Ionic liquid, preparation method and application thereof, and hydraulic support liquid

Abstract

The invention provides ionic liquid, a preparation method and application thereof and hydraulic support liquid, and relates to the technical field of hydraulic liquid. The ionic liquid provided by the invention is environment-friendly, can be uniformly dispersed in water to form the hydraulic support liquid, and forms a high-strength physical adsorption film with metal on a friction surface, so that the extreme pressure anti-wear performance of the hydraulic support liquid is improved, the antifriction effect is improved, and the anti-corrosion performance of the hydraulic support liquid can also be remarkably improved by the ionic liquid. And on the other hand, the hydraulic support liquid provided by the invention has low requirements on the quality of water, can be suitable for regions with higher hard water grades, and is wide in application range.

Description

Technical Field

[0001] The invention relates to the technical field of hydraulic fluid, and in particular to an ionic liquid and a preparation method and application thereof, and a hydraulic support fluid. Background Art

[0002] The hydraulic support system in coal mines is a key device installed on the coal mining face and is a key device for modern coal mining. The hydraulic support system can provide necessary support, lifting, movement, overload protection and other functions for coal mining. The related functions of the hydraulic support system are realized through hydraulic support fluid. Therefore, the hydraulic support fluid is called the "blood" of the hydraulic support system.

[0003] Since hydraulic support fluid is used in large quantities and is updated quickly, if it leaks or is directly discharged without purification, it is very easy to pollute groundwater and cause harm to the human body. Therefore, environmentally friendly hydraulic support fluid has become an increasing focus of research. At present, there are few reports on the application of environmentally friendly ionic liquids as lubricating and anti-rust additives in the field of hydraulic support fluids. Summary of the invention

[0004] The purpose of the present invention is to provide an ionic liquid and a preparation method and application thereof, and a hydraulic support fluid. The ionic liquid provided by the present invention is environmentally friendly, and the hydraulic support fluid prepared by using the ionic liquid can significantly improve the tribological properties, and has good anti-corrosion performance and excellent friction reduction performance.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides an ionic liquid having a structure shown in Formula 1:

[0007]

[0008] The present invention provides a method for preparing the ionic liquid of the above scheme, comprising the following steps: mixing an alcohol solution of dimer acid and an aqueous solution of choline hydroxide, and performing an esterification reaction to obtain the ionic liquid.

[0009] Preferably, the molar ratio of the dimer acid to choline hydroxide is 1:2.

[0010] Preferably, the alcohol solution of dimer acid comprises an ethanol solution of dimer acid; and the concentration of dimer acid in the alcohol solution of dimer acid is 95-98 wt %.

[0011] Preferably, the concentration of choline hydroxide in the aqueous solution of choline hydroxide is 95-98 wt %.

[0012] Preferably, the temperature of the esterification reaction is 20-35° C., and the time is 12-24 hours.

[0013] Preferably, after the esterification reaction is completed, the obtained product liquid is further subjected to reduced pressure distillation and vacuum drying.

[0014] The present invention provides the use of the ionic liquid described in the above scheme or the ionic liquid prepared by the preparation method described in the above scheme in hydraulic support fluid.

[0015] The present invention provides a hydraulic support fluid, which comprises 0.1-1.5% of ionic liquid and the remainder of water in terms of mass percentage;

[0016] The ionic liquid is the ionic liquid described in the above scheme or the ionic liquid prepared by the preparation method described in the above scheme.

[0017] Preferably, the hydraulic support fluid also includes 0.01-0.1% of anti-foaming agent and 0.01-0.02% of dye.

[0018] The ionic liquid provided by the present application is environmentally friendly, can be evenly dispersed in water to form a hydraulic support fluid, and can form a high-strength physical adsorption film with the metal on the friction surface, thereby improving the extreme pressure and anti-wear performance of the hydraulic support fluid, improving the friction reduction effect, and the ionic liquid can also significantly improve the anti-corrosion performance of the hydraulic support fluid. On the other hand, the hydraulic support fluid provided by the present invention does not have high requirements on the quality of water, can be used in areas with high hard water levels, and has a wide range of applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 FTIR spectra of dimer acid, choline hydroxide and ionic liquid [cho][dimer];

[0020] Figure 2 The storage stability test diagrams of Example 3 (left) and Comparative Example 5 (right) are shown. DETAILED DESCRIPTION

[0021] The present invention provides an ionic liquid having a structure shown in Formula 1:

[0022]

[0023] The present invention provides a method for preparing the ionic liquid of the above scheme, comprising the following steps: mixing an alcohol solution of dimer acid and an aqueous solution of choline hydroxide, and performing an esterification reaction to obtain the ionic liquid.

[0024] In the present invention, unless otherwise specified, the raw materials used are commercially available products well known in the art.

[0025] In the present invention, the alcohol solution of dimer acid preferably includes an ethanol solution of dimer acid; the concentration of dimer acid in the alcohol solution of dimer acid is preferably 95-98wt%; in a specific embodiment of the present invention, the concentration of dimer acid in the alcohol solution of dimer acid can be 95wt%, 96wt%, 97wt% or 98wt%.

[0026] In the present invention, the concentration of the aqueous solution of choline hydroxide is preferably 95-98 wt %; in a specific embodiment of the present invention, the concentration of the aqueous solution of choline hydroxide may be 95 wt %, 96 wt %, 97 wt % or 98 wt %.

[0027] In the present invention, the molar ratio of the dimer acid to choline hydroxide is preferably 1:2.

[0028] In the present invention, the temperature of the esterification reaction is preferably 20-35°C (i.e. room temperature), and the time of the esterification reaction is preferably 12-24h; in a specific embodiment, the time of the esterification reaction can be specifically 12h, 15h, 18h, 20h or 24h.

[0029] In the present invention, the esterification reaction is preferably carried out under stirring conditions.

[0030] In the present invention, the equation of the esterification reaction is as follows:

[0031]

[0032] After the esterification reaction is completed, the present invention preferably further comprises subjecting the obtained product liquid to reduced pressure distillation and vacuum drying to obtain the ionic liquid.

[0033] In the present invention, the temperature of the reduced pressure distillation is preferably 30-80°C; in a specific embodiment, the temperature of the reduced pressure distillation can be 30°C, 50°C, 60°C, 70°C or 80°C.

[0034] In the present invention, the vacuum drying temperature is preferably 50-100°C, and the time is preferably 24-48 hours; in a specific embodiment, the vacuum drying temperature can be 50°C, 60, 80°C or 100°C, and the vacuum drying time can be 24 hours, 30 hours, 36 hours or 48 hours. The present invention has no special requirements for the vacuum degree of the vacuum drying.

[0035] The present invention provides the use of the ionic liquid described in the above scheme or the ionic liquid prepared by the preparation method described in the above scheme in hydraulic support fluid.

[0036] The invention provides a hydraulic support fluid, which comprises 0.1-1.5% of the above ionic liquid and the remainder of water in terms of mass percentage.

[0037] In terms of mass percentage, the hydraulic support fluid provided by the present invention includes 0.1-1.5% of ionic liquid; in a specific embodiment, the mass content of the ionic liquid can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1% or 1.2%. The present invention controls the content of the ionic liquid within the above range, which can avoid the turbidity of the hydraulic support fluid caused by excessive content due to solubility limitation; and can also give the hydraulic support fluid good extrusion anti-wear performance, friction reduction performance and anti-emulsification performance.

[0038] In terms of mass percentage, the hydraulic support fluid provided by the present invention preferably includes 0.01-0.1% of antifoaming agent; in a specific embodiment, the mass content of the antifoaming agent can be 0.01%, 0.02%, 0.04%, 0.06%, 0.08% or 0.1%. In the present invention, the antifoaming agent is preferably one or more of an organosilicon antifoaming agent and a polyether antifoaming agent. The present invention does not make special requirements on the specific types of the organosilicon antifoaming agent and the polyether antifoaming agent, and the organosilicon antifoaming agent and the polyether antifoaming agent well known in the art can be used. In the embodiment of the present invention, the antifoaming agent MS 575 is specifically used.

[0039] The hydraulic support fluid provided by the present invention preferably includes 0.01-0.02% of dye in terms of mass percentage. In the present invention, the dye preferably includes toluidine.

[0040] The hydraulic support fluid provided by the present invention also includes a water surplus. The present invention has no special requirements for the water, and any water known in the art can be used, such as deionized water, tap water, and one or more of the eight levels of artificial hard water prepared according to the MT 76-2011 standard. In the present invention, the eight levels of artificial hard water prepared according to the MT 76-2011 standard are 5, 10, 15, 20, 25, 30, 35, and 40 levels (based on the concentration of anions and cations in the water, the larger the level, the higher the hard water level and the higher the ion concentration).

[0041] The present application adopts a specific ionic liquid, which can be evenly dispersed in water to form a hydraulic support fluid, and forms a high-strength physical adsorption film with the metal on the friction surface, thereby improving the extreme pressure and anti-wear performance of the hydraulic support fluid, improving the friction reduction effect, and the ionic liquid can also significantly improve the anti-corrosion performance of the hydraulic support fluid. On the other hand, the hydraulic support fluid provided by the present invention does not have high requirements on the quality of water, can be used in areas with high hard water levels, and has a wide range of applications.

[0042] The present invention has no special requirements for the preparation method of the hydraulic support fluid. The components are directly mixed and stirred at room temperature for 30 to 40 minutes at a stirring speed of 300 to 400 rpm to obtain the hydraulic support fluid.

[0043] The ionic liquid and its preparation method and application, and hydraulic support fluid provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present invention.

[0044] The preparation of the ionic liquids in the following examples is as follows:

[0045] To an ethanol solution of dimer acid (10 mmol) at a concentration of 98 wt% was added an equal amount of an aqueous solution of choline hydroxide (20 mmol) at a concentration of 98 wt%, and the resulting mixture was magnetically stirred at room temperature for 12 h, then distilled under reduced pressure at 50°C, and finally dried in vacuo at 70°C for 48 h to obtain the ionic liquid [cho][dimer].

[0046] Figure 1 FTIR spectra of dimer acid, choline hydroxide and ionic liquid [cho][dimer] are shown in Figure 1. Figure 1 It can be seen that dimer acid has a peak at 1760 cm -1 The absorption peak at is attributed to its carbonyl stretching; after one-step synthesis, due to COO-N + The influence of bond formation, the carbonyl stretching of ionic liquid [cho][dimer] compared with pure acid is from 1709cm -1 becomes 1573cm -1 ; The above results indicate that dimer acid anions exist in the ionic liquid, that is, the target ionic liquid [cho][dimer] is successfully synthesized after dimer acid reacts with choline hydroxide.

[0047] Example 1

[0048] The raw materials and mass percentages of the hydraulic support fluid are: 0.5% of ionic liquid [cho][dimer], 0.02% of antifoaming agent (specifically MS 575), 0.01% of dye (specifically toluidine), and the balance of hard water with a hardness level of 15 prepared according to the MT 76-2011 standard; the above components are added into a container in sequence, mechanical stirring is turned on, and stirring is continued for 30 minutes to obtain the hydraulic support fluid.

[0049] Example 2

[0050] The raw materials and mass percentages of the hydraulic support fluid are: ionic liquid [cho][dimer] 1%, antifoaming agent (specifically MS 575) 0.02%, dye (specifically toluidine) 0.01%, and the balance of hard water with a hardness level of 15 prepared according to MT 76-2011 standard; the above components are added into a container in sequence, mechanical stirring is turned on, and stirring is continued for 30 minutes to obtain the hydraulic support fluid.

[0051] Example 3

[0052] The raw materials and mass percentages of the hydraulic support fluid are: ionic liquid [cho][dimer] 1%, antifoaming agent (specifically MS 575) 0.02%, dye (specifically toluidine) 0.01%, and the balance of hard water with a hardness level of 20 prepared according to MT 76-2011 standard; the above components are added into a container in sequence, mechanical stirring is turned on, and stirring is continued for 30 minutes to obtain the hydraulic support fluid.

[0053] Comparative Example 1

[0054] The preparation method of Comparative Example 1 is the same as that of Example 2, except that the ionic liquid prepared in the present application is not added.

[0055] Comparative Example 2

[0056] The preparation method of Comparative Example 2 is the same as that of Example 2, except that the ionic liquid prepared in the present application is not added, and the same mass fraction of a commonly used water-based hydraulic fluid compound on the market - RM9707 (a water-based hydraulic fluid compound produced by Zhongke Runmei (Qingdao) Materials Technology Co., Ltd.) is added.

[0057] Comparative Example 3

[0058] The preparation method of Comparative Example 3 is the same as that of Example 2, except that the ionic liquid is LP104 (alkyl imidazole hexafluorophosphate).

[0059] Comparative Example 4

[0060] The preparation method of Comparative Example 4 is the same as that of Example 2, except that the ionic liquid is a ricinoleic acid-based ionic liquid having a structure shown in Formula 2:

[0061]

[0062] Comparative Example 5

[0063] The preparation method of Comparative Example 5 is the same as that of Example 3, except that the ionic liquid prepared in the present application is not added, and the same mass fraction of a commonly used water-based hydraulic fluid compounding agent on the market - RM9707 is added.

[0064] The anti-rust performance of hydraulic support fluid was tested according to JB / T 9189-2016 "Test Method for Rust Prevention of Water-Based Materials - Cast Iron Chips Test"; the lubricity of hydraulic support fluid (P B ) puts forward clear requirements (>392N), according to GB / T 3142-2019 on the lubricity of hydraulic support fluid (P B) was tested; according to NB / SHVT0882-2014 SRV testing machine method for determination of extreme pressure properties of lubricating materials, the friction coefficient was tested experimentally to evaluate the tribological properties of the prepared hydraulic support fluid. The test conditions were 25°C (temperature), 100N (load), 25Hz (frequency), 30min (running time), and 1mm (stroke). The storage stability test was a self-built method. The specific operation was as follows: 200mL of the sample was placed in a -20°C environment for 21 days, and then placed at room temperature. After the sample temperature rose to room temperature, the sample was observed for precipitation or precipitation.

[0065] The hydraulic support fluid prepared in the embodiment and the comparative example is in a fluid state, and its typical detection performance data are shown in Table 1 and Table 2.

[0066] Table 1 Liquid phase corrosion performance and P of hydraulic support fluids prepared in Examples and Comparative Examples B Performance Data

[0067]

[0068] Table 2 Friction performance data of hydraulic support fluids prepared in Examples and Comparative Examples under SRV conditions

[0069] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Friction coefficient 0.13 0.11 0.14 0.4 0.24 0.31 0.15

[0070] It can be seen from Table 1 and Table 2 that the introduction of ionic liquid in the present application can significantly improve the anti-corrosion performance, lubrication performance and anti-wear performance of the hydraulic support fluid (the smaller the SRV friction coefficient in Table 2, the better the anti-wear performance).

[0071] Figure 2 The storage stability test diagrams of Example 3 (left) and Comparative Example 5 (right) are shown. Figure 2 It can be seen that the introduction of ionic liquid in the present application can significantly improve the storage stability of the hydraulic support fluid. Even in the hard water level of 20 prepared according to the MT 76-2011 standard, it can still remain stable without precipitation; while the hydraulic support fluid of comparative example 5 is turbid and the system is unstable.

[0072] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An ionic liquid, characterized in that It has the structure shown in formula 1:

2. The method for preparing the ionic liquid according to claim 1, characterized in that: The method comprises the following steps: mixing an alcohol solution of dimer acid and an aqueous solution of choline hydroxide, and performing an esterification reaction to obtain the ionic liquid.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the dimer acid to choline hydroxide is 1:

2.

4. The preparation method according to claim 2, characterized in that: The alcohol solution of dimer acid comprises an ethanol solution of dimer acid; the concentration of dimer acid in the alcohol solution of dimer acid is 95-98 wt %.

5. The preparation method according to claim 2, characterized in that: The concentration of choline hydroxide in the aqueous solution of choline hydroxide is 95-98 wt %.

6. The preparation method according to any one of claims 2 to 5, characterized in that: The temperature of the esterification reaction is 20-35° C. and the time is 12-24 hours.

7. The preparation method according to claim 2, characterized in that: After the esterification reaction is completed, the obtained product liquid is subjected to reduced pressure distillation and vacuum drying.

8. Use of the ionic liquid according to claim 1 or the ionic liquid prepared by the preparation method according to any one of claims 2 to 7 in hydraulic support fluid.

9. A hydraulic support fluid, characterized in that: Calculated by mass percentage, it includes 0.1-1.5% of ionic liquid and the remainder of water; The ionic liquid is the ionic liquid according to claim 1 or the ionic liquid prepared by the preparation method according to any one of claims 2 to 7.

10. The hydraulic support fluid according to claim 9, characterized in that: The hydraulic support fluid also includes 0.01-0.1% of antifoaming agent and 0.01-0.02% of dye.

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