CN111548774A - Cooling liquid for plug-in hybrid electric vehicle and preparation process thereof - Google Patents
Cooling liquid for plug-in hybrid electric vehicle and preparation process thereof Download PDFInfo
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- CN111548774A CN111548774A CN202010409339.2A CN202010409339A CN111548774A CN 111548774 A CN111548774 A CN 111548774A CN 202010409339 A CN202010409339 A CN 202010409339A CN 111548774 A CN111548774 A CN 111548774A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
The invention relates to the technical field of engine cooling liquid, in particular to cooling liquid for a plug-in hybrid power vehicle and a preparation process thereof. Compared with the prior art, the invention has low production cost, and the anti-corrosion additive consisting of polyethylene glycol, glycerol and poly-tricarboxylic acid is added on the basis of the traditional cooling liquid, and is firmly adsorbed on the surface of metal in a net structure, thereby not only having the protection function on the traditional metals of red copper, brass, steel, cast iron, soldering tin and cast aluminum, but also forming a powerful chelate with special metals of zinc, nickel and the like, thereby achieving the purpose of corrosion resistance and improving the inhibition and protection performance on cavitation corrosion. The preparation process determines that the polyethylene glycol, the glycerol and the poly-tricarboxylic acid can form a stable net structure, and simultaneously, the structure of the product is not damaged by adding other additives.
Description
Technical Field
The invention relates to the technical field of engine cooling liquid, in particular to cooling liquid for a plug-in hybrid electric vehicle and a preparation process thereof.
Background
The rapid development of the automobile industry drives the development and production of cooling liquid. The engine cooling liquid is a circulating medium in an engine cooling system, and the heat conductivity, the high boiling point and the low freezing point of the cooling liquid effectively inhibit boiling at high temperature and low-temperature icing so as to protect the engine.
Plug-in hybrid vehicles currently under development are classified into 3 types: a series hybrid type, a parallel hybrid type, and a series-parallel hybrid type. According to design requirements, the working temperatures of an engine, an intercooler, a generator, a motor and a side speed reducer are all higher than 373.0K, and the high-temperature heat source components are relatively arranged; the working temperature of the rectifier, the motor frequency converter and the system controller (including an engine control system, an energy management system, a vehicle control system and the like) is less than or equal to 333.0K, and the rectifier, the motor frequency converter and the system controller are relatively low-temperature heat source components. The high temperature heat source and the low temperature heat source are made of special metal materials, such as zinc, nickel and the like. The traditional cooling liquid generally uses ethylene glycol and deionized water as base liquid, and is supplemented with inorganic or organic additives. The product has good anti-corrosion effect on materials such as red copper, brass, steel, cast iron, soldering tin, cast aluminum and the like, but has no anti-corrosion effect on materials such as zinc, nickel and the like. Therefore, the conventional coolant cannot meet the corrosion prevention requirements. In order to solve this problem abroad, all-organic acid type engine coolants have been used. The all-organic acid type engine coolant is limited in use due to high production cost and easy cavitation corrosion, and has poor corrosion protection on zinc and nickel. The invention develops the cooling liquid for the plug-in hybrid electric vehicle and the research on the preparation process thereof from the viewpoint of the additive of the core of the cooling liquid.
Disclosure of Invention
In order to overcome the defects of the technical defects, the invention provides the cooling liquid for the plug-in hybrid electric vehicle and the preparation process thereof, and solves the problem that the existing engine cooling liquid in China lacks the protection on materials such as zinc, nickel and the like of a cooling liquid system.
The key point of the coolant for the plug-in hybrid electric vehicle is that the raw material components comprise the following components in percentage by mass: 35-90% of ethylene glycol, 0.01-5% of anti-corrosion additive, 0.05-3% of fatty carboxylic acid, 0.1-1% of alkali metal salt, 0.05-0.5% of sodium benzoate, 0.001-0.05% of defoaming agent and the balance of deionized water;
the anti-corrosion additive is prepared from the following components in percentage by mass of 1: 2: (1-8) polyethylene glycol, glycerol and poly-tricarboxylic acid.
Preferably, the molecular structural formula of the polytriatomic carboxylic acid is as follows:
the polymerization degree n is 1 to 10.
Preferably, the molecular weight of the polyethylene glycol is 600-1600.
Preferably, the anti-corrosion additive is prepared from the following components in a mass ratio of 1: 2: (1-5) polyethylene glycol, glycerol and poly-tricarboxylic acid.
Preferably, the fatty carboxylic acid is one or a mixture of C6-C12 monocarboxylic acid and C6-C12 dicarboxylic acid.
Preferably, the alkali metal salt is one or a mixture of two of sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
Preferably, the defoaming agent is one or a mixture of silicone and polyether.
Preferably, the dye also comprises a coloring agent with the mass fraction of 0.0001-0.01%, wherein the coloring agent is one of fluorescent green, fluorescent yellow, fluorescent red, bromothymol blue or methyl red.
The preparation method of the cooling liquid for the plug-in hybrid electric vehicle is characterized by comprising the following steps:
step one, preparing an anti-corrosion additive: preparing 0.01-1.5 mol/L aqueous solution from polyethylene glycol, glycerol, polytriatomic carboxylic acid and deionized water at 50 ℃, stirring for 30 minutes, and cooling to room temperature;
step two, after uniformly mixing ethylene glycol and deionized water, sequentially stirring and adding aliphatic carboxylic acid, alkali metal salt and sodium benzoate, and stirring for 30 minutes to obtain a primary mixed solution;
thirdly, dropwise adding the anti-corrosion additive into the primary mixed liquid, and controlling the dropwise adding speed to keep the reaction temperature at 25-50 ℃;
step four, adding a defoaming agent and a coloring agent into the solution prepared in the step three, and stirring for 30 minutes;
and step five, filtering the solution obtained in the step four to obtain the product.
Preferably, the dropping speed in the third step is 1.2-2.5 mL/min.
The beneficial effects are that: compared with the prior art, the cooling liquid for the plug-in hybrid electric vehicle provided by the invention does not contain amine substances, nitrite, phosphate, imidazole and other substances with high toxicity and strong pollution, does not contain silicate, borate and other inorganic preservatives, has low production cost, is added with an anti-corrosion additive consisting of polyethylene glycol, glycerol and poly-tribasic carboxylic acid on the basis of the traditional cooling liquid, is firmly adsorbed on the surface of metal in a net structure, has a protection effect on the traditional metals of red copper, brass, steel, cast iron, soldering tin and cast aluminum, can form a powerful chelate with zinc, nickel and other special metals, achieves the aim of corrosion prevention, greatly reduces the pitting corrosion of the engine cooling liquid on an engine cooling system, improves the inhibition and protection performance on corrosion, does not generate gel or form precipitates, the preparation method is stable in a relatively low concentration and a relatively large pH change range, the preparation process is simple, the polyethylene glycol, the glycerol and the poly-tricarboxylic acid can form a stable net structure, and the structure of a product is not damaged by adding other additives.
Detailed description of the invention
In order to make the technical solution of the present invention better understood by those skilled in the art, the present invention will be described in detail below with reference to the accompanying tables and specific embodiments.
Example 1
The raw materials are as follows: 35% of ethylene glycol, 0.01% of anti-corrosion additive, 0.05% of fatty carboxylic acid, 0.1% of sodium hydroxide, 0.05% of sodium benzoate, 0.001% of polydimethylsiloxane, 0.0001% of coloring agent and the balance of deionized water; the fatty carboxylic acid is undecane dicarboxylic acid and octanoic acid at a mass ratio of 1: 4.
The preparation process comprises the following steps: at the temperature of 50 ℃, mixing a mixture of 1: 2: 1 polyethylene glycol (molecular weight 600), glycerol, poly (tricarboxylic acid) (molecular structural formula:
the polymerization degree n is 1) and deionized water are prepared into water solution with the concentration of 0.01mol/L, the water solution is stirred for 30 minutes to obtain the anticorrosion additive, and the anticorrosion additive is cooled to room temperature for standby; uniformly mixing ethylene glycol and deionized water according to the formula amount, then sequentially stirring and adding undecanedioic acid, caprylic acid, sodium hydroxide and sodium benzoate according to the formula amount, and stirring for 30 minutes to obtain a primary mixed solution; then, dropwise adding the anti-corrosion additive with the formula amount into the primary mixed liquid at the speed of 1.2-2.5mL/min, and keeping the reaction temperature at 25-35 ℃; and after the dropwise addition is finished, adding polydimethylsiloxane and a coloring agent in a formula amount, stirring for 30 minutes, and filtering to obtain a finished product.
Example 2
The raw materials are as follows: 90% of ethylene glycol, 5% of an anti-corrosion additive, 3% of fatty carboxylic acid, 1% of potassium hydroxide, 0.5% of sodium benzoate, 0.05% of polyethylene glycol siloxane, 0.01% of a coloring agent and the balance of deionized water; the aliphatic carboxylic acid is caproic acid and pimelic acid with the mass ratio of 1: 2.
The preparation process comprises the following steps: at the temperature of 50 ℃, mixing a mixture of 1: 2: 8 polyethylene glycol (molecular weight 800), glycerol, poly (tricarboxylic acid) (molecular structural formula:
polymerization degree n is 5) and deionized water are prepared into water solution with the concentration of 1.5mol/L, the water solution is stirred for 30 minutes to obtain the anticorrosion additive, and the anticorrosion additive is cooled to room temperature for standby; uniformly mixing the ethylene glycol and the deionized water according to the formula ratioSequentially stirring and adding the undecane diacid, the octanoic acid, the sodium hydroxide and the sodium benzoate according to the formula amount, and stirring for 30 minutes to obtain a primary mixed solution; then, dropwise adding the anti-corrosion additive in the formula amount into the primary mixed liquid at the speed of 1.2-2.5mL/min, and maintaining the reaction temperature at 45-50 ℃; and after the dropwise addition is finished, adding the polyethylene glycol siloxane and the coloring agent according to the formula amount, stirring for 30 minutes, and filtering to obtain a finished product.
Example 3
The raw materials are as follows: 70% of ethylene glycol, 3.4% of an anti-corrosion additive, 2.1% of aliphatic carboxylic acid, 0.6% of calcium hydroxide, 0.3% of sodium benzoate, 0.017% of GP type glycerol polyether, 0.0008% of a coloring agent and the balance deionized water; the fatty carboxylic acid is mixed with the following components in a mass ratio of 1: 6 undecanedioic acid and dodecanoic acid.
The preparation process comprises the following steps: at the temperature of 50 ℃, mixing a mixture of 1: 2: 5 polyethylene glycol (molecular weight 1200), glycerol, poly (tricarboxylic acid) (molecular structural formula:
the polymerization degree n is 8) and deionized water are prepared into water solution with the concentration of 1.2mol/L, the water solution is stirred for 30 minutes to obtain the anticorrosion additive, and the anticorrosion additive is cooled to room temperature for standby; uniformly mixing ethylene glycol and deionized water according to the formula amount, then sequentially stirring and adding undecanedioic acid, caprylic acid, sodium hydroxide and sodium benzoate according to the formula amount, and stirring for 30 minutes to obtain a primary mixed solution; then, dropwise adding the anti-corrosion additive in the formula amount into the primary mixed liquid at the speed of 1.2-2.5mL/min, and maintaining the reaction temperature at 35-45 ℃; after the dropwise addition is finished, GP type glyceryl polyether and a coloring agent in the formula amount are added, stirred for 30 minutes and filtered to obtain a finished product.
Example 4
The raw materials are as follows: 48 percent of ethylene glycol, 0.08 percent of anticorrosive additive, 1.4 percent of aliphatic carboxylic acid, 0.4 percent of barium hydroxide, 0.1 percent of sodium benzoate, 0.0035 percent of GPE type polyoxyethylene (polyoxypropylene) ether, 0.003 percent of coloring agent and the balance of deionized water; the fatty carboxylic acid is prepared from 2: 1 sebacic acid and dodecanoic acid.
The preparation process comprises the following steps: at 50 ℃, mixing the mass ratioIs 1: 2: 2 polyethylene glycol (molecular weight 1600), glycerol, poly-tricarboxylic acid (molecular structural formula:
polymerization degree n is 10) and deionized water are prepared into water solution with the concentration of 0.08mol/L, the water solution is stirred for 30 minutes to obtain the anti-corrosion additive, and the anti-corrosion additive is cooled to room temperature for standby; uniformly mixing ethylene glycol and deionized water according to the formula amount, then sequentially stirring and adding undecanedioic acid, caprylic acid, sodium hydroxide and sodium benzoate according to the formula amount, and stirring for 30 minutes to obtain a primary mixed solution; then, dropwise adding the anti-corrosion additive in the formula amount into the primary mixed liquid at the speed of 1.2-2.5mL/min, and maintaining the reaction temperature at 35-50 ℃; after the dropwise addition is finished, GPE type polyoxyethylene (polyoxypropylene) ether and a coloring agent in the formula amount are added, the mixture is stirred for 30 minutes, and then the mixture is filtered to obtain a finished product.
Comparative example 1
Basf (BASF) Glysantin G64
Comparative example 2
Basf (BASF) Glysantin G65
The corrosion performance test was performed for each of examples 1 to 4 and comparative examples 1 to 2, and the test results are shown in the following table:
the method is determined by referring to the method specified in SH/T0085-1991 standard, the material and the size of the used metal test piece both meet the requirements of SH/T0085-1991, the test temperature is 88 +/-2 ℃, and the test time is 336h +/-2 h.
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Red copper, mg/tablet | 0.5 | 0.4 | 0.5 | 0.6 | 1.2 | 1.0 |
| Brass, mg/piece | 1.2 | 1.0 | 0.9 | 0.9 | 1.5 | 1.4 |
| Steel, mg/piece | 1.7 | 2.6 | 2.1 | 1.3 | 4.3 | 2.8 |
| Iron, mg/tablet | 3.5 | 4.2 | 3.1 | 2.1 | 4.7 | 6.8 |
| Solder, mg/tablet | 1.6 | 3.5 | 3.1 | 2.8 | 5.7 | 8.2 |
| Cast aluminium, mg/sheet | 0.4 | 0.5 | 0.6 | 0.5 | 7.5 | 8.1 |
| Zinc, mg/tablet | 0.6 | 0.6 | 1.1 | 0.3 | 142 | 265 |
| Nickel, mg/tablet | 0.3 | 0.9 | 0.6 | 0.7 | 333 | 468 |
As can be seen from the above table, the cooling liquid prepared by the invention has good multi-metal corrosion inhibition capability, the corrosion quality change of each metal test piece is obviously better than that of a comparative example, and the cooling liquid has excellent inhibition effect on the corrosion of zinc and nickel.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (10)
1. A coolant for a plug-in hybrid vehicle is characterized by comprising the following raw material components in parts by mass: 35-90% of ethylene glycol, 0.01-5% of anti-corrosion additive, 0.05-3% of fatty carboxylic acid, 0.1-1% of alkali metal salt, 0.05-0.5% of sodium benzoate, 0.001-0.05% of defoaming agent and the balance of deionized water;
the anti-corrosion additive is prepared from the following components in percentage by mass of 1: 2: (1-8) polyethylene glycol, glycerol and poly-tricarboxylic acid.
2. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the molecular structural formula of the poly-tricarboxylic acid is as follows:
the polymerization degree n is 1 to 10.
3. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the molecular weight of the polyethylene glycol is 600-1600.
4. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the anti-corrosion additive is prepared from the following components in percentage by mass of 1: 2: (1-5) polyethylene glycol, glycerol and poly-tricarboxylic acid.
5. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the aliphatic carboxylic acid is one or a mixture of more of C6-C12 monocarboxylic acid and C6-C12 dicarboxylic acid.
6. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the alkali metal salt is one or a mixture of two of sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide.
7. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the defoaming agent is one or a mixture of organic silicon and polyether.
8. The coolant for a plug-in hybrid vehicle according to claim 1, characterized in that: the fluorescent dye also comprises a coloring agent with the mass fraction of 0.0001-0.01%, wherein the coloring agent is one of fluorescent green, fluorescent yellow, fluorescent red, bromothymol blue or methyl red.
9. A method of producing the coolant for a plug-in hybrid vehicle according to any one of claims 1 to 8, characterized by comprising the steps of:
step one, preparing an anti-corrosion additive: preparing 0.01-1.5 mol/L aqueous solution from polyethylene glycol, glycerol, poly-tricarboxylic acid and deionized water at 50 ℃, stirring for 30 minutes, and cooling to room temperature;
step two, after uniformly mixing ethylene glycol and deionized water, sequentially stirring and adding aliphatic carboxylic acid, alkali metal salt and sodium benzoate, and stirring for 30 minutes to obtain a primary mixed solution;
thirdly, dropwise adding the anti-corrosion additive into the primary mixed liquid, and controlling the dropwise adding speed to keep the reaction temperature at 25-50 ℃;
step four, adding a defoaming agent and a coloring agent into the solution prepared in the step three, and stirring for 30 minutes;
and step five, filtering the solution obtained in the step four to obtain the product.
10. The method for preparing a coolant for a plug-in hybrid vehicle according to claim 9, wherein the dropping speed in step three is 1.2 to 2.5 mL/min.
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| CN202010409339.2A CN111548774A (en) | 2020-05-14 | 2020-05-14 | Cooling liquid for plug-in hybrid electric vehicle and preparation process thereof |
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| CN202010409339.2A CN111548774A (en) | 2020-05-14 | 2020-05-14 | Cooling liquid for plug-in hybrid electric vehicle and preparation process thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521914A (en) * | 2020-12-10 | 2021-03-19 | 广东石油化工学院 | Heat management liquid and preparation method thereof |
| CN112745808A (en) * | 2021-01-19 | 2021-05-04 | 广东石油化工学院 | Heat management system liquid and preparation method thereof |
| CN114106786A (en) * | 2021-01-25 | 2022-03-01 | 广东石油化工学院 | Thermal management system fluid composition |
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| CN114106786A (en) * | 2021-01-25 | 2022-03-01 | 广东石油化工学院 | Thermal management system fluid composition |
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