CN109439404B - Synthetic ester type flame-retardant hydraulic oil - Google Patents

Synthetic ester type flame-retardant hydraulic oil Download PDF

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CN109439404B
CN109439404B CN201811346259.6A CN201811346259A CN109439404B CN 109439404 B CN109439404 B CN 109439404B CN 201811346259 A CN201811346259 A CN 201811346259A CN 109439404 B CN109439404 B CN 109439404B
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hydraulic oil
ester type
synthetic ester
type flame
retardant hydraulic
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CN109439404A (en
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何盛俊
李琦
黄旻晔
谷云
陈伟涛
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Wuxi Gorunjie Chemical Co ltd
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Wuxi Gorunjie Chemical Co ltd
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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • 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
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • 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
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Abstract

The invention discloses synthetic ester type flame-retardant hydraulic oil. The synthetic ester type flame-retardant hydraulic oil comprises the following components in percentage by weight: 96-98% of trimethylolpropane oleate, 0.1-0.7% of alkyl diphenol, 0.2-1.4% of vulcanized di-tert-butylphenol, 0.05-0.3% of methylbenzotriazole, 0.2-1.4% of octyl butyl diphenylamine, 0.1-0.4% of phosphate, 0.001-0.05% of ethylene glycol/propylene glycol copolymer, 0.25-1% of alkyl phosphate ammonium salt and 0.001-0.01% of antifoaming agent. Compared with the existing flame-retardant hydraulic oil, the synthetic ester type flame-retardant hydraulic oil has smaller wear-mark diameter (less than or equal to 2.5mm), higher FZG failure grade (12 grade), and longer oxidation life of the rotary oxygen bomb method than 400 minutes, and is very suitable for hydraulic systems in various high-temperature, high-pressure and cold working environments.

Description

Synthetic ester type flame-retardant hydraulic oil
Technical Field
The invention belongs to the field of hydraulic systems, and particularly relates to synthetic ester type flame-retardant hydraulic oil.
Background
The hydraulic oil is a hydraulic medium used by a hydraulic system utilizing hydraulic pressure energy, plays roles of energy transfer, system lubrication, corrosion prevention, rust prevention, cooling and the like in the hydraulic system, and provides various requirements for the hydraulic oil due to the continuous rise of the operating pressure of a vane pump and a plunger pump and the abrasion of a friction pair. In the actual use process, various problems such as low flash point, poor lubricity, large foam and air release values, poor oxidation stability and the like are often exposed to common hydraulic oil, so that the application of the common hydraulic oil to high-power and high-pressure mining equipment, ship equipment and liquid steel metallurgical equipment in a high-temperature environment is greatly limited.
Patent document CN105001946A discloses an ester-type flame-retardant hydraulic oil containing sulfurized trimethylolpropane oleate as a base oil, wherein the wear-point diameter of the hydraulic oil is greater than 0.3mm, and the FZG test fails when reaching grade 11. Patent document CN102292424A discloses a flame-retardant hydraulic oil composition using trimethylolpropane oleate as base oil, the hydraulic oil has a wear-scar diameter of more than 0.3mm, fails when the FZG test reaches 11 grades, and has an oxidation life of less than 300 minutes by the spin-oxygen bomb method. The flame-retardant/flame-retardant hydraulic oil has limited bearing capacity, and is greatly limited to be applied to high-power and high-pressure mining equipment, ship equipment and liquid steel metallurgical equipment in a high-temperature environment.
Disclosure of Invention
The invention aims to improve the existing flame-retardant hydraulic oil taking the trimethylolpropane oleate synthetic ester as the base oil so as to ensure that the flame-retardant hydraulic oil has smaller wear-scar diameter and higher FZG failure grade.
In order to achieve the purpose, the invention provides the following technical scheme:
the synthetic ester type flame-retardant hydraulic oil comprises the following components in percentage by weight: 96-98% of trimethylolpropane oleate, 0.1-0.7% of alkyl diphenol, 0.2-1.4% of vulcanized di-tert-butylphenol, 0.05-0.3% of methylbenzotriazole, 0.2-1.4% of octyl butyl diphenylamine, 0.1-0.4% of phosphate, 0.001-0.05% of ethylene glycol/propylene glycol copolymer, 0.25-1% of alkyl phosphate ammonium salt and 0.001-0.01% of antifoaming agent.
Preferably, the synthetic ester type flame-retardant hydraulic oil comprises the following components in percentage by weight: 96-98% of trimethylolpropane oleate, 0.3-0.5% of alkyl diphenol, 0.6-1% of vulcanized di-tert-butylphenol, 0.2-0.3% of methylbenzotriazole, 0.6-1% of octyl butyl diphenylamine, 0.15-0.2% of phosphate, 0.02-0.03% of ethylene glycol/propylene glycol copolymer, 0.375-0.5% of alkyl phosphate ammonium salt and 0.001-0.01% of antifoaming agent.
More preferably, the weight ratio of the alkyl diphenol to the vulcanized di-tert-butyl phenol to the octyl butyl diphenylamine is 1:2: 2.
More preferably, the weight ratio of the phosphate to the ammonium alkyl phosphate is 2: 5.
Preferably, the iodine value of the trimethylolpropane oleate is 80-90g I2/100g。
Compared with the existing flame-retardant hydraulic oil, the flame-retardant hydraulic oil has smaller wear-mark diameter (less than or equal to 2.5mm) and higher FZG failure grade (12 grade), the oxidation life of the rotary oxygen bomb method is longer than 400 minutes, the bearing capacity of the flame-retardant hydraulic oil is obviously improved, and the flame-retardant hydraulic oil is very suitable for hydraulic systems in various high-temperature, high-pressure and severe cold working environments.
Detailed Description
The technical solutions in the present disclosure will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present disclosure, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The synthetic ester type flame-retardant hydraulic oil is prepared from the following raw materials in percentage by weight: trimethylolpropane oleate (iodine value of 80-90g I)2100g) 96.478%, alkyl diphenol (gu' an huahui, model 702, chemical name: 0.5% of 4, 4-methylene (2.6-di-tert-butylphenol)), 1.0% of vulcanized di-tert-butylphenol (basf, model L115), 0.3% of methylbenzotriazole, 1.0% of octylbutyldiphenylamine, 0.2% of phosphate (9-octadecen-1-ol phosphate), 0.02% of ethylene glycol/propylene glycol copolymer (Lu bo, model 5172), 0.5% of alkyl phosphate ammonium salt (Vanlube 672), and 0.002% of composite antifoaming agent (1# antifoaming agent, the main components of which are polydimethylsiloxane and polyoxypropylene ethylene oxide glyceryl ether);
the preparation process comprises the following steps: adding trimethylolpropane oleate into a reaction kettle, adding alkyl diphenol, sulfurized di-tert-butyl phenol, methylbenzotriazole and octyl butyl diphenylamine into the reaction kettle, heating to 80-90 ℃, keeping the temperature, continuously stirring for half an hour until solid substances are completely dissolved, then cooling to 50-60 ℃, sequentially adding phosphate, ethylene glycol/propylene glycol copolymer, alkyl phosphate ammonium salt and composite antifoaming agent, and then continuously stirring for 1 hour to obtain the synthetic ester type flame-retardant hydraulic oil.
Example 2
The synthetic ester type flame-retardant hydraulic oil is prepared from the following raw materials in percentage by weight: trimethylolpropane oleate (iodine value of 80-90g I)2Per 100g) 97.743%, alkyl diphenol (Gu' an Huahui, type 702)03%, sulfurized di-tert-butylphenol (basf, model L115), tolyltriazole 0.2%, octylbutyldiphenylamine 0.6%, phosphate ester (9-octadecen-1-ol phosphate ester) 0.15%, ethylene glycol/propylene glycol copolymer (lubosun, model 5172) 0.03%, alkyl phosphate ester ammonium salt (Vanlube 672) 0.375%, composite antifoaming agent (# 1 antifoaming agent) 0.002%; the procedure was the same as in example 1.
The hydraulic fluids of the products of examples 1-2 of the present invention were tested for their performance and the results are shown in table 1 below.
Table 1 product Performance test results
Test items Test method Example 1 Example 2
Kinematic viscosity (mm) at 40 ℃2/s) GB/T265 48.3 46.7
Viscosity index GB/T115 188 190
Open flash point (. degree.C.) GB/T3536 324 326
Pour point (. degree. C.) GB/T3535 -41 -40
Air release value (min) SH/T 0308 0.48 0.51
Oxidation stability (h) GB/T 12581 1400 1350
Rotating oxygen bomb (150 deg.C), min SH/T 0193 568 432
Corrosion of copper sheet (100 deg.C, 3h), grade GB/T5096 1a 1a
Rust (distilled water) in liquid phase with or without rust stains GB/T 11143 Non-rust Non-rust
The diameter of the abrasion spot (196N,60min,1200r/min, 1h), mm SH/T 0189 0.23 0.24
FZG (8.3/90), stage SH/T0306 12 12
As can be seen from the data in table 1, the beneficial effects of the present invention are: the synthetic ester base oil is used as a main raw material, a plurality of additives are used as auxiliary materials, and the additives are matched in a synergistic manner, so that the product has excellent oxidation resistance, high flash point, good abrasion resistance and excellent antifriction performance, meanwhile, the product also has excellent viscosity-temperature performance, low-temperature use characteristics, excellent corrosion resistance and rust resistance and excellent oxidation stability, the viscosity of the oil product is ensured to have good retentivity under the harsh working condition of low temperature of-40 ℃ to-35 ℃, and the synthetic ester base oil is very suitable for hydraulic systems in various high-temperature, high-pressure and cold working environments.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. The synthetic ester type flame-retardant hydraulic oil comprises the following components in percentage by weight: 96-98% of trimethylolpropane oleate, 0.1-0.7% of alkyl diphenol, 0.2-1.4% of vulcanized di-tert-butylphenol, 0.05-0.3% of methylbenzotriazole, 0.2-1.4% of octyl butyl diphenylamine, 0.1-0.4% of phosphate, 0.001-0.05% of ethylene glycol/propylene glycol copolymer, 0.25-1% of alkyl phosphate amine salt and 0.001-0.01% of antifoaming agent.
2. The synthetic ester type flame-retardant hydraulic oil according to claim 1, characterized in that: the synthetic ester type flame-retardant hydraulic oil comprises the following components in percentage by weight: 96-98% of trimethylolpropane oleate, 0.3-0.5% of alkyl diphenol, 0.6-1% of vulcanized di-tert-butylphenol, 0.2-0.3% of methylbenzotriazole, 0.6-1% of octyl butyl diphenylamine, 0.15-0.2% of phosphate, 0.02-0.03% of ethylene glycol/propylene glycol copolymer, 0.375-0.5% of alkyl phosphate amine salt and 0.001-0.01% of antifoaming agent.
3. The synthetic ester type flame-retardant hydraulic oil according to claim 1 or 2, characterized in that: the weight ratio of the alkyl diphenol to the sulfurized di-tert-butylphenol to the octyl butyl diphenylamine is 1:2: 2.
4. The synthetic ester type flame-retardant hydraulic oil according to claim 1 or 2, characterized in that: the weight ratio of the phosphate to the alkyl phosphate amine salt is 2: 5.
5. The synthetic ester type flame-retardant hydraulic oil according to claim 1, characterized in that: the iodine value of the trimethylolpropane oleate is 80-90 gI2/100g。
6. The synthetic ester type flame-retardant hydraulic oil according to claim 1, characterized in that: the anti-foaming agent is an oil-soluble anti-foaming agent.
CN201811346259.6A 2018-11-13 2018-11-13 Synthetic ester type flame-retardant hydraulic oil Active CN109439404B (en)

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CN110628485A (en) * 2019-09-09 2019-12-31 山东瑞兴阻燃科技有限公司 Synthetic ester type flame-retardant hydraulic oil

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WO1991016389A1 (en) * 1990-04-12 1991-10-31 Atochem North America, Inc. Fire resistant hydraulic fluids
CN101812355A (en) * 2009-12-18 2010-08-25 益田润石（北京）化工有限公司 Novel synthetic fire-resistant hydraulic oil composition
CN103614192A (en) * 2013-11-19 2014-03-05 沈阳理工大学 Sulfur and phosphorus-containing automobile gear lubricating oil
CN104342226A (en) * 2014-09-24 2015-02-11 中国石油化工股份有限公司 Use of trimethylolpropane oleate, trimethylolpropane oleate containing composition and use of trimethylolpropane oleate containing composition
CN104450088A (en) * 2014-11-28 2015-03-25 沈阳理工大学 Automobile gear lubricant taking trimethylolpropane easter as base oil

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DE19819656A1 (en) * 1998-05-02 1999-11-04 Henkel Kgaa Process for the preparation of polyol esters
CN101113383B (en) * 2007-07-03 2010-04-21 杭州新港石油化工有限公司 Ester flame-proof hydraulic-oil containing nano abrasion-resistant additive and production method thereof
CN105001946B (en) * 2015-05-30 2017-11-10 山东北方淄特特种油股份有限公司 Ester type fire-resistant hydraulic fluid and its production method
CN105482881A (en) * 2015-12-28 2016-04-13 芜湖市创源新材料有限公司 Novel flame-retardant type synthetic hydraulic oil for coal mine
US10190067B2 (en) * 2016-02-24 2019-01-29 Washington State University High performance environmentally acceptable hydraulic fluid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991016389A1 (en) * 1990-04-12 1991-10-31 Atochem North America, Inc. Fire resistant hydraulic fluids
CN101812355A (en) * 2009-12-18 2010-08-25 益田润石（北京）化工有限公司 Novel synthetic fire-resistant hydraulic oil composition
CN103614192A (en) * 2013-11-19 2014-03-05 沈阳理工大学 Sulfur and phosphorus-containing automobile gear lubricating oil
CN104342226A (en) * 2014-09-24 2015-02-11 中国石油化工股份有限公司 Use of trimethylolpropane oleate, trimethylolpropane oleate containing composition and use of trimethylolpropane oleate containing composition
CN104450088A (en) * 2014-11-28 2015-03-25 沈阳理工大学 Automobile gear lubricant taking trimethylolpropane easter as base oil

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Denomination of invention: A synthetic ester type flame resistant hydraulic oil

Granted publication date: 20211119

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