CN102101842A - Naphthyl-functionalized ionic liquid having abrasion resistance and preparation method thereof - Google Patents
Naphthyl-functionalized ionic liquid having abrasion resistance and preparation method thereof Download PDFInfo
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- CN102101842A CN102101842A CN2009101177402A CN200910117740A CN102101842A CN 102101842 A CN102101842 A CN 102101842A CN 2009101177402 A CN2009101177402 A CN 2009101177402A CN 200910117740 A CN200910117740 A CN 200910117740A CN 102101842 A CN102101842 A CN 102101842A
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- ionic liquid
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- naphthyl
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Abstract
The invention discloses a naphthyl-functionalized ionic liquid having abrasion resistance and a preparation method thereof. The cation of the ionic liquid is alkylimidazole with a naphthyl functional group, and the anion is bromine ion, tetrafluoroborate ion, hexafluorophosphate ion or difluoromethyl sulfamide (trifluoromethyl sulfamide) ion. When being used as a lubricating agent for a steel/aluminum rubbing pair, the ionic liquid has excellent abrasion resistance; and compared with the common ionic liquid, the abrasion resistance of the ionic liquid disclosed by the invention is enhanced by two orders of magnitude.
Description
Technical field
The present invention relates to a kind of naphthyl functionalized ion liquid and preparation method thereof with resistance to abrasion.
Background technology
Because ionic liquid has extremely low volatility, uninflammability, high thermostability and chemical stability, high ionic conductivity, broad electrochemical window, advantages such as yin, yang ionic controllability, so ionic liquid has been subjected to paying close attention to and becoming rapidly widely the research focus in fields such as organic synthesis, electrochemistry, nanochemistry, catalytic chemistry and polymer chemistry.Calendar year 2001, Liu Weimin etc. find first that in the world ionic liquid is the multi-usage lubricant (Chem.Commun.21 (2001) 2244) of a class excellent performance.Chemical physics institute in Chinese Academy of Sciences Lanzhou has carried out a series of research to ion liquid tribological property and has caused numerous domestic and international researchists' interest that (Wear 256 (2004) 44 since then; 200410097689.0; J.Mater.Chem.16 (2006) 1529; Tribol.Lett.32 (2008) 73; Chem.Mater.20 (2008) 2719; ACS Appl.Mater.Interfaces 1 (2009) 467; Chem.Soc.Rev.38 (2009) 2590).
In recent years, the new function design of ionic liquid, synthetic become one of field, forward position that ionic liquid studies with using.By autotelic some functional group such as amido (Chem.Commun. (2005) 868), sulfydryl (J.Am.Chem.Soc.124 (2002) 926), urea groups (J.Am.Chem.Soc.126 (2004) 3026), sulfonic group (J.Org.Chem.70 (2005) 3251) etc. are incorporated into the ionic liquid that obtains functionalization on the ion liquid organic cation, these ionic liquids have obtained widespread use as novel green solvent or function medium in various fields.In addition, the ionic liquid of discovery phosphonic acid ester functionalization such as Liu Weimin has very excellent tribological property (200310117751.3; Chem.Lett 33 (2004) 524).Therefore have property design of ionic liquid and synthetic one of the ion liquid research focus that remains.
Summary of the invention
The object of the present invention is to provide a kind of naphthyl functionalized ion liquid with resistance to abrasion.
Another object of the present invention provides a kind of preparation method with naphthyl functionalized ion liquid of resistance to abrasion.
We have synthesized a kind of ionic liquid of naphthyl functionalization first, and this ionic liquid is not seen bibliographical information so far.Ion liquid positively charged ion is the alkyl imidazole that has naphthyl functional group, and negatively charged ion is bromide anion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions or two (trifluoromethyl sulphonamide) ion.
A kind of naphthyl functionalized ion liquid with resistance to abrasion is characterized in that ionic liquid has following structure:
Wherein, R represents CH
3, C
4H
9Or C
8H
17, X
-Represent Br
-, BF
4 -, PF
6 -Perhaps N (CF
3SO
2)
2 -
We have by synthetic concrete ionic liquid:
[NMMIm]Br：R＝CH
3，X＝Br；[NMMIm]BF
4：R＝CH
3，X＝BF
4；
[NMMIm]PF
6：R＝CH
3，X＝PF
6；[NMMIm]NTf
2：R＝CH
3，X＝N(CF
3SO
2)
2；
[NMBIm]Br：R＝C
4H
9，X＝Br；[NMBIm]BF
4：R＝C
4H
9，X＝BF
4；
[NMBIm]PF
6：R＝C
4H
9，X＝PF
6；[NMBIm]NTf
2：R＝C
4H
9，X＝N(CF
3SO
2)
2；
[NMOIm]Br：R＝C
8H
17，X＝Br；[NMOIm]BF
4：R＝C
8H
17，X＝BF
4；
[NMOIm]PF
6：R＝C
8H
17，X＝PF
6；[NMOIm]NTf
2：R＝C
8H
17，X＝N(CF
3SO
2)
2.
The ion liquid preparation feedback equation of the present invention is as follows:
R is CH in the reaction formula
3, C
4H
9Or C
8H
17, M is Na, NH
4Or Li, X
-Be Br
-, BF
4 -, PF
6 -Or N (CF
3SO
2)
2 -
A kind of preparation method with naphthyl functionalized ion liquid of resistance to abrasion, it is characterized in that: get equimolar menaphthyl bromine and Methylimidazole or butyl imidazole or octyl group imidazoles and under argon shield, join in the reactor, with the Virahol is to remove after solvent reacts 48-72 hour down in refluxing to desolvate, with sherwood oil and ethyl acetate washing, use acetone recrystallization then, obtain the ionic liquid of bromo; The bromo ionic liquid is dissolved in the mixing solutions of 1: 1 water and methyl alcohol, adds excessive ammonium hexafluorophosphate, sodium tetrafluoroborate or two (trifluoromethyl sulphonamide) lithium under room temperature stirring reaction 18-48 hour, obtain the naphthyl functionalized ion liquid.
With
1HNMR has characterized ion liquid structure, and physicochemical property such as its viscosity, density, surface tension, refractive index, fusing point, heat decomposition temperature and optical property are studied.The result shows that naphthyl is introduced the ion liquid physicochemical property in back change has been taken place, and viscosity obviously improves, and significant variation has also taken place for the position and the intensity at UV, visible light and fluorescent absorption peak.
Table 1: the ion liquid physicals of partial synthesis
| Ionic liquid | Viscosity (mm 2/s) 40℃ | Viscosity (mm 2/s) 100℃ | Viscosity index | Density (kg/m 3) 25℃ | 25 ℃ of refraction coefficients | 25 ℃ of surface tension |
| ?[NMBIm]NTf 2 | 295.9 | 17.9 | 52.4 | 1425 | 1.5079 | 37.8 |
| ?[NMOIm]NTf 2 | 370.5 | 21.2 | 60.1 | 1337 | 1.5058 | 35.6 |
Table 2: synthesize ion liquid heat decomposition temperature and fusing point
| Ionic liquid | Decomposition temperature ℃ | Fusing point ℃ |
| [NMMIm]Br | 284 | 134 |
| [NMMIm]BF 4 | 338 | 82 |
| [NMMIm]PF 6 | 332 | 132 |
| [NMMIm]NTf 2 | 417 | 31 |
| [NMBIm]Br | 275 | 88 |
| [NMBIm]BF 4 | 335 | 59 |
| [NMBIm]PF 6 | 331 | 91 |
| [NMBIm]NTf 2 | 413 | |
| [NMOIm]Br | 267 | 98 |
| [NMOIm]BF 4 | 332 | 55 |
| [NMOIm]PF 6 | 329 | 85 |
| [NMOIm]NTf 2 | 405 |
The little vibration friction abrasion testing machine of SRV-IV that adopts German optimol grease company to produce has been estimated the invention ionic liquid 1-of institute menaphthyl-3-butyl imidazole two (trifluoromethyl sulphonamide) ([NMBIm] NTf
2) and 1-menaphthyl-3-octyl group imidazoles two (trifluoromethyl sulphonamide) ([NMOIm] NTf
2) as the friction and wear behavior of steel/aluminium friction pair, and (L-F106) contrast with conventional ion liquid 1-methyl-3-hexyl imidazoles two (trifluoromethyl sulphonamide).Select load 50N for use, frequency 20Hz, amplitude 1mm, experimental period 30min, experimentally trying is AISI 52100 steel balls, following sample is AISI 2024 aluminium blocks.The result shows, common ionic liquid is the frictional coefficient instability during as the lubricant of steel/aluminium friction pair, and resistance to abrasion is poor.And institute's synthetic functionalized ion liquid has very low and frictional coefficient and the very abrasion resistance of excellence stably, and fastness to wear improves two orders of magnitude than common ionic liquid.
Table 3: synthetic ionic liquid [NMBIm] NTf of institute
2[NMOIm] NTf
2And L-F106 wear volume and average friction coefficient under these conditions
| Ionic liquid | Average friction coefficient | Wear volume (mm 3) |
| [NMBIm]NTf 2 | 0.145 | 3.65 |
| [NMOIm]NTf 2 | 0.138 | 3.28 |
| L-F106 | 0.180 | 455.10 |
Ionic liquid of the present invention also is expected to play a role in lubricated field etc. at analytical chemistry, catalytic chemistry and as basic oil additives.
Embodiment
For a better understanding of the present invention, describe by embodiment.
Embodiment 1:
Synthesizing of 1-menaphthyl-3-imidazole-butyl bromide ionic liquid ([NMBIm] Br)
13.27g (0.06mol) brooethyl naphthalene and 8.87g (0.072mol) butyl imidazole are joined in the there-necked flask that contains the 180ml Virahol; under the argon shield in 95 ℃ of reflux 72h.; remove upper organic phase after being chilled to room temperature; wash with sherwood oil and ethyl acetate the water-soluble back of surplus materials; steam to desolventize at last and use acetone recrystallization, obtain 16.57g1-menaphthyl-3-imidazole-butyl bromide ionic liquid (productive rate 80%).
1H?NMR(DMSO-d
6，400MHz)：9.52(1H，N＝CH)，8.00-7.52(9H)，5.64(2H，NCH
2)，4.20(2H)，1.77(2H)，1.23(2H)，0.87(3H).
Embodiment 2:
1-menaphthyl-3-butyl imidazole Tetrafluoroboric acid ionic liquid ([NMBIm] BF
4) synthetic
3.45g (0.01mol) 1-menaphthyl-3-imidazole-butyl bromide is dissolved in the mixing solutions of 100ml water and methyl alcohol, 1.32g (0.012mol) sodium tetrafluoroborate is dissolved in 10ml water and is added drop-wise in the above-mentioned solution, stirred 24 hours under the room temperature, be spin-dried for methyl alcohol and use ethyl acetate extraction after stopping to stir, wash anhydrous magnesium sulfate drying behind the organic layer with water, last solvent evaporated gets 2.83g1-menaphthyl-3-butyl imidazole Tetrafluoroboric acid ionic liquid (productive rate: 80%).
1H?NMR(DMSO-d
6，400MHz)：9.31(1H，N＝CH)，7.99-7.51(9H)，5.60(2H，NCH
2)，4.17(2H)，1.77(2H)，1.25(2H)，0.89(3H).
Embodiment 3:
1-menaphthyl-3-butyl imidazole phosphofluoric acid ionic liquid ([NMBIm] PF
6) synthetic
3.45g (0.01mol) 1-menaphthyl-3-imidazole-butyl bromide is dissolved in the mixing solutions of 100ml water and methyl alcohol, 1.96g (0.012mol) ammonium hexafluorophosphate is dissolved in 10ml water and is added drop-wise in the above-mentioned solution, stirred 24 hours under the room temperature, be spin-dried for methyl alcohol and use ethyl acetate extraction after stopping to stir, wash anhydrous magnesium sulfate drying behind the organic layer with water, last solvent evaporated gets 3.67g1-menaphthyl-3-butyl imidazole Tetrafluoroboric acid ionic liquid (productive rate: 89%).
1H?NMR(DMSO-d
6，400MHz)：9.32(1H，N＝CH)，8.00-7.51(9H)，5.60(2H，NCH
2)，4.18(2H)，1.78(2H)，1.25(2H)，0.89(3H).
Embodiment 4:
1-menaphthyl-3-butyl imidazole two (trifluoromethyl sulphonamide) ionic liquid ([NMBIm] NTf
2) synthetic
3.45g (0.01mol) 1-menaphthyl-3-imidazole-butyl bromide is dissolved in the mixing solutions of 100ml water and methyl alcohol, 3.45g (0.012mol) two (trifluoromethyl sulphonamide) lithium is dissolved in 10ml water and is added drop-wise in the above-mentioned solution, stirred 24 hours under the room temperature, be spin-dried for methyl alcohol and use ethyl acetate extraction after stopping to stir, wash anhydrous magnesium sulfate drying behind the organic layer with water, last solvent evaporated gets 4.91g1-menaphthyl-3-butyl imidazole Tetrafluoroboric acid ionic liquid (productive rate: 90%).
1H?NMR(DMSO-d
6，400MHz)：9.35(1H，N＝CH)，8.00-7.53(9H)，5.62(2H，NCH
2)，4.19(2H)，1.78(2H)，1.26(2H)，0.90(3H).
Claims (3)
1. naphthyl functionalized ion liquid with resistance to abrasion, it is characterized in that ion liquid positively charged ion is the alkyl imidazole that has naphthyl functional group, negatively charged ion is bromide anion, tetrafluoroborate ion, hexafluorophosphoricacid acid ions or two (trifluoromethyl sulphonamide) ion.
2. ionic liquid as claimed in claim 1 is characterized in that ionic liquid has following structure:
3. preparation method of ionic liquid as claimed in claim 1 or 2, it is characterized in that: get equimolar menaphthyl bromine and Methylimidazole or butyl imidazole or octyl group imidazoles and under argon shield, join in the reactor, with the Virahol is to remove after solvent reacts 48-72 hour down in refluxing to desolvate, with sherwood oil and ethyl acetate washing, use acetone recrystallization then, obtain the ionic liquid of bromo; The bromo ionic liquid is dissolved in the mixing solutions of 1: 1 water and methyl alcohol, adds excessive ammonium hexafluorophosphate, sodium tetrafluoroborate or two (trifluoromethyl sulphonamide) lithium under room temperature stirring reaction 18-48 hour, obtain the naphthyl functionalized ion liquid.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102415387A (en) * | 2011-09-26 | 2012-04-18 | 齐齐哈尔大学 | Surface active ionic liquid bactericide and application thereof in sterilization of oilfield injection water |
| CN106167466A (en) * | 2016-07-26 | 2016-11-30 | 中国科学院兰州化学物理研究所 | A kind of ionic liquid containing natural grease ring structure and its preparation method and application |
| CN106947569A (en) * | 2017-03-13 | 2017-07-14 | 深圳市合诚润滑材料有限公司 | Planetary gear lubricating grease |
-
2009
- 2009-12-18 CN CN2009101177402A patent/CN102101842A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102415387A (en) * | 2011-09-26 | 2012-04-18 | 齐齐哈尔大学 | Surface active ionic liquid bactericide and application thereof in sterilization of oilfield injection water |
| CN102415387B (en) * | 2011-09-26 | 2013-09-04 | 齐齐哈尔大学 | Surface active ionic liquid bactericide and application thereof in sterilization of oilfield injection water |
| CN106167466A (en) * | 2016-07-26 | 2016-11-30 | 中国科学院兰州化学物理研究所 | A kind of ionic liquid containing natural grease ring structure and its preparation method and application |
| CN106167466B (en) * | 2016-07-26 | 2019-04-05 | 中国科学院兰州化学物理研究所 | A kind of ionic liquid and its preparation method and application containing natural alicyclic structure |
| CN106947569A (en) * | 2017-03-13 | 2017-07-14 | 深圳市合诚润滑材料有限公司 | Planetary gear lubricating grease |
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Application publication date: 20110622 |