CN106187902B - Ionic liquid containing alkyl naphthalene structure and preparation method and application thereof - Google Patents

Ionic liquid containing alkyl naphthalene structure and preparation method and application thereof Download PDF

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CN106187902B
CN106187902B CN201610592516.9A CN201610592516A CN106187902B CN 106187902 B CN106187902 B CN 106187902B CN 201610592516 A CN201610592516 A CN 201610592516A CN 106187902 B CN106187902 B CN 106187902B
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ionic liquid
alkyl
methylimidazole
alkyl naphthalene
brominated
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CN106187902A (en
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高平
刘维民
冯大鹏
孙晓军
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D233/56—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • 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
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/44—Five-membered ring containing nitrogen and carbon only
    • C10M133/46—Imidazoles
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

The invention discloses an ionic liquid containing an alkyl naphthalene structure, and a preparation method and application thereof. The invention utilizes a quaternary ammonium salt ion exchange method to synthesize the ionic liquid containing alkyl naphthalene structure, and the molecular formula is [ CH3C3H3N2CnH2n+1]C12H9O2The chemical name is 1-alkyl-3-methylimidazolium naphthalene acetate, and the selected anion raw material is a derivative of a natural product, and special preparation and advanced functionalization are not needed; the reaction flow can be shortened; the reaction operation is simple, and the controllability is strong. The ionic liquid is used as an antifriction additive to be applied to alkyl naphthalene lubricating oil or lubricating grease taking alkyl naphthalene as base oil.

Description

Ionic liquid containing alkyl naphthalene structure and preparation method and application thereof
Technical Field
The invention relates to an ionic liquid containing an alkyl naphthalene structure, and a preparation method and application thereof. The ionic liquid is used as an antifriction additive to be applied to alkyl naphthalene lubricating oil or lubricating grease taking alkyl naphthalene as base oil.
Background
The alkyl naphthalene used as non-pour point depressant is a kind of basic oil of AP IV class and is used to prepare various synthetic lubricating oils. Its advantages are high thermal and oxidizing stability, high hydrolytic stability, high solubility and effect of additive, high compatibility with sealing part and high anti-emulsifying performance, and no poison. Therefore, it is widely used in various types of friction members (US4238343, 4912277, 5254274, 6127324).
The core naphthalene ring of the alkyl naphthalene is composed of two electron-rich conjugated large pi-bond six-membered rings, and the two conjugated aromatic rings endow the compound with unique thermal oxidation stability. However, since such compounds are nonpolar compounds, the adsorption force to the substrate is weak, and the boundary lubrication film is easily broken during friction, and thus the extreme pressure performance thereof is relatively weak. The ionic liquid is a strong polar compound, and has unique solubility, high thermal stability and extremely low vapor pressure. Studies have shown that different functional groups in the ionic liquid structure can significantly alter its properties. If the unique designability of the ionic liquid is utilized, naphthalene rings are introduced into the ionic liquid by a chemical synthesis method, so that the respective excellent performances of the alkyl naphthalene and the ionic liquid are combined, the adsorption capacity of the alkyl naphthalene and the substrate is favorably enhanced, and the tribological performance of the alkyl naphthalene and the substrate is improved.
Disclosure of Invention
The invention aims to provide an ionic liquid containing an alkyl naphthalene structure, and a preparation method and application thereof.
The ionic liquid containing alkyl naphthalene structure is characterized in that the structural formula is shown as the formula (I), and the molecular formula is [ CH ]3C3H3N2CnH2n+1]C12H9O2The chemical name is 1-alkyl-3-methylimidazolium naphthalene acetate,
Figure 274970DEST_PATH_IMAGE001
a compound of the formula (I),
wherein n is an integer of 4 to 10.
The synthesis method of the ionic liquid is represented by a chemical reaction equation of a formula (II):
Figure 97433DEST_PATH_IMAGE002
the compound of the formula (II),
wherein n is an integer of 4 to 10.
The ionic liquid containing the alkyl naphthalene structure is obtained by reacting brominated 1-alkyl-3-methylimidazole with sodium naphthalene acetate.
A preparation method of ionic liquid containing alkyl naphthalene structure is characterized in that 1-alkyl-3-methylimidazole bromide and sodium naphthalene acetate are used as raw materials, the reaction temperature is 20-90 ℃, and the reaction time is 2-10 hours; and after the reaction is finished, washing and drying to obtain the target product.
The molar ratio of the brominated 1-alkyl-3-methylimidazole to the sodium naphthaleneacetate is 1: 1.1-3.6.
The brominated 1-alkyl-3-methylimidazole is brominated 1-butyl-3-methylimidazole, brominated 1-hexyl-3-methylimidazole, brominated 1-octyl-3-methylimidazole or brominated 1-decyl-3-methylimidazole.
In the laboratory, our specific preparation process is: adding brominated 1-alkyl-3-methylimidazole into a round-bottom flask, adding sodium naphthalene acetate aqueous solution during stirring, stirring for 1-5 hours at 20-90 ℃, extracting for three times by using dichloromethane, washing a dichloromethane phase for three times by using water, drying over night by using anhydrous magnesium sulfate, evaporating the solvent under reduced pressure, and then extracting for 1 hour under reduced pressure at the temperature of 100 ℃/0.1 mmHg to remove water possibly contained, thereby obtaining the target product.
The ionic liquid is dispersed in alkyl naphthalene base oil by ultrasonic as an antifriction additive. Based on the total weight of the lubricating oil, the addition amount of the ionic liquid is 0.1-2.0 wt%.
Literature reports that the general process for preparing the ionic liquid by the two-step method is to prepare a halide salt containing a target cation through quaternization, and then replace the halide ion with a target anion or add Lewis acid to react with the halide salt to obtain the target ionic liquid. By utilizing the unique designability of the ionic liquid and functionalizing the anions and cations, the ionic liquid with expected performance can be obtained. Researchers have done a lot of work in recent years aiming at the functionalization of cations and synthesized ionic liquids with different properties. But less functionalization studies for anions were conducted. In addition, in order to realize the functionalization of the ionic liquid, some larger groups are inevitably introduced, and the melting point of the ionic liquid is inevitably increased, so that the applicable range of the functionalized ionic liquid is limited.
The invention relates to an ionic liquid containing alkyl naphthalene structure, which is synthesized by using a quaternary ammonium salt ion exchange method. The anion raw material selected by the invention is a derivative of a natural product, and special preparation and advanced functionalization are not needed; the reaction flow can be shortened, and the controllability is strong. Because of the asymmetric anion, the final product is a yellowish or yellow viscous transparent liquid at room temperature (25 ℃). Viscosity at 20 ℃ of 280-450 mm2·s-1Pour point<-30 ℃ and the initial thermal decomposition temperature > 350 ℃.
The novelty of the invention lies in: naphthalene rings are introduced into the ionic liquid by a chemical synthesis method. The ionic liquid has negative charges, and is easily combined with positive charge points of a friction pair in the friction process to form a stable transition state. And the configuration of the transition state is very ordered, a certain thickness can be kept, and the friction reducing and wear resisting effects are achieved in the friction process. The tribological properties are therefore good. The nitrogen atom in the heterocyclic ring of the imidazole part is beneficial to improving the thermal stability of the conjugated heterocyclic ring and endowing the lubricant with good extreme pressure anti-wear performance and high flash point, and in addition, nitrogen is easy to adsorb on the surface of metal in the friction process to passivate the active point of the metal, thereby inhibiting the corrosion of the metal and the oxidation or degradation of the lubricant. The core naphthalene ring of the alkyl naphthalene is composed of two electron-rich conjugated large pi-bond six-membered rings, and the two conjugated aromatic rings endow the compound with unique thermal oxidation stability. However, since such compounds are nonpolar compounds, the adsorption force to the substrate is weak, and the boundary lubrication film is easily broken during friction, and thus the extreme pressure performance thereof is relatively weak. The ionic liquid is a strong polar compound, naphthalene rings are introduced into the ionic liquid by a chemical synthesis method, so that the adsorption capacity of alkyl naphthalene and a substrate is enhanced, and the alkyl naphthalene is not easy to decompose under the shearing action, so that the tribological performance of the alkyl naphthalene is improved.
The invention has the advantages that: the excellent performances of alkyl naphthalene and ionic liquid are combined by a chemical synthesis method, and the compound has a wide liquid phase temperature range and excellent high and low temperature performances. Due to the similarity of molecular structures, the compound has good compatibility with alkylnaphthalene, and can be used as an antifriction additive to be applied to alkylnaphthalene lubricating oil or lubricating grease taking alkylnaphthalene as base oil.
The tribological performance of the lubricant is evaluated by a frictional wear tester under simulated vacuum conditions. The experimental conditions are as follows: degree of vacuum 10-4pa; a load of 3N; the rotating speed is 300 rpm; time, 1 h. The test ball on the experiment is Si3N4Ball or 9Cr18 steel ball, bottomThe test disc is a 9Cr18 steel disc with a radius of 24 mm.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be merely illustrative of specific embodiments of the present invention and are not intended to limit the application of the process.
Example 1
Synthesizing 1-butyl-3-methylimidazolium naphthalene acetate.
52.56g (0.24mol) of 1-butyl-3-methylimidazole bromide was added to a round-bottomed flask, and while stirring, an aqueous solution of sodium naphthaleneacetate [ containing 56.2g (0.27mol) of sodium naphthaleneacetate ] was added, stirred at 40 ℃ for 2 hours, extracted three times with dichloromethane, and the dichloromethane solution was washed three times with distilled water, then dried over anhydrous magnesium sulfate overnight, the solvent was distilled off under reduced pressure, and then extracted under reduced pressure at 100 ℃/0.1 mmHg for 1 hour to obtain the objective product.
Example 2
Synthesizing 1-hexyl-3-methylimidazolium naphthalene acetate.
59.28g (0.24mol) of 1-hexyl-3-methylimidazole bromide was added to a round-bottomed flask, an aqueous solution of sodium naphthaleneacetate [ containing 58.3g (0.28mol) of sodium naphthaleneacetate ] was added while stirring, stirred at 40 ℃ for 3 hours, extracted three times with dichloromethane, the dichloromethane solution was washed three times with distilled water, then dried over anhydrous magnesium sulfate overnight, the solvent was distilled off under reduced pressure, and then extracted under reduced pressure at 100 ℃/0.1 mmHg for 1 hour to obtain the objective product.
Example 3
Synthesizing 1-octyl-3-methylimidazolium naphthalene acetate.
Into a round-bottomed flask, 66.00g (0.24mol) of 1-octyl-3-methylimidazole bromide was added, and while stirring, an aqueous solution of sodium naphthaleneacetate [ containing 62.4g (0.30mol) of sodium naphthaleneacetate ] was added, stirred at 50 ℃ for 4 hours, extracted three times with dichloromethane, and the dichloromethane solution was washed three times with distilled water, then dried over anhydrous magnesium sulfate overnight, the solvent was distilled off under reduced pressure, and then extracted under reduced pressure at 100 ℃/0.1 mmHg for 1 hour to obtain the objective product.
Example 4
Synthesizing 1-decyl-3-methylimidazolium naphthalene acetate.
In a round-bottomed flask, 72.72g (0.24mol) of 1-decyl-3-methylimidazole bromide was added, and while stirring, an aqueous solution of sodium naphthaleneacetate [ containing 64.5g (0.31mol) of sodium naphthaleneacetate ] was added, stirred at 50 ℃ for 4 hours, extracted three times with dichloromethane, and the dichloromethane solution was washed three times with distilled water, then dried over anhydrous magnesium sulfate overnight, the solvent was distilled off under reduced pressure, and then extracted under reduced pressure at 100 ℃/0.1 mmHg for 1 hour to obtain the objective product.
Example 5
The ionic liquids of examples 1 to 4 were ultrasonically dispersed in alkyl naphthalene base oil in the dosage amounts of 1.5%, 1.0%, 0.6% and 0.4% by mass, and the tribological properties thereof were evaluated by a simulated vacuum condition friction wear tester, and the results are shown in table 1.
Table 1 example 5 experimental results
Figure 52882DEST_PATH_IMAGE003
The results in table 1 show that the compounds of the present invention have good friction reducing properties when applied to alkyl naphthalene base oils.

Claims (3)

1. The application of the ionic liquid containing the alkyl naphthalene structure is characterized in that the ionic liquid containing the alkyl naphthalene structure is dispersed in alkyl naphthalene base oil in an ultrasonic mode to serve as an anti-friction additive;
the structural formula of the ionic liquid is shown as a formula (I), and the molecular formula of the ionic liquid is [ CH ]3C3H3N2CnH2n+1]C12H9O2，
The chemical name is 1-alkyl-3-methylimidazolium naphthalene acetate,
Figure FDF0000006951110000011
wherein n is an integer of 4-10;
the preparation method of the ionic liquid comprises the following specific steps: the method comprises the following steps of (1) taking brominated 1-alkyl-3-methylimidazole and sodium naphthalene acetate as raw materials, reacting at the temperature of 40-90 ℃ for 2-10 hours; and after the reaction is finished, washing and drying to obtain the target product.
2. Use according to claim 1, wherein the molar ratio of 1-alkyl-3-methylimidazole bromide to sodium naphthaleneacetate is from 1:1.1 to 3.6.
3. Use according to claim 1 or 2, characterized in that the brominated 1-alkyl-3-methylimidazole is brominated 1-butyl-3-methylimidazole, brominated 1-hexyl-3-methylimidazole, brominated 1-octyl-3-methylimidazole or brominated 1-decyl-3-methylimidazole.
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