子液体的阳离子,以不同取代基的氨基酸负离子作为阴离子,离子液体的正负离子容易通过极性基团吸附在金属界面上,形成有效的边界吸附膜,边界吸附膜的存在阻碍了水与金属的直接接触,延缓了金属在水中的腐蚀速率。同时,离子液体本身包含的氮、磷元素易使其与基底发生摩擦化学反应,形成摩擦化学反应膜,阻隔了摩擦副之间的直接接触,使其具有良好的润滑性能。且本发明提供的氨基酸离子液体水基添加剂可以生物降解,对环境友好,无污染,并具有良好的溶解性,本发明制得的氨基酸离子液体水基添加剂亦能够充分溶解于不同极性的有机溶剂如氯仿、甲醇,和水中,作为钢/钢摩擦副的润滑剂时,具有优良的减摩抗磨性能以及高承载能力。
附图说明
下面结合附图和具体实施方式对本发明作进一步详细的说明。
图1为将不同浓度P4444-Trp氨基酸离子液体水基添加剂作为钢/钢摩擦副润滑剂时,在25℃条件下的Tafel曲线图。
具体实施方式
本发明提供了一种氨基酸离子液体水基添加剂,结构式如式1所示:
在本发明中,所述R1、R2、R3和R4独立地为C1~C18的烷基,所述R1、R2、R3和R4独立地优选包括甲基、乙基、丙基、丁基、异丁基、戊基、异戊基、辛基、异辛基、癸基、异癸基、十二烷基、十四烷基、十六烷基或十八烷基。本发明采用的碳原子数能够使制备得到的氨基酸离子液体水基添加剂在摩擦磨损过程中生成厚度大的保护膜,提高氨基酸离子液体水基添加剂的润滑性能和抗磨性能。
在本发明中,所述X为P或N。本发明以季磷盐离子或季铵盐离子作为离子液体的阳离子,以不同取代基的氨基酸负离子作为阴离子,离子液体的正负离子能够与金属表面发生吸附,形成物理吸附膜,阻碍了水与金属的直接接触,延缓了金属在水中的腐蚀速率。
在本发明中,所述R包括式a~g中的一种:
本发明通过在分子结构中引入不同R基团作为阴离子,R基团可以与水分子中的氢键相互作用,充当两性离子,使R基团具有的手性和其它性质结合到离子液体中,氨基酸离子液体水基添加剂可以生物降解,对环境友好,无污染。
本发明还提供了上述技术方案所述氨基酸离子液体水基添加剂的制备方法,包括以下步骤:
将四烷基氢氧化物、氨基酸和水混合,进行酸碱中和反应后,得到所述氨基酸离子液体水基添加剂;
所述氨基酸包括色氨酸、半胱氨酸、赖氨酸、苯丙氨酸、丝氨酸、蛋氨酸或组氨酸;
所述四烷基氢氧化物中的烷基的碳个数独立地为1~18;
所述四烷基氢氧化物为四烷基氢氧化磷或四烷基氢氧化铵。
在本发明中,若无特殊说明,所采用原料均为本领域常规市售产品。
在本发明中,所述四烷基氢氧化物和氨基酸的摩尔比优选为1:1~1:1.4,进一步优选为1:1。
本发明对所述混合没有特殊的限定,采用本领域技术人员熟知的混合方式即可,具体的如机械搅拌。
在本发明中,所述酸碱中和反应的温度优选为室温,时间优选为4~24h,进一步优选为24h。
酸碱中和反应结束后,本发明优选将反应后得到的产物依次进行第一减压蒸餾、溶解、水洗、干燥和第二减压蒸餾。本发明对所述第一减压蒸馏的具体操作没有特殊的限定,采用本领域技术人员熟知的减压蒸馏方式即可。本发明通过第一减压蒸馏有效的去除酸碱中和反应产物中的溶剂。在本发明中,所述溶解优选在二氯甲烷中进行。本发明通过溶解有效地去除酸碱中和反应产物中残留的固体。本发明对所述水洗的具体操作方式没有特殊的限定,采用本领域技术人员熟知的水洗方式即可。本发明对所述水洗的次数没有特殊的限定,能够将酸碱中和反应产物中未反应的原料去除即可。本发明对所述干燥的具体操作方式没有特殊的限定,采用本领域技术人员熟知的干燥方式即可。本发明对所述第二减压蒸馏的具体操作没有特殊的限定,采用本领域技术人员熟知的减压蒸馏方式即可。本发明通过第二减压蒸馏有效的去除酸碱中和反应产物中的溶剂,得到氨基酸离子液体水基添加剂。
本发明还提供了上述技术方案所述的氨基酸离子液体水基添加剂或由本发明还提供了上述技术方案所述制备方法制得的氨基酸离子液体水基添加剂在水基润滑加工液或切削液的制备领域中的应用。
本发明对于所述水基润滑加工液或切削液的制备方式没有特殊的限定,采用本领域技术人员熟知的制备方式即可。
下面结合实施例对本发明提供的氨基酸离子液体水基添加剂及其制备方法和应用进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
本发明实施例优选采用德国耐驰公司生产的STA449 F3 TGA-DSC同步热分析仪测定制备得到的氨基酸离子液体水基添加剂的热稳定性。
本发明实施例优选采用德国Optimol油脂公司生产的SRV-ΙV微振动摩擦磨损试验机对制备得到的氨基酸离子液体水基添加剂的减摩抗磨性能进行评价。其中,SRV-ΙV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:温度25℃,频率25Hz,振幅1mm,实验时间30min;试验上试球为Φ10mm的AISI 52100,硬度为59~61HRC的钢球。
钢/钢摩擦副中,下试样为Φ24mm、厚度7.9mm,硬度为59~61HRC的AISI 52100钢块,试验所采用载荷为100N;下试样的磨损体积由BRUKER-NPFLEX三维光学轮廓仪测得。
实施例1
按摩尔比为1:1的比例称取四丁基氢氧化磷和组氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式2所示)。
其中,阳离子部分的质谱计算值:259.2549,实测值:259.2540,阴离子部分的质谱计算值:154.0617,实测值:154.0620。
实施例2
按摩尔比为1;1的比例称取四丁基氢氧化磷和丝氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式3所示)。
其中,阳离子部分的质谱计算值:259.2549,实测值:259.2541,阴离子部分的质谱计算值:104.0348,实测值:104.0351。
实施例3
按摩尔比为1:1的比例称取四丁基氢氧化磷和色氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到淡黄色氨基酸离子液体水基添加剂(结构式如式4所示)。
其中,阳离子部分的质谱计算值:259.2549,实测值:259.2544,阴离子部分的质谱计算值:203.0821,实测值:203.0821。
实施例4
按摩尔比为1:1的比例称取四丁基氢氧化磷和苯丙氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式5所示)。
其中,阳离子部分的质谱计算值:259.2549,实测值:259.2542,阴离子部分的质谱计算值:164.0712,实测值:164.0714。
实施例5
按摩尔比为1:1的比例称取四丁基氢氧化磷和赖氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式6所示)。
其中,阳离子部分的质谱计算值:259.2549,实测值:259.2540,阴离子部分的质谱计算值:145.0977,实测值:145.0983。
实施例6
按摩尔比为1:1的比例称取四丁基氢氧化磷和蛋氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式7所示)。
其中,阳离子部分的质谱计算值:259.2545,实测值:259.2540,阴离子部分的质谱计算值:148.0441,实测值:148.0432。
实施例7
按摩尔比为1:1的比例称取四丁基氢氧化磷和半胱氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式8所示)。
其中,阳离子部分的质谱计算值:259.2544,实测值:259.2540,阴离子部分的质谱计算值:119.0041,实测值:119.0047。
实施例8
按摩尔比为1:1的比例称取四丁基氢氧化铵和半胱氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式9所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例9
按摩尔比为1:1的比例称取四丁基氢氧化铵和组氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式10所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例10
按摩尔比为1:1的比例称取四丁基氢氧化铵和色氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到淡黄色氨基酸离子液体水基添加剂(结构式如式11所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例11
按摩尔比为1:1的比例称取四辛基氢氧化磷和色氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到淡黄色氨基酸离子液体水基添加剂(结构式如式12所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例12
按摩尔比为1:1的比例称取四辛基氢氧化磷和丝氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式13所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例13
按摩尔比为1:1的比例称取四辛基氢氧化铵和组氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式14所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例14
按摩尔比为1:1的比例称取四乙基氢氧化磷和组氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式15所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例15
按摩尔比为1:1的比例称取四乙基氢氧化铵和组氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到白色氨基酸离子液体水基添加剂(结构式如式16所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例16
按摩尔比为1:1的比例称取四(十八烷基)氢氧化铵和色氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到淡黄色氨基酸离子液体水基添加剂(结构式如式17所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
实施例17
按摩尔比为1:1.4的比例称取四(十八烷基)氢氧化铵和色氨酸,溶于水后,室温下搅拌反应24h。反应结束后,减压蒸除溶剂,固体物用二氯甲烷溶解,水洗除去未反应的原料,之后干燥有机相,减压蒸出溶剂得到淡黄色氨基酸离子液体水基添加剂(结构式如式18所示)。
对制备得到的氨基酸离子液体水基添加剂的溶解性、润滑性能和抗摩擦性能进行测试,测试结果与实施例1~7结果相似。
溶解性性能测试
将1g实施例1~2、4~7制得的氨基酸离子液体水基添加剂分别溶解于100mL的氯仿、甲醇和水中,观察溶解结果。
表1为实施例1~2、4~7制得的氨基酸离子液体水基添加剂的溶解性测试结果,从表1的结果可以看出,本发明制得的氨基酸离子液体水基添加剂在不同极性的溶剂和水中均表现出优异的溶解性。
表1实施例1~2、4~7制得的氨基酸离子液体水基添加剂的溶解性
摩擦磨损性能测试
将实施例3制得的P4444-Trp氨基酸离子液体水基添加剂,分别按照P4444-Trp与水的质量比为0.3:100、0.5:100、1:100、1.5:100和2:100的比例加水溶解,制备得到P4444-Trp润滑组合物为钢/钢摩擦副润滑剂,分别记作0.3%P4444-Trp、0.5%P4444-Trp、1%P4444-Trp、1.5%P4444-Trp和2%P4444-Trp。
利用德国Optimol油脂公司生产的SRV-ΙV微振动摩擦磨损试验机评价实施例3制得的P4444-Trp氨基酸离子液体的水溶性润滑组合物的摩擦磨损性能,测试结果参见表2~6。
表2为不同浓度对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响
表2为不同浓度对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响,实验条件为:载荷100N,频率25Hz,振幅1mm,实验时间30min,温度25℃,P4444-Trp在润滑组合物中的浓度为0.3%~2%,实验上试球为直径为10mm钢球,下试样为直径为24mm,厚度7.9mm钢块。实验结果表明,随着P4444-Trp在润滑剂中浓度的增大,平均摩擦系数和平均磨损体积逐渐减小,与纯水相比,P4444-Trp润滑组合物的减摩抗磨性能有极大的提高。
表3为不同频率对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响
表3是为不同频率对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响,实验条件为:载荷100N,振幅1mm,实验时间30min,温度25℃,频率10~50Hz,P4444-Trp在润滑组合物中的浓度为1%,实验上试球为直径为10mm钢球,下试样为直径为24mm,厚度7.9mm钢块。实验结果表明,P4444-Trp润滑组合物的减摩性能随频率增大都有了极大的提高。
表4为不同载荷对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响
表4是P4444-Trp润滑组合物和水作为钢/钢摩擦副润滑剂的摩擦系数和磨损体积数据,实验条件为:载荷50N~150N,频率25Hz,振幅1mm,实验时间30min,温度25℃,P4444-Trp在润滑组合物中的浓度为1%,实验上试球为直径为10mm钢球,下试样为直径为24mm,厚度7.9mm钢块。实验结果表明,P4444-Trp润滑组合物的减摩抗磨性能在100N时较好。
表5为不同氨基酸离子液体水基添加剂对润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响
表5为不同氨基酸离子液体水基添加剂对润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的平均摩擦系数和平均磨损体积的影响,实验条件为:载荷100N,频率25Hz,振幅1mm,实验时间30min,温度25℃,实验上试球为直径为10mm钢球,下试样为直径为24mm,厚度7.9mm钢块。实验结果表明,与纯水相比,氨基酸离子液体水基添加剂对润滑组合物的减摩抗磨性能有了极大的提高。
表6为不同浓度对P4444-Trp润滑组合物为钢/钢摩擦副润滑剂在25℃条件下的电化学腐蚀的影响
图1为将不同浓度P4444-Trp氨基酸离子液体水基添加剂作为钢/钢摩擦副润滑剂时,在25℃条件下的Tafel曲线图。结合表6和图1分析可知,以铁电极,铂电极和饱和甘汞电极构成三电极体系,0.3%P4444-Trp,1%P4444-Trp和2%P4444-Trp的腐蚀电流密度接近,而与水的腐蚀电流密度(Icorr)差一个数量级。这表明,P4444-Trp能有效的提高铁的防腐蚀性能。抗腐蚀性能的提高归因于通过在基体表明吸附离子液体形成保护膜,从而阻止铁的腐蚀。实验结果表明与纯水相比,润滑组合物的抗腐蚀性能有了极大的提高。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (6)
2.根据权利要求1所述的氨基酸离子液体水基添加剂,其特征在于,所述R1、R2、R3和R4独立地包括甲基、乙基、丙基、丁基、异丁基、戊基、异戊基、辛基、异辛基、癸基、异癸基、十二烷基、十四烷基、十六烷基或十八烷基。
3.权利要求1或2所述氨基酸离子液体水基添加剂的制备方法,其特征在于,包括以下步骤:
将四烷基氢氧化物、氨基酸和水混合,进行酸碱中和反应后,得到所述氨基酸离子液体水基添加剂;
所述氨基酸包括色氨酸、半胱氨酸、赖氨酸、苯丙氨酸、丝氨酸、蛋氨酸或组氨酸;
所述四烷基氢氧化物中的烷基的碳个数独立地为1~18;
所述四烷基氢氧化物为四烷基氢氧化磷或四烷基氢氧化铵。
4.根据权利要求3所述的制备方法,其特征在于,所述四烷基氢氧化物和氨基酸的摩尔比为1:1~1:1.4。
5.根据权利要求3所述的制备方法,其特征在于,所述酸碱中和反应的温度为室温,时间为4~24h。
6.权利要求1或2所述的氨基酸离子液体水基添加剂或由权利要求3~5任一项所述制备方法制得的氨基酸离子液体水基添加剂在水基润滑加工液或切削液的制备领域中的应用。
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