CN112029561A - Modified graphene-based water-based flame-retardant hydraulic oil - Google Patents
Modified graphene-based water-based flame-retardant hydraulic oil Download PDFInfo
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- CN112029561A CN112029561A CN202010702523.6A CN202010702523A CN112029561A CN 112029561 A CN112029561 A CN 112029561A CN 202010702523 A CN202010702523 A CN 202010702523A CN 112029561 A CN112029561 A CN 112029561A
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- hydraulic oil
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- 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
- C10M173/00—Lubricating compositions containing more than 10% water
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- 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
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/14—Inorganic compounds or elements as ingredients in lubricant compositions inorganic compounds surface treated with organic compounds
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
The invention belongs to the technical field of hydraulic oil, and particularly relates to modified graphene-based water-based flame-retardant hydraulic oil, which comprises an oiliness agent, polyether modified graphene, water, a functional additive and the like in components, wherein the polyether is added into a hydraulic oil system in a component form, and the graphene oxide is subjected to graft modification on the other hand, so that the lubricating and wear-reducing performance of the hydraulic oil is improved, the loss of the system lubricity caused by the replacement of the oiliness agent by the water component is compensated, and the compatibility between two phases of water and oil is promoted.
Description
Technical Field
The invention belongs to the technical field of hydraulic oil, and particularly relates to water-based flame-retardant hydraulic oil based on modified graphene.
Background
The hydraulic system oil is called hydraulic oil for short, and the hydraulic oil is lubricating oil and is used as a working medium in a hydraulic transmission system. The hydraulic oil is prepared by adding petroleum product additives such as antiwear and antioxidant into petroleum lubricant oiliness agent or synthetic lubricant, is widely used in machine tools, mine engineering machinery, steel-making machinery, transportation machinery, aviation, aerospace and other aspects, and plays an important role in industrial and agricultural production.
Compared with the traditional oil-based hydraulic oil, the water-based hydraulic oil is more environment-friendly, meanwhile, due to the intervention of water components, the cooling performance of a hydraulic oil system is better, the risk that the hydraulic oil catches fire in the using process is reduced, but the lubricating effect of the water-based hydraulic oil is not as good as that of oil-based hydraulic oil. In some hydraulic oil systems, in order to take the advantages of the two into consideration, the oiliness agent and the water are compounded under the condition of almost equal quantity, so that a large amount of dispersing agent is often added to realize the intermiscibility and stability between oil and water, and the oil product cost is increased; compared with the traditional oil-based hydraulic oil which takes all organic oil as a matrix, the semi-oil and semi-water hydraulic oil still has a difference in lubricity.
Disclosure of Invention
In order to solve the technical problems, the invention provides water-based flame-retardant hydraulic oil based on modified graphene, which comprises an oiliness agent, polyether modified graphene, water, a functional additive and the like,
the hydraulic oil comprises the following components in parts by weight:
the preparation method of the polyether modified graphene comprises the following steps:
fully dispersing graphene oxide in deionized water, adding amino-terminated polyether, dispersing, heating to a reflux state, fully reacting, filtering, drying,
the method specifically comprises the following steps: adding graphene oxide prepared by a Hummers method into deionized water according to the proportion of 1-15 mg/mL, adding amino-terminated polyether into the deionized water according to the proportion of 50-100 mg/mL after sufficient ultrasonic dispersion, heating to reflux temperature after sufficient ultrasonic dispersion for reflux reaction for 5-15 hours, carrying out suction filtration, drying the obtained filter cake,
the polyether is water-soluble polyether, and the polyether is water-soluble polyether,
the functional additive mainly comprises an antirust agent, an antioxidant and the like,
the rust inhibitor comprises 4, 5-dihydroimidazole, benzotriazole, barium petroleum sulfonate and the like,
the antioxidant includes amine antioxidant, phenol antioxidant, etc.
The hydraulic oil system has higher water content and good cooling and flame-retardant properties, and can form a layer of flame-retardant steam when contacting with flame; according to the scheme, graphite substances are added into a water-based hydraulic oil system, graphene is not only a lubricating and antifriction additive, but also has certain flame retardant property, and the requirements of water-based hydraulic oil are met; meanwhile, polyether modification is also introduced in the scheme, the polyether is added into a hydraulic oil system in a component form, and the graphene oxide is grafted and modified by adopting the polyether specially, so that the lubricating and anti-wear performance of the hydraulic oil is further improved, the loss of the system lubricity caused by replacing an oiliness agent with a water component is well compensated, the compatibility stability between water and oil phases is also promoted, an additional surfactant is replaced to a certain extent, and in addition, the oil product is endowed with excellent anti-foaming and air release performances.
The wear resistance of the oil product can completely meet the requirement of a hydraulic system on lubrication, the working stability of the hydraulic system can be maintained, the oil product has good compatibility with metal and non-metal materials, and based on excellent flame retardant property, the oil product can be used for the hydraulic system close to high temperature and heat source, so that the oil product can be suitable for the fireproof hydraulic system of large-scale high-temperature units in the industries of metallurgy, mining, building materials, chemical engineering and the like, such as hydraulic transmission and hydraulic servo systems of various open furnaces, converters, electric furnaces, vacuum induction furnaces, soaking furnaces and heat treatment furnaces, continuous casting machines, continuous rolling machines, pipe rolling machines, wire rolling machines and coking industries, and is also suitable for the hydraulic systems of power stations, coal mines, chemical fertilizers and other equipment requiring flame resistance and.
Detailed Description
The polyether modified graphene in each of the following examples and comparative examples was prepared by the following operations:
adding 4 parts by weight of graphene oxide (model SE2430W, made by Henzhou sixth-element materials science and technology Co., Ltd.) into 600 parts by weight of deionized water, performing ultrasonic dispersion for 90 minutes to be sufficient, adding 35 parts by weight of amino-terminated polyether (Hensmeid-230), performing ultrasonic dispersion for 20 minutes to be sufficient, heating the obtained dispersion system to 100 ℃, performing reflux reaction for 8 hours, performing suction filtration, fully stirring and cleaning the obtained filter cake with ethanol, performing suction filtration again, and drying the filter cake at 80 ℃ for 7 hours to obtain 32.6 parts by weight of polyether modified graphene.
No graphite substance is found in the filtrate and the cleaning solution after suction filtration, so that it is considered that the 4 parts by weight of graphene oxide substantially enter the final 32.6 parts by weight of modified product (it is also stated that the amino-terminated polyether in the modification process has reached an excess), and therefore, the weight ratio of the graphite substance to the polyether in the modified graphene is calculated to be approximately 1: 7.15 (this ratio is referred to in comparative example 1).
Example 1
The water-based flame-retardant hydraulic oil based on the modified graphene comprises the following components in parts by weight
At normal temperature (25 ℃, the same applies below), the polyether is firstly added into the oily agent, after stirring for 20 minutes, the benzotriazole and the antioxidant 1010 are added, after stirring for 10 minutes, the polyether modified graphene is added, stirring is carried out for 20 minutes, and finally the water is added, and stirring is carried out for 40 minutes to be full.
Comparative example 1
The modified graphene oxide is not modified, the amino-terminated polyether grafted to the graphene oxide in a corresponding amount is directly added into a hydraulic oil system, and the components and the proportion are the same as those in example 1:
at normal temperature, firstly adding the polyether ArChine Syntrend 60-HB-5200 and the amino-terminated polyether (Hensmei D-230) into the oily agent, stirring for 20 minutes, then adding the benzotriazole and the antioxidant 1010, stirring for 10 minutes, then adding the graphene oxide, stirring for 20 minutes, finally adding the water, and stirring for 40 minutes to be full.
Example 2
The water-based flame-retardant hydraulic oil based on the modified graphene comprises the following components in parts by weight
At normal temperature, firstly adding the polyether into the oily agent, stirring for 20 minutes, then adding the benzotriazole and the antioxidant 1010, stirring for 10 minutes, then adding the polyether modified graphene, stirring for 10 minutes, finally adding the water, and stirring for 50 minutes to be full.
Comparative example 2
The modified graphene oxide is not modified, the amino-terminated polyether grafted to the graphene oxide in a corresponding amount is directly added into a hydraulic oil system, and the components and the proportion are the same as those in example 2:
at normal temperature, firstly adding the polyether ArChine Syntrend 60-HB-5200 and amino-terminated polyether (Hensmei D-230) into the oily agent, stirring for 20 minutes, then adding the benzotriazole and the antioxidant 1010, stirring for 10 minutes, then adding the polyether modified graphene, stirring for 10 minutes, finally adding the water, and stirring for 50 minutes to be full.
Example 3
The water-based flame-retardant hydraulic oil based on the modified graphene comprises the following components in parts by weight
At normal temperature, the polyether is added into the oily agent, stirred for 10 minutes, added with the barium petroleum sulfonate and the antioxidant 1076, stirred for 10 minutes, added with the polyether modified graphene, stirred for 15 minutes, added with the water and stirred for 40 minutes to be full.
Comparative example 3
The modified graphene oxide is not modified, the amino-terminated polyether grafted to the graphene oxide in a corresponding amount is directly added into a hydraulic oil system, and the components and the proportion are the same as those in example 3:
at normal temperature, firstly adding the polyether ArChine Syntrend 60-HB-5200 and amino-terminated polyether (Hensmei D-230) into the oily agent, stirring for 10 minutes, then adding the barium petroleum sulfonate and the antioxidant 1076, stirring for 10 minutes, then adding the polyether modified graphene, stirring for 15 minutes, finally adding the water, and stirring for 40 minutes to be full.
Comparative example
The polyether in the embodiment 1 is replaced by sodium dodecyl benzene sulfonate, and the rest components and the mixture ratio are the same as those in the embodiment 1:
at normal temperature, firstly adding the sodium dodecyl benzene sulfonate into the oily agent, stirring for 20 minutes, then adding the benzotriazole and the antioxidant 1010, stirring for 10 minutes, then adding the polyether modified graphene, stirring for 20 minutes, finally adding the water, and stirring for 40 minutes to be full.
Comparative example 4
The modified graphene oxide is not modified, the amino-terminated polyether grafted to the graphene oxide in a corresponding amount is directly added into a hydraulic oil system, and the components and the proportion are the same as those in the comparative example:
at normal temperature, the sodium dodecyl benzene sulfonate and the amino-terminated polyether (hensimei D-230) are added into the oily agent, stirred for 20 minutes, then the benzotriazole and the antioxidant 1010 are added, stirred for 10 minutes, then the graphene oxide is added, stirred for 20 minutes, finally the water is added, and stirred for 40 minutes to be full.
The hydraulic oils compounded in the above examples and comparative examples (comparative examples) were tested for wear resistance by the four-ball method according to the standard SH/T0189-1992 (after the hydraulic oils were stirred and mixed, they were allowed to stand at room temperature for 24 hours under the conditions of 40kg/60min/75 ℃/1200rpm, the test results are shown in Table 1),
TABLE 1
| Diameter of abrasion mark | |
| Example 1 | 0.24mm |
| Comparative example 1 | 0.43mm |
| Example 2 | 0.36mm |
| Comparative example 2 | 0.45mm |
| Example 3 | 0.29mm |
| Comparative example 3 | 0.42mm |
| Comparative example | 0.28mm |
| Comparative example 4 | 0.50mm |
Each 100mL of the hydraulic oil prepared in each of the above examples and comparative examples (comparative examples) by stirring and mixing was put into a transparent glass reagent bottle of the same specification at room temperature, and the presence or absence of delamination and sedimentation was observed and recorded, and the results are shown in Table 2,
TABLE 2
As can be analyzed from the above table, compared with the case where the terminal amino polyether and the graphene oxide are added to the hydraulic oil system, grafting and combining of the graphene oxide with the terminal amino polyether in advance is beneficial to increase of dispersion stability of the graphene substance in the oil product and improvement of antifriction lubricity of the oil product, and is also beneficial to improvement of dispersion compatibility between the oil phase and the water phase in the system, and prevention of premature delamination of the water phase and the oil phase, which also promotes development of the water-based hydraulic oil with excellent flame retardancy. And in combination with the comparative example and comparative example 4, the amino-terminated polyether grafted graphite material can contribute significantly to the dispersion compatibility between the oil phase and the water phase in the presence of polyether.
Claims (8)
1. The utility model provides a waterborne fire-resistant hydraulic oil based on modified graphene which characterized in that: the hydraulic oil comprises an oiliness agent, polyether modified graphene, water and a functional additive.
2. The aqueous flame-retardant hydraulic oil based on modified graphene of claim 1, wherein: the hydraulic oil comprises the following components in parts by weight
3. The aqueous flame-retardant hydraulic oil based on modified graphene as claimed in claim 1 or 2, wherein: the polyether is water-soluble polyether.
4. The aqueous flame-retardant hydraulic oil based on modified graphene as claimed in claim 1 or 2, wherein: the preparation method of the polyether modified graphene comprises the following steps,
fully dispersing graphene oxide in deionized water, adding amino-terminated polyether, dispersing, heating to a reflux state, fully reacting, filtering, and drying.
5. The aqueous flame-retardant hydraulic oil based on modified graphene according to claim 4, wherein: the preparation method of the polyether modified graphene comprises the following steps,
adding graphene oxide prepared by a Hummers method into deionized water according to the proportion of 1-15 mg/mL, adding amino-terminated polyether into the deionized water according to the proportion of 50-100 mg/mL after sufficient ultrasonic dispersion, heating to reflux temperature after sufficient ultrasonic dispersion, carrying out reflux reaction for 5-15 hours, carrying out suction filtration, and drying the obtained filter cake.
6. The aqueous flame-retardant hydraulic oil based on modified graphene as claimed in claim 1 or 2, wherein: the functional additive comprises an antirust agent and an antioxidant.
7. The aqueous flame-retardant hydraulic oil based on modified graphene of claim 6, wherein: the antirust agent is one or a combination of more of 4, 5-dihydroimidazole, benzotriazole and barium petroleum sulfonate.
8. The aqueous flame-retardant hydraulic oil based on modified graphene of claim 6, wherein: the antioxidant is amine antioxidant or phenol antioxidant.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114214103A (en) * | 2021-12-22 | 2022-03-22 | 河北中煤神海科技发展有限公司 | Hard water resistant lubricant, concentrated solution for hydraulic support and preparation method thereof |
| CN114231336A (en) * | 2021-12-21 | 2022-03-25 | 奎克化学（中国）有限公司 | Composite preservative and preparation method and application thereof |
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2020
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| CN109054975A (en) * | 2018-07-23 | 2018-12-21 | 中国科学院上海高等研究院 | A kind of graphite oxide alkenyl Pickering lotion and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114231336A (en) * | 2021-12-21 | 2022-03-25 | 奎克化学（中国）有限公司 | Composite preservative and preparation method and application thereof |
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