CN111961521A - Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof - Google Patents
Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof Download PDFInfo
- Publication number
- CN111961521A CN111961521A CN202010882291.7A CN202010882291A CN111961521A CN 111961521 A CN111961521 A CN 111961521A CN 202010882291 A CN202010882291 A CN 202010882291A CN 111961521 A CN111961521 A CN 111961521A
- Authority
- CN
- China
- Prior art keywords
- brake fluid
- triethylene glycol
- borate
- glycol monomethyl
- monomethyl ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of 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
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- 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
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/082—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type monocarboxylic
-
- 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
- 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
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
-
- 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
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives 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
- 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
- C10M2215/066—Arylene diamines
-
- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/0615—Esters derived from boron used as base material
Landscapes
- 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 provides a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, an antioxidant, a corrosion inhibitor and a pH value regulator. The invention also provides a preparation method of the borate type synthetic brake fluid with ultralow low-temperature viscosity. The invention breaks through the lower limit of the low-temperature fluidity of the existing borate type brake fluid, simultaneously meets the specification requirements of Class products of HZY6 grade in national standard of international standard ISO4925:2005 'road vehicle-non-petroleum base brake fluid specification' and China GB12981-2012 'motor vehicle brake fluid', and can ensure the brake to be sensitive and timely under the condition of extremely cold climate; moreover, the dry and wet boiling points are very high and stable, and air resistance is not easy to occur; the lubricating property is good, and the braking is stable; the corrosion to metal materials of a braking system is small, the swelling to rubber parts is small, and the oxidation resistance and the thermal stability are excellent.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to an automobile brake fluid, and particularly relates to an ultralow-low-temperature-viscosity borate type synthetic brake fluid and a preparation method thereof.
Background
The automobile brake fluid is also called brake oil, and is a functional liquid used for transmitting brake energy in an automobile hydraulic brake system. When a driver brakes, momentum is transmitted to each wheel slave pump through a piston of a brake master pump and brake fluid to push each brake shoe (caliper) friction plate to expand and press a brake disc fixed on the wheel to generate friction braking, so that the aim of stopping the vehicle is fulfilled.
Since the automobile in the 30 th of the 20 th century began to use brake fluid, the automobile brake fluid has been developed through three main development stages, namely alcohol type, mineral oil type and synthetic type. The alcohol type brake fluid is prepared by blending refined castor oil and low-carbon alcohol, has low boiling point, is easy to generate air resistance, and is easy to generate brake delay to cause brake failure when used at low temperature. The mineral oil brake fluid is prepared by using low-boiling-point mineral oil fraction as base oil and adding antioxidant, antirust agent, coloring agent and the like, has poor adaptability to natural rubber cups, is easy to crack and cause accidents, is incompatible with water, and is easy to generate air resistance at high temperature after entering a small amount of water to influence the transmission of braking force. Therefore, alcohol type and mineral oil type brake fluid is basically not used in China and other countries. At present, most countries mainly use synthetic brake fluid. Synthetic brake fluids are mainly classified into alcohol-ether type, ester type and silicone oil type. Alcohol-ether brake fluid begins to appear in the 50 s of the 20 th century, has higher equilibrium reflux boiling point and lower low-temperature viscosity, but is easy to absorb moisture in air, so that the high-temperature performance is reduced, and air resistance is easy to generate; meanwhile, the corrosion of the metal parts is accelerated due to the increase of the water absorption amount. The development of the silicone oil type brake fluid starts in 1967, and compared with alcohol-ether type and ester type brake fluids, the silicone oil type brake fluid has the main advantages of excellent high-temperature and low-temperature performance, all-weather brake fluid, good lubricating property, corrosion resistance and antirust property, no moisture absorption and long service life; the disadvantages are high cost and incompatibility with other types of brake fluids. So, up to now, the silicon oil type brake fluid is mainly used in the vehicles of the army, and the vehicles in other countries are less used. Ester brake fluid begins to appear in the early 70 s of the 20 th century, countries compete for development and the most used ester brake fluid belongs to borate type, wherein the borate of the base fluid enables the brake fluid to have better high-temperature air resistance and water resistance, and a diluent and an additive are required to be added for adjusting the low-temperature fluidity of the brake fluid, the compatibility with rubber, the metal corrosion resistance and the oxidation resistance. However, the existing borate type brake fluid products generally have the following problems:
firstly, boric acid ester is required to be synthesized firstly in preparation, and the process is tedious;
secondly, the boric acid ester base liquid has large low-temperature viscosity and poor fluidity;
thirdly, the swelling effect of the added diluent on the rubber cup is large, such as patent CN 104611092A;
fourthly, the added alcohol water-absorbing rubber expansion inhibitor can reduce the high-temperature air resistance of the brake fluid, such as patent CN 106190450A;
and fifthly, the introduced additive has poor compatibility with the base fluid, and particularly when the automobile runs at high speed frequently, the brake fluid is heated, the additive in the brake fluid can generate precipitation, so that the performance of the brake fluid is influenced, and the brake system of the automobile can be blocked.
The performance and quality condition of brake fluid are directly related to the safety of motor vehicles and drivers, and with the rapid development of the automobile industry, the automobile brake technology is also continuously improved, and particularly, compared with an ABS anti-lock brake system which is more complex and precise than a conventional brake system, the ABS anti-lock brake system has higher requirements on the performances of the brake fluid in the aspects of low-temperature flowing, high-temperature air resistance, lubrication, thermal stability, oxidation resistance, corrosion and swelling reduction and the like, so that the national standard GB12981 is formulated by strictly requiring the quality of the brake fluid of the automobile in China. The GB12981-2012 motor vehicle brake fluid standard defines 4 grades of motor vehicle brake fluid, which are HZY3, HZY4, HZY5 and HZY6 from low to high respectively, and respectively correspond to the brake fluid international standard of ISO4925:2005 Class3, Class4, Class5 and Class6 in the road vehicle-non-petroleum-based brake fluid specification. Currently, HZY3, HZY4 and a small amount of HZY5 are commonly available on the market, while HZY6 is almost none. The HZY6 emphasizes the ultralow low-temperature kinematic viscosity, so that the brake fluid has better low-temperature resistance and good brake response speed even in extremely cold regions. With the improvement of the light weight requirement of the automobile, the trend of light weight and miniaturization of the brake system is gradually increased, and the use of high-grade brake fluid with ultralow viscosity can use small inner diameter of the brake pipeline, so that the purpose of reducing weight is achieved.
Disclosure of Invention
The invention aims to provide an ultralow-low-temperature viscosity borate type synthetic brake fluid and a preparation method thereof, and aims to solve the problems that in the existing borate type brake fluid technology, the preparation process of a base fluid is redundant, a diluent swells a rubber cup, an alcohol water-absorbing rubber expansion inhibitor reduces the high-temperature air resistance of the brake fluid, the compatibility of an additive and the base fluid is poor, and the kinematic viscosity at the temperature of-40 ℃ cannot meet the requirements of Class6 in the international standard ISO4925:2005 (road vehicle-non-petroleum-based brake fluid specification) and HZY6 grade product specification in national standard GB12981-2012 (motor vehicle brake fluid) of China.
The invention provides a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator, in the borate type synthetic brake fluid with ultralow low-temperature viscosity, the weight percentage of the triethylene glycol monomethyl ether borate (MH-510) is 60-70%, 15 to 25 percent of triethylene glycol monomethyl ether (MTG), 5 to 15 percent of triethylene glycol monobutyl ether (TBG), the weight percentage of the rubber expansion inhibitor is 7 to 12 percent, the weight percentage of the antioxidant is 0.2 to 0.6 percent, the weight percentage of the corrosion inhibitor is 0.2-0.6%, and the weight percentage of the pH value regulator is 0.8-1.5%.
Further, the triethylene glycol monomethyl ether borate (MH-510), the triethylene glycol monomethyl ether (MTG) and the triethylene glycol monobutyl ether (TBG) are of industrial grade.
Further, the rubber swelling inhibitor is modified polyether polyol.
Further, the method for modifying the polyether polyol comprises the following steps: adding toluene into a reaction container, and adding polyalcohol into the reaction container under stirring, wherein the mass ratio of the toluene to the polyalcohol is (2-3): 1, adding a Double Metal Cyanide (DMC) catalyst, introducing nitrogen, heating to 30-60 ℃, and then dropwise adding propylene oxide, wherein the molar ratio of the propylene oxide to the polyhydric alcohol is (5-7): controlling the temperature below 50 ℃ during dripping and the dripping speed within 5-6 hours after dripping is finished, heating to 70-100 ℃ after dripping is finished, preserving the temperature for 1-3 hours, cooling to below 40 ℃, adding ammonia water for neutralization, standing overnight, and removing toluene and unreacted propylene oxide through filtration and reduced pressure distillation to obtain the modified polyether polyol.
Further, the polyhydric alcohol is selected from any one of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylolpropane and tris (2-hydroxyethyl) isocyanurate or a combination of two or more of the above in any proportion.
Furthermore, the antioxidant is p-hydroxyanisole and any one or the combination of two of bisphenol A, 2, 6-di-tert-butyl-p-cresol or N', N-diphenyl-p-phenylenediamine in any proportion.
Further, the corrosion inhibitor is a compound mixture of sodium polyacrylate and benzotriazole or methyl benzotriazole.
Further, the pH value regulator is one or a combination of two of di-n-butylamine, tri-n-butylamine, methyldiethanolamine, ethyldiethanolamine, butylamine ether, methylpropylamine ether, ethylenepropylamine ether, ethylenepropyleneglycol amine ether and borax in any proportion.
The invention also provides a preparation method of the ultralow-low-temperature viscosity borate type synthetic brake fluid, which comprises the steps of weighing triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator according to the weight percentage, sequentially adding the triethylene glycol monomethyl ether borate (MH-510), the triethylene glycol monomethyl ether (MTG), the triethylene glycol monobutyl ether (TBG) and the rubber expansion inhibitor into a reaction container, sequentially adding the antioxidant, the corrosion inhibitor and the pH value regulator into the reaction container, stirring at the temperature of 50-60 ℃ and at the normal pressure of 50-60 r/min, filtering the mixture into a finished product tank after all the materials are dissolved, and thus obtaining the ultralow-low-temperature viscosity borate type synthetic brake fluid.
Further, the triethylene glycol monomethyl ether borate (MH-510) is used as a base liquid.
Table 1 general boronic acid ester commercial indicator data
As can be seen from Table 1, the equilibrium reflux boiling point and the wet equilibrium reflux boiling point of MH-510 are higher than those of HZY6, the kinematic viscosity at-40 ℃ is very close to that of HZY6, and the product can meet the requirements by adding a certain amount of diluent, and in addition, the MH-510 has the functions of antifriction lubrication and the like. Therefore, MH-510 is selected as the raw material of the base liquid.
Further, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are used as diluents. The diluent is mainly used for reducing the viscosity of the brake fluid, wherein triethylene glycol monomethyl ether (MTG) is high in boiling point, low in viscosity and good in diluting effect, but when the diluent is used alone, the rubber cup can shrink. Triethylene glycol monobutyl ether (TBG) has higher rubber expansibility. Through experimental summary, it is appropriate to select 15% -25% of MTG and 5% -15% of TBG combined diluent.
Furthermore, sodium polyacrylate in the corrosion inhibitor has a strong hydrophilic group, and the length of a molecular chain can influence the fluidity of brake fluid, so that the weight average molecular weight of the sodium polyacrylate is limited to 1000-2000. The weight percentage of the additive is about 0.05 percent.
The invention has the beneficial effects that:
firstly, a finished product of triethylene glycol monomethyl ether borate (MH-510) is selected as a base liquid, so that the complexity of a synthesis process is avoided, the controllability of the purity of raw materials is strong, and the production is efficient and simple.
And secondly, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are selected as diluents, so that the boiling point is high, the low-temperature kinematic viscosity of the brake fluid at the temperature of-40 ℃ is effectively reduced, and the dilution effect is good.
Adding a conventional alcohol rubber expansion inhibitor into the brake fluid, although the low-temperature fluidity of the brake fluid and the compatibility with rubber can be improved, the high-temperature gas resistance of the brake fluid is reduced on the contrary because the conventional alcohol rubber expansion inhibitor is a water-absorbing substance, and the hydroxyl value and viscosity of the modified polyether polyol are controlled by introducing long-chain alkyl alcohol and a stable five-membered nitrogen ring into the molecular structure of the polyether polyol and utilizing the steric hindrance effect and the electronic action of a carbon nitrogen heterocycle and regulating and controlling the molar ratio of epoxypropane to polyhydric alcohol in the synthesis process of the modified polyether polyol, so that the low-temperature stability of the brake fluid is improved, and the excellent high-temperature gas resistance of the brake fluid is ensured.
The tetra-borate, the borate and the triethylene glycol monobutyl ether (TBG) have an expansion effect on the rubber cup, and the triethylene glycol monomethyl ether (MTG) and the modified polyether polyol have a contraction effect on the rubber cup. The invention balances the two functions, breaks through the lower limit of the low-temperature fluidity of the existing borate type brake fluid, and ensures that the expansion size of the rubber cup meets the specification requirements of HZY6 grade products in the national standard of International Standard ISO4925:2005, Class6 in road vehicle-non-petroleum base brake fluid Specification and China GB12981-2012, motor vehicle brake fluid.
And fifthly, the sodium polyacrylate is a linear soluble high molecular compound, the molecular chain of the sodium polyacrylate stretches due to the electrostatic repulsion action of carboxyl on the molecular chain, a functional group with adsorbability is formed on the surface, and the compatibility and the stability of the base liquid, the diluent and the additive in the system are enhanced by utilizing the steric hindrance effect and the solvation effect of the functional group. The sodium polyacrylate is used as a corrosion inhibitor, so that the stability of the brake fluid is obviously improved, and the precipitation phenomenon can not occur even if the brake fluid is used for a long time.
And sixthly, benzotriazole and p-hydroxyanisole are used as an anticorrosive additive combination, so that the benzotriazole has a good anticorrosive effect on metals such as copper, and the p-hydroxyanisole has a good effect on preventing the metals and rubber from being oxidized.
And seventhly, the methyl diethanol amine is used as a pH value regulator, so that the brake fluid turbidity phenomenon caused by the influence of the triethanolamine on the hydrolysis stability of the polymethyl ether borate is avoided.
Eighthly, the brake can be guaranteed to be sensitive and timely under the condition of extremely cold weather; moreover, the dry and wet boiling points are very high and stable, and air resistance is not easy to occur; the lubricating property is good, and the braking is stable; the corrosion to metal materials of a braking system is small, the swelling to rubber parts is small, and the oxidation resistance and the thermal stability are excellent. In addition, the production process of the invention does not involve synthesis, so that the purity controllability of various raw materials for blending products is strong, and the production is efficient and simple.
Detailed Description
Example 1
The invention relates to a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator. In the ultralow-low-temperature-viscosity borate type synthetic brake fluid, the weight percentage of triethylene glycol monomethyl ether borate (MH-510) is 65%, the weight percentage of triethylene glycol monomethyl ether (MTG) is 15%, the weight percentage of triethylene glycol monobutyl ether (TBG) is 8%, the weight percentage of a rubber expansion inhibitor is 10%, the weight percentage of an antioxidant is 0.6%, the weight percentage of a corrosion inhibitor is 0.4%, and the weight percentage of a pH value regulator is 1.0%.
The invention relates to a preparation method of a borate type synthetic brake fluid with ultralow low-temperature viscosity, which comprises the following steps: sequentially adding triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG) and a rubber expansion inhibitor into a reaction vessel according to the weight percentage, then sequentially adding an antioxidant, a corrosion inhibitor and a pH value regulator into the reaction vessel, stirring the mixture for 60min at the temperature of 50 ℃ and the normal pressure at the stirring speed of 50r/min, and filtering the mixture into a finished product tank after all the materials are dissolved to prepare the borate type synthetic brake fluid with ultralow low temperature viscosity.
Further, the triethylene glycol monomethyl ether borate (MH-510) is used as a base liquid.
Further, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are used as diluents.
Further, the rubber swelling inhibitor is modified polyether polyol, wherein the preparation process of the modified polyether polyol is as follows: adding toluene into a reaction container, adding tris (2-hydroxyethyl) isocyanurate under stirring, then adding double metal cyanide, introducing nitrogen, heating to 45 ℃, then dropwise adding propylene oxide, controlling the temperature of dropwise adding to be below 50 ℃ and the dropwise adding speed within 5-6 hours, after dropwise adding, heating to 80 ℃, keeping the temperature for 2 hours, cooling to be below 40 ℃, adding ammonia water for neutralization, standing overnight, filtering, and distilling under reduced pressure to remove toluene and unreacted propylene oxide, thus obtaining the modified polyether polyol, wherein the molar ratio of propylene oxide to tris (2-hydroxyethyl) isocyanurate is 6: 1, the mass ratio of toluene to tris (2-hydroxyethyl) isocyanurate is 2.5: 1.
furthermore, the antioxidant is p-hydroxyanisole and N', N-diphenyl-p-phenylenediamine which are respectively 0.3 percent by weight.
Further, the corrosion inhibitor is 0.05 percent of sodium polyacrylate and 0.35 percent of benzotriazole in percentage by weight.
Further, the pH value regulator is methyldiethanolamine.
Example 2
The invention relates to a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator. In the ultralow-low-temperature-viscosity borate type synthetic brake fluid, the weight percentage of triethylene glycol monomethyl ether borate (MH-510) is 68%, the weight percentage of triethylene glycol monomethyl ether (MTG) is 16%, the weight percentage of triethylene glycol monobutyl ether (TBG) is 6%, the weight percentage of a rubber expansion inhibitor is 8%, the weight percentage of an antioxidant is 0.5%, the weight percentage of a corrosion inhibitor is 0.5%, and the weight percentage of a pH value regulator is 1.0%.
The invention relates to a preparation method of a borate type synthetic brake fluid with ultralow low-temperature viscosity, which comprises the following steps: sequentially adding triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG) and a rubber expansion inhibitor into a reaction vessel according to the weight percentage, then sequentially adding an antioxidant, a corrosion inhibitor and a pH value regulator into the reaction vessel, stirring the mixture for 60min at the temperature of 50 ℃ and the normal pressure at the stirring speed of 50r/min, and filtering the mixture into a finished product tank after all the materials are dissolved to prepare the borate type synthetic brake fluid with ultralow low temperature viscosity.
Further, the triethylene glycol monomethyl ether borate (MH-510) is used as a base liquid.
Further, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are used as diluents.
Further, the rubber swelling inhibitor is modified polyether polyol, wherein the preparation process of the modified polyether polyol is as follows: adding toluene into a reaction container, adding tris (2-hydroxyethyl) isocyanurate under stirring, then adding double metal cyanide, introducing nitrogen, heating to 45 ℃, then dropwise adding propylene oxide, controlling the temperature of dropwise adding to be below 50 ℃ and the dropwise adding speed within 5-6 hours, after dropwise adding, heating to 80 ℃, keeping the temperature for 2 hours, cooling to be below 40 ℃, adding ammonia water for neutralization, standing overnight, filtering, and distilling under reduced pressure to remove toluene and unreacted propylene oxide, thus obtaining the modified polyether polyol, wherein the molar ratio of propylene oxide to tris (2-hydroxyethyl) isocyanurate is 6: 1, the mass ratio of toluene to tris (2-hydroxyethyl) isocyanurate is 2.5: 1.
furthermore, the antioxidant is p-hydroxyanisole and N', N-diphenyl-p-phenylenediamine which are respectively 0.3 percent by weight.
Further, the corrosion inhibitor is 0.05 percent of sodium polyacrylate and 0.35 percent of benzotriazole in percentage by weight.
Further, the pH value regulator is triethanolamine.
Example 3
The invention relates to a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator. In the ultralow-low-temperature-viscosity borate type synthetic brake fluid, the weight percentage of triethylene glycol monomethyl ether borate (MH-510) is 62%, the weight percentage of triethylene glycol monomethyl ether (MTG) is 17%, the weight percentage of triethylene glycol monobutyl ether (TBG) is 9%, the weight percentage of a rubber expansion inhibitor is 10%, the weight percentage of an antioxidant is 0.5%, the weight percentage of a corrosion inhibitor is 0.5%, and the weight percentage of a pH value regulator is 1.0%.
The invention relates to a preparation method of a borate type synthetic brake fluid with ultralow low-temperature viscosity, which comprises the following steps: sequentially adding triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG) and a rubber expansion inhibitor into a reaction vessel according to the weight percentage, then sequentially adding an antioxidant, a corrosion inhibitor and a pH value regulator into the reaction vessel, stirring the mixture for 60min at the temperature of 50 ℃ and the normal pressure at the stirring speed of 50r/min, and filtering the mixture into a finished product tank after all the materials are dissolved to prepare the borate type synthetic brake fluid with ultralow low temperature viscosity.
Further, the triethylene glycol monomethyl ether borate (MH-510) is used as a base liquid.
Further, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are used as diluents.
Further, the rubber swelling inhibitor is modified polyether polyol, wherein the preparation process of the modified polyether polyol is as follows: adding toluene into a reaction container, adding tris (2-hydroxyethyl) isocyanurate under stirring, then adding double metal cyanide, introducing nitrogen, heating to 45 ℃, then dropwise adding propylene oxide, controlling the temperature of dropwise adding to be below 50 ℃ and the dropwise adding speed within 5-6 hours, after dropwise adding, heating to 80 ℃, keeping the temperature for 2 hours, cooling to be below 40 ℃, adding ammonia water for neutralization, standing overnight, filtering, and distilling under reduced pressure to remove toluene and unreacted propylene oxide, thus obtaining the modified polyether polyol, wherein the molar ratio of propylene oxide to tris (2-hydroxyethyl) isocyanurate is 6: 1, the mass ratio of toluene to tris (2-hydroxyethyl) isocyanurate is 2.5: 1.
furthermore, the antioxidant is p-hydroxyanisole and N', N-diphenyl-p-phenylenediamine which are respectively 0.3 percent by weight.
Further, the corrosion inhibitor is 0.05 percent of sodium polyacrylate and 0.35 percent of benzotriazole in percentage by weight.
Further, the pH value regulator is butyl amine ether.
Example 4
The invention relates to a borate type synthetic brake fluid with ultralow low-temperature viscosity, which consists of triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG), a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator. In the ultralow-low-temperature viscosity borate type synthetic brake fluid, the weight percentage of triethylene glycol monomethyl ether borate (MH-510) is 65%, the weight percentage of triethylene glycol monomethyl ether (MTG) is 18%, the weight percentage of triethylene glycol monobutyl ether (TBG) is 7%, the weight percentage of rubber expansion inhibitor is 8%, the weight percentage of antioxidant is 0.5%, the weight percentage of corrosion inhibitor is 0.5%, and the weight percentage of pH value regulator is 1.0%.
The invention relates to a preparation method of a borate type synthetic brake fluid with ultralow low-temperature viscosity, which comprises the following steps: sequentially adding triethylene glycol monomethyl ether borate (MH-510), triethylene glycol monomethyl ether (MTG), triethylene glycol monobutyl ether (TBG) and a rubber expansion inhibitor into a reaction vessel according to the weight percentage, then sequentially adding an antioxidant, a corrosion inhibitor and a pH value regulator into the reaction vessel, stirring the mixture for 60min at the temperature of 50 ℃ and the normal pressure at the stirring speed of 50r/min, and filtering the mixture into a finished product tank after all the materials are dissolved to prepare the borate type synthetic brake fluid with ultralow low temperature viscosity.
Further, the triethylene glycol monomethyl ether borate (MH-510) is used as a base liquid.
Further, triethylene glycol monomethyl ether (MTG) and triethylene glycol monobutyl ether (TBG) are used as diluents.
Further, the rubber swelling inhibitor is modified polyether polyol, wherein the preparation process of the modified polyether polyol is as follows: adding toluene into a reaction container, adding tris (2-hydroxyethyl) isocyanurate under stirring, then adding double metal cyanide, introducing nitrogen, heating to 45 ℃, then dropwise adding propylene oxide, controlling the temperature of dropwise adding to be below 50 ℃ and the dropwise adding speed within 5-6 hours, after dropwise adding, heating to 80 ℃, keeping the temperature for 2 hours, cooling to be below 40 ℃, adding ammonia water for neutralization, standing overnight, filtering, and distilling under reduced pressure to remove toluene and unreacted propylene oxide, thus obtaining the modified polyether polyol, wherein the molar ratio of propylene oxide to tris (2-hydroxyethyl) isocyanurate is 6: 1, the mass ratio of toluene to tris (2-hydroxyethyl) isocyanurate is 2.5: 1.
furthermore, the antioxidant is p-hydroxyanisole and N', N-diphenyl-p-phenylenediamine which are respectively 0.3 percent by weight.
Furthermore, the corrosion inhibitor is benzotriazole.
Further, the pH value regulator is methyldiethanolamine.
Comparative example 1 (patent CN 104611092 a):
the weight percentage of the ingredients is as follows: triethylene glycol monomethyl ether borate is 61%, diethylene glycol dibutyl ether is 20.1%, tetraethylene glycol is 17%, bisphenol A is 0.3%, sodium nitrite is 0.6%, and ethanolamine is 1.0%.
Comparative example 2 (patent CN106190450 a):
430 kg of triethylene glycol monomethyl ether borate, 120 kg of polyethylene glycol monobutyl ether borate, 200 kg of triethylene glycol monomethyl ether, 80 kg of triethylene glycol dimethyl ether, PEG-188160 kg, 2 kg of bisphenol A, 1 kg of benzotriazole and 7 kg of butyl amine ether are sequentially added into a reaction kettle, stirred for 120min at 80 ℃ under normal pressure, and the raw materials are fully dissolved and then filtered to obtain the high-performance liquid.
The embodiment of the invention is compared with a comparative example and HZY6 grade product specification index data in national standard GB12981-2012 brake fluid for motor vehicles in Table 2.
TABLE 2
The data in table 2 show that the synthetic brake fluid provided by the invention has good high-temperature gas resistance, low-temperature fluidity and circulation stability, and various physical and chemical detection values of the embodiment all meet the specification index requirements of the HZY6 grade product in national standard GB12981-2012 brake fluid for motor vehicles in our country.
Comparing the results of examples 1-3 and example 4 in table 2, it can be seen that the present invention, by introducing the special sodium polyacrylate corrosion inhibitor, also enhances the circulation stability of the brake fluid on the premise of reducing the corrosivity of the brake fluid to metals, so that the automobile can still maintain good braking performance after frequent braking.
Comparing the data of examples 1-4 and comparative examples 1 and 2 in Table 2, it can be seen that the addition of the specially-made modified polyether polyol in the invention not only improves the low-temperature fluidity of the brake fluid, but also does not affect the high-temperature air resistance;
in comparative example 1, the rubber swell was large due to the addition of the borate, ether, and alcohol in improper proportions.
In comparative examples 1 and 2, since alcohol which was not modified was added, the prepared brake fluid absorbed water to result in a lower equilibrium reflux boiling point.
The above description is only a few embodiments of the present invention, and does not represent any limitation to the technical solution of the present invention. Any simple modification, equivalent change and modification made to the embodiment of the present invention according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (9)
1. The boric acid ester type synthetic brake fluid with ultralow low-temperature viscosity is characterized in that: the ultra-low temperature viscosity borate type synthetic brake fluid consists of 60-70 wt% of triethylene glycol monomethyl ether borate, 15-25 wt% of triethylene glycol monomethyl ether, 5-15 wt% of triethylene glycol monobutyl ether, 7-12 wt% of rubber expansion inhibitor, 0.2-0.6 wt% of antioxidant, 0.2-0.6 wt% of corrosion inhibitor and 0.8-1.5 wt% of pH value regulator.
2. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: the triethylene glycol monomethyl ether borate, the triethylene glycol monomethyl ether and the triethylene glycol monobutyl ether are of industrial grade.
3. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: the rubber expansion inhibitor is modified polyether polyol.
4. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 3, characterized in that: the method for modifying the polyether polyol comprises the following steps: adding toluene into a reaction container, and adding polyalcohol into the reaction container under stirring, wherein the mass ratio of the toluene to the polyalcohol is (2-3): 1, adding a double metal cyanide catalyst, introducing nitrogen, heating to 30-60 ℃, and then dropwise adding propylene oxide, wherein the molar ratio of the propylene oxide to the polyhydric alcohol is (5-7): controlling the temperature below 50 ℃ during dripping and the dripping speed within 5-6 hours after dripping is finished, heating to 70-100 ℃ after dripping is finished, keeping the temperature for 1-3 hours, cooling to below 40 ℃, adding ammonia water for neutralization, standing overnight, and removing toluene and unreacted propylene oxide through filtration and reduced pressure distillation to obtain the modified polyether polyol.
5. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 4, characterized in that: the polyhydric alcohol is selected from any one of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylolpropane and tris (2-hydroxyethyl) isocyanurate or a combination of two or more of the above in any proportion.
6. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: the antioxidant is one or the combination of two of p-hydroxyanisole and bisphenol A, 2, 6-di-tert-butyl-p-cresol or N', N-diphenyl-p-phenylenediamine in any proportion.
7. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: the corrosion inhibitor is a compound mixture of sodium polyacrylate and benzotriazole or methyl benzotriazole.
8. The ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: the pH value regulator is one or a combination of two of di-n-butylamine, tri-n-butylamine, methyldiethanolamine, ethyldiethanolamine, butylamine ether, methylpropylamine ether, ethylenepropylamine ether, methoxypropylamine ether and borax in any proportion.
9. A method for preparing the ultralow low-temperature viscosity borate type synthetic brake fluid according to claim 1, characterized in that: weighing triethylene glycol monomethyl ether borate, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, a rubber expansion inhibitor, an antioxidant, a corrosion inhibitor and a pH value regulator according to the weight percentage, sequentially adding the triethylene glycol monomethyl ether borate, the triethylene glycol monomethyl ether, the triethylene glycol monobutyl ether and the rubber expansion inhibitor into a reaction container, then sequentially adding the antioxidant, the corrosion inhibitor and the pH value regulator into the reaction container, stirring at the temperature of 50-60 ℃ and the normal pressure at the rotating speed of 50-60 r/min, filtering to a finished product tank after all materials are dissolved, and thus obtaining the ultralow low temperature viscosity borate type synthetic brake fluid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010882291.7A CN111961521A (en) | 2020-08-28 | 2020-08-28 | Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010882291.7A CN111961521A (en) | 2020-08-28 | 2020-08-28 | Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111961521A true CN111961521A (en) | 2020-11-20 |
Family
ID=73400439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010882291.7A Pending CN111961521A (en) | 2020-08-28 | 2020-08-28 | Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111961521A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122357A (en) * | 2021-04-19 | 2021-07-16 | 中国石油化工股份有限公司 | Motor vehicle brake fluid composition and preparation method thereof |
| CN114410368A (en) * | 2022-01-21 | 2022-04-29 | 巴诺德(厦门)制动科技有限公司 | Novel automobile brake fluid and preparation method thereof |
| CN114907907A (en) * | 2022-04-21 | 2022-08-16 | 安徽天驰先锋油品制造有限公司 | Preparation method of automobile brake fluid |
| CN116240062A (en) * | 2023-02-27 | 2023-06-09 | 福建莱克石化有限公司 | Electric automobile brake fluid and manufacturing method thereof |
| CN117448068A (en) * | 2023-10-30 | 2024-01-26 | 安徽天驰先锋油品制造有限公司 | Brake fluid for severe cold areas and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611092A (en) * | 2015-02-12 | 2015-05-13 | 辽宁润迪汽车环保科技股份有限公司 | Advanced locomotive brake fluid composition |
| CN107903387A (en) * | 2017-11-28 | 2018-04-13 | 山东诺威新材料有限公司 | The method for improving polyether polyol building-up process oxypropylene conversion ratio |
| CN111100727A (en) * | 2019-12-25 | 2020-05-05 | 上海本牧实业有限公司 | Synthetic brake fluid and preparation method thereof |
-
2020
- 2020-08-28 CN CN202010882291.7A patent/CN111961521A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611092A (en) * | 2015-02-12 | 2015-05-13 | 辽宁润迪汽车环保科技股份有限公司 | Advanced locomotive brake fluid composition |
| CN107903387A (en) * | 2017-11-28 | 2018-04-13 | 山东诺威新材料有限公司 | The method for improving polyether polyol building-up process oxypropylene conversion ratio |
| CN111100727A (en) * | 2019-12-25 | 2020-05-05 | 上海本牧实业有限公司 | Synthetic brake fluid and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 艾少华等: "HZY6机动车辆制动液的研制", 《粘接》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113122357A (en) * | 2021-04-19 | 2021-07-16 | 中国石油化工股份有限公司 | Motor vehicle brake fluid composition and preparation method thereof |
| CN113122357B (en) * | 2021-04-19 | 2023-01-24 | 中国石油化工股份有限公司 | Brake fluid composition for motor vehicle and preparation method thereof |
| CN114410368A (en) * | 2022-01-21 | 2022-04-29 | 巴诺德(厦门)制动科技有限公司 | Novel automobile brake fluid and preparation method thereof |
| CN114907907A (en) * | 2022-04-21 | 2022-08-16 | 安徽天驰先锋油品制造有限公司 | Preparation method of automobile brake fluid |
| CN116240062A (en) * | 2023-02-27 | 2023-06-09 | 福建莱克石化有限公司 | Electric automobile brake fluid and manufacturing method thereof |
| CN117448068A (en) * | 2023-10-30 | 2024-01-26 | 安徽天驰先锋油品制造有限公司 | Brake fluid for severe cold areas and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111961521A (en) | Ultralow-low-temperature-viscosity borate type synthetic brake fluid and preparation method thereof | |
| CN113122357A (en) | Motor vehicle brake fluid composition and preparation method thereof | |
| CN102363735A (en) | Preparation method of alcohol ether boric acid ester type DOT4 braking fluid | |
| CN102433213B (en) | Preparation method for high-grade borate type brake fluid | |
| CN104611092A (en) | Advanced locomotive brake fluid composition | |
| CN111100727A (en) | Synthetic brake fluid and preparation method thereof | |
| CN101619258A (en) | Method for preparing boric acid ester automobile braking fluid with high performance | |
| CN104629884A (en) | Advanced automobile brake fluid composition | |
| CN111763550A (en) | Brake fluid and preparation method thereof | |
| CN107828480B (en) | High-performance synthetic power-assisted steering oil composition and preparation method thereof | |
| CN114410368A (en) | Novel automobile brake fluid and preparation method thereof | |
| CN102337173B (en) | Anti-shearing long-life power steering fluid composition | |
| CN107573998B (en) | DOT6 borate type brake fluid | |
| CN101955840A (en) | High boiling point boric acid ester type synthetic brake fluid and preparation method thereof | |
| CN110041991B (en) | Vegetable oil-based high-temperature-resistant lubricating oil and preparation method thereof | |
| CN117448068B (en) | Brake fluid for severe cold areas and preparation method thereof | |
| CN1207373C (en) | Braking liquid of car and its preparing process | |
| CN116496826B (en) | High-performance automobile brake fluid and preparation method thereof | |
| CA1083593A (en) | Silane ester ether derivatives for hydraulic fluid | |
| CN110747035A (en) | Heat-insulation wear-resistant modification method for lubricating oil | |
| CN101294116B (en) | Transmission liquid for independent hydraulically controlled clutch system | |
| CN117625295B (en) | Dry film lubricant and preparation method thereof | |
| CN1315494A (en) | High-grade braking liquid for car and its preparing process | |
| CN116286151B (en) | High-boiling-point low-corrosion vehicle brake fluid and preparation method thereof | |
| CN110845419B (en) | Extreme pressure antiwear agent and road vehicle gear oil containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201120 |