WO2021134941A1

WO2021134941A1 - Quick bright quenching oil and preparation method therefor

Info

Publication number: WO2021134941A1
Application number: PCT/CN2020/081595
Authority: WO
Inventors: 左永平; 聂晓霖; 夏佰成
Original assignee: 南京科润工业介质股份有限公司; 南京科润工业技术有限公司
Priority date: 2019-12-30
Filing date: 2020-03-27
Publication date: 2021-07-08
Also published as: CN111074045B; CN111074045A

Abstract

Quick bright quenching oil, prepared by mixing the following components in percentage by weight: a basic oil: 80-92%; a refrigerant: 4-10%; a surfactant: 1.5-5%; an auxiliary dispersant: 0.5-3%; and an antioxidant: 0.5-2%. Also provided is a preparation method for the quenching oil. The present invention has excellent cooling performance, thermal oxidation stability, brightness, and oil-water separation performance; according to the preparation method for the quenching oil, by adding a basic oil into the system at twice, various additives in the formula can be well dispersed, thereby improving the stability of the additives in the oil product system and improving the application effect of the oil product.

Description

Quick bright quenching oil and preparation method thereof

Technical field

The invention relates to a fast bright quenching oil, and also relates to a preparation method of the quenching oil, belonging to the technical field of metal processing oils.

Background technique

Quenching is an important process in heat treatment, and cooling after quenching is an essential part. Through quenching, the potential of metal materials can be fully utilized to meet the requirements of various products and workpieces for metal materials. The performance of steel after quenching is determined by the microstructure after quenching, and the quenched microstructure is determined by the composition of the steel, the size of the part and the quenching process.

At present, the most widely used quenching medium is quenching oil, and the mineral oil used for quenching is usually based on a highly refined neutral paraffin base oil, which has high flash point, low viscosity, less oily smoke, less grease, and It has the advantages of good oxidation resistance, thermal stability, and long service life, so it is suitable for use as a quenching medium. However, the low-viscosity quenching oil is prone to aging during the quenching process, generating carbon black and oxidation products, which will cause the quenched workpiece to appear blue and black. In the cleaning step after the workpiece is quenched, if the oil-water separation effect of the quenching oil is not good, the residual quenching oil in the cleaning tank will be emulsified, resulting in waste liquid.

With the continuous development of industry and the continuous strict requirements on the appearance of quenched workpieces, quenching oil is required to have suitable cooling speed, better brightness and anti-emulsification characteristics. In the prior art, only additives are used to improve the cooling rate, brightness and demulsibility of quenching oil. However, quenching oil with various additives added has poor stability, and interference between different types of additives will reduce the oil. The performance of the product.

technical problem

In order to solve the problems in the prior art, the present invention provides a fast bright quenching oil, which not only has excellent cooling performance, but also has good thermal oxidation stability and brightness, and also has good oil-water separation. Performance (demulsibility).

Technical solutions

A fast bright quenching oil, mixed with the following components by weight percentage: base oil 80~92%, refrigerant 4~10%, surfactant 1.5~5%, auxiliary dispersant 0.5~3% and Antioxidant 0.5~2%.

Wherein, the kinematic viscosity of the base oil at 40° C. is not greater than 30 mm ² /s; wherein, the base oil is a mixture of one or more components in refined mineral base oil.

Wherein, the saturated hydrocarbon content in the mineral base oil is greater than or equal to 90%, the naphthenic content is greater than or equal to 40%, and the viscosity index of the base oil is greater than or equal to 90.

The base oil of the quenching oil of the present invention is selected in this viscosity range to provide a better cooling effect, and a higher viscosity base oil will reduce the cooling rate of the rapid quenching oil. At the same time, the content and viscosity index of saturated hydrocarbons and naphthenic hydrocarbons in the base oil are defined to ensure that the fast bright quenching oil has better oxidation stability, while improving its compatibility with additives and reducing the effect of aging products of the base oil on quenching The influence of the surface of the workpiece.

Wherein, the refrigerant is at least one of polyisobutylene, ethylene-propylene random copolymer, polymethacrylate, petroleum sulfonate or dialkylnaphthalene.

Wherein, the molecular weight of the synthetic polymer in the polyisobutylene, ethylene-propylene random copolymer, polymethacrylate and dialkylnaphthalene is 300-10000; preferably, the molecular weight is 500-5000.

The molecular weight of the synthetic polymer refrigerant of the present invention is 500-5000. Choosing such a refrigerant can form a sufficient adsorption film on the surface of the workpiece, increase the heat transfer coefficient of the quenching medium, and thereby increase the cooling rate of the fast bright quenching oil , Refrigerants with too high or too low molecular weight will reduce the cooling rate.

Wherein, the surfactant is imidazoline oleate and/or oleic acid amide.

In the present invention, imidazoline oleate or oleic acid amide is selected as the surfactant, and polyisobutylene succinimide with N content (mass fraction) ≥1.8% and molecular weight above 1000 is used as auxiliary dispersant, which is better Reduce the aging products of the base oil and the effect of carbon black on the surface of the quenched workpiece, improve the brightness of the fast bright quenching oil, and when the quenching oil contains more water, the surfactant can form at the interface between the water and the oil The honeycomb interface structure makes it easier to demulsify and provides good demulsification performance.

Wherein, the auxiliary dispersant is polyisobutylene succinimide; wherein the molecular weight of polyisobutylene in the polyisobutylene succinimide is ≥1000; wherein the mass percentage of N in the polyisobutylene succinimide is ≥1.8% .

Wherein, the antioxidant is a mixture of phenolic antioxidants and amine antioxidants; wherein, the phenolic antioxidants are 2,6-di-tert-butyl-p-cresol or macromolecular phenols in the shielding phenol Antioxidant; Amine type antioxidant is one of alkyl diphenylamine, alkyl phenyl-α-naphthylamine or octyl butyl diphenylamine.

Wherein, the mixing mass ratio of the phenol-type antioxidant and the amine-type antioxidant is 1:1.5-3.

The antioxidant of the present invention is a combination of a phenolic antioxidant and an amine antioxidant in a mass ratio of 1:1.5-3, and the two can fully exert a synergistic effect and improve the antioxidant performance of oil products. When the mass ratio between the two is too high, the amine antioxidant cannot provide sufficient high-temperature oxidation resistance, and cannot provide the anti-oxidation requirements of the quenching oil at a higher temperature during the quenching process of the workpiece; when the mass ratio is too low, the phenolic antioxidant Can not provide sufficient low-temperature anti-oxidation, can not guarantee the anti-oxidation requirements of the quenching oil tank at the normal use temperature.

The above-mentioned preparation method of fast bright quenching oil specifically includes the following steps:

(1) Mix the refrigerant, antioxidant and part of the base oil according to the formula, stir evenly, add the auxiliary dispersant of the formula to the mixture, heat up to 70~80℃, keep for 2.5~3h;

(2) Add all the remaining base oil, cool the material to 40~50°C, add the formulated amount of surfactant and continue to stir for 1~1.5h, cool to room temperature and then fill the equipment.

In the quenching oil preparation method of the present invention, the base oil is divided into two adding systems, which can well disperse various additives in the formula, thereby improving the stability of the additives in the oil system and prolonging the use effect of the oil.

Beneficial effect

The fast bright quenching oil of the present invention adopts the base oil component and a specific ratio of antioxidant composition, which can make the oil have good thermal oxidation stability, thereby improving its brightening effect during quenching. The auxiliary dispersant makes the oil have good oil-water separation performance (demulsibility); the formula uses a polymer refrigerant with a molecular weight of 500 to 5000 as the refrigerant, which can form a sufficient adsorption film on the surface of the workpiece, thereby Improve the cooling rate of the quenching oil; the preparation method of the quenching oil of the present invention, by dividing the base oil into two systems, can well disperse various additives in the formulation, thereby improving the stability of the additives in the oil system and extending The effect of oil use.

Embodiments of the present invention

The technical scheme of the present invention will be further described below in conjunction with specific embodiments.

The following examples and comparative examples prepare fast bright quenching oil based on raw materials. The raw materials used in the present invention can be purchased from the market.

The preparation methods of the fast bright quenching oil of this embodiment all include the following steps:

Example 1

The fast bright quenching oil of the present invention is prepared by mixing the following components by weight percentage:

Refined mineral oil (40℃ kinematic viscosity 10mm ² /s, saturated hydrocarbon content 92%, cycloalkane content 45%, viscosity index 92) 89%, polyisobutylene (molecular weight 500) 4%, polymethacrylate (molecular weight 5000)

2%, imidazoline oleate 2%, polyisobutylene succinimide (molecular weight 1000, N mass percentage 2%) 1%, 2,6-di-tert-butyl-p-cresol 0.5% and alkyl two Aniline 1.5%.

The quenching oil of Example 1 was prepared by the following method:

(1) Add 30% refined mineral oil and formula amount of polyisobutylene, polymethacrylate, 2,6-dibutyl-p-cresol and alkyl diphenylamine to the reactor and mix in sequence, stir well and then add to the formula Amount of polyisobutylene succinimide, heat up to 70℃, keep it for 3h;

(2) Add the remaining 59% of refined mineral oil to the mixture in step (1). After the temperature is lowered to 50°C, add the formula amount of imidazoline oleate and continue to stir for 1.5 hours. After cooling to room temperature, it is used for filling equipment.

Example 2

Refined mineral oil (40℃ kinematic viscosity 20mm ² /s, saturated hydrocarbon content 95%, cycloalkane content 40%, viscosity index 100) 84%, ethylene-propylene random copolymer (molecular weight 3000) 4%, polymethacrylic acid Ester (molecular weight 2000) 5%, petroleum sulfonate (molecular weight 1000) 1%, oleic acid amide 5%, polyisobutylene succinimide (molecular weight 2300, N content 1.8%) 0.5%, liquid polymer phenol 0.2% And alkylphenyl-α-naphthylamine 0.3%.

The quenching oil of Example 2 was prepared by the following method:

(1) Add 40% refined mineral oil and formula amount of ethylene-propylene random copolymer, polymethacrylate, petroleum sulfonate, liquid high molecular phenol and alkylphenyl-α-naphthylamine into the reaction in sequence Mix in the kettle, stir evenly, add the amount of polyisobutylene succinimide with the formula, heat up to 80°C, keep it for 3h;

(2) Add the remaining 44% refined mineral oil to the mixture in step (1). After the temperature is lowered to 50°C, add the formula amount of oleic acid amide and continue to stir for 1 hour. After the temperature is lowered to room temperature, it is used for filling equipment.

Example 3

The fast bright quenching oil of the present invention is made by mixing the following components by weight percentage: refined mineral oil (40°C kinematic viscosity 30mm ² /s, saturated hydrocarbon content 98%, naphthenic hydrocarbon content 40%, viscosity index 110) 92% , Dialkylnaphthalene (molecular weight 3000) 1%, polyisobutylene (molecular weight 2000) 3%, imidazoline oleate 1.5%, polyisobutylene succinimide (molecular weight 2300, N content 1.8%) 2%, sulfide 0.2% of base phenol and 0.3% of octylbutyl diphenylamine.

The quenching oil of Example 3 was prepared by the following method:

(1) Add 35% refined mineral oil and formula amount of dialkyl naphthalene, petroleum pitch, thioether-based phenol and octyl butyl diphenylamine into the reactor in turn and mix, stir evenly, and add formula amount of polyisobutylene butylene Diimide, heat up to 75℃, keep for 2.5h;

(2) Add the remaining 57% refined mineral oil to the mixture in step (1). After cooling to 40°C, add the formula amount of imidazoline oleate and continue stirring for 1.5 hours. After cooling to room temperature, it is used for filling equipment.

Example 4

The fast bright quenching oil of the present invention is prepared by mixing the following components by weight percentage: refined mineral oil (40℃ kinematic viscosity 17mm ² /s, saturated hydrocarbon content 95%, naphthenic hydrocarbon content 45%, viscosity index 105) 80% , Polymethacrylate (molecular weight 5000) 10%, imidazoline oleate 2%, oleic acid amide 3%

Polyisobutylene succinimide (molecular weight 2300, N content 2%) 3%, 2,6-di-tert-butyl p-cresol 0.5% and octyl butyl diphenylamine 1.5%.

The quenching oil of Example 4 was prepared by the following method:

(1) Add 40% refined mineral oil and formula amount of polymethacrylate, 2,6-dibutyl-p-cresol and octylbutyl diphenylamine into the reaction kettle and mix in sequence, stir well and add formula amount The temperature of polyisobutylene succinimide is increased to 70℃ for 3h;

(2) Add the remaining 40% refined mineral oil to the mixture in step (1). After the temperature is lowered to 40°C, add the formula amount of imidazoline oleate and oleic acid amide and continue to stir for 2 hours, then cool to room temperature and then fill. spare.

Comparative Example 1

The quenching oil formula is: refined mineral oil (40℃ kinematic viscosity 10mm ² /s, saturated hydrocarbon content 85%, cycloalkane content 35%, viscosity index 87) 89%, polyisobutylene (molecular weight 500) 4%, polymethacrylic acid Ester (molecular weight 5000) 2%, imidazoline oleate 2%, polyisobutylene succinimide (molecular weight 1000, N content 1%) 1%, 2,6-di-tert-butyl-p-cresol 1% and alkane Diphenylamine 0.5%.

Process: Pour all refined mineral oil into the kettle, heat up to 80°C, and add the formula amount of polyisobutylene, polymethacrylate, imidazoline oleate, polyisobutylene succinimide, 2,6-di Butyl-p-cresol and alkyl diphenylamine, stir well, keep for 3h, cool down to room temperature, and then pour equipment for use.

Comparative Example 2

The quenching oil formula is: refined mineral oil (40℃ kinematic viscosity 10mm ² /s, saturated hydrocarbon content 85%, cycloalkane content 35%, viscosity index 87) 90%, polyisobutylene (molecular weight 500) 4%, polymethacrylic acid Ester (molecular weight 5000) 2%, imidazoline oleate 2%, 2,6-di-tert-butyl-p-cresol 1% and alkyl diphenylamine 0.5%.

Process: Pour all refined mineral oil into the kettle, heat it up to 80°C, add the formula amount of polyisobutylene, polymethacrylate, imidazoline oleate, 2,6-dibutyl-p-cresol and alkyl group in sequence Diphenylamine, stir evenly, keep it for 3h, cool down to room temperature, and pour equipment for use.

The quenching oil test results of Examples 1 to 4 and Comparative Examples 1 to 2 are shown in Table 1:

Table 1 Test data of physical and chemical properties of the comparative examples of the above examples

Re-test the samples after storage for one year:

Table 2 Partial performance retest after sample storage for one year

[0061] It can be seen from Table 1 and Table 2 that compared to Comparative Examples 1 to 2, the fast bright quenching oil prepared in Examples 1 to 4 has excellent cooling performance, thermal oxidation stability and brightness, and takes into account the separation of oil and water. performance.

The fast bright quenching oil of the present invention not only has excellent oxidation resistance, but also can prolong the use requirements of low-viscosity quenching oil for the quenched workpiece, improve the brightening effect during quenching, and take into account the oil-water separation performance, and reduce the cleaning of the quenching oil on the quenched workpiece. Emulsification occurred during the process.

Claims

A fast bright quenching oil, which is characterized in that it is mixed with the following components by weight percentage: base oil 80~92%, refrigerant 4~10%, surfactant 1.5~5%, auxiliary dispersant 0.5 ~3% and antioxidant 0.5~2%.
The fast bright quenching oil according to claim 1, characterized in that: the kinematic viscosity of the base oil at 40°C is not more than 30mm 2 /s; wherein, the base oil is composed of one or more of mineral base oils mixture.
The fast bright quenching oil according to claim 1, wherein the saturated hydrocarbon content in the mineral base oil is ≥90%, the naphthenic hydrocarbon content is ≥40%, and the viscosity index of the base oil is ≥90.
The fast bright quenching oil according to claim 1, wherein the refrigerant is selected from polyisobutylene, ethylene-propylene random copolymer, polymethacrylate, petroleum sulfonate or dialkylnaphthalene At least one.
The fast bright quenching oil according to claim 1, wherein the molecular weight of the synthetic polymer of polyisobutylene, ethylene-propylene random copolymer, polymethacrylate and dialkylnaphthalene is 300~10000 .
The fast bright quenching oil according to claim 1, wherein the surfactant is imidazoline oleate and/or oleic acid amide.
The fast bright quenching oil according to claim 1, wherein the auxiliary dispersant is polyisobutylene succinimide; wherein the molecular weight of polyisobutylene in the polyisobutylene succinimide is ≥1000; wherein, the polyisobutylene The mass percentage of N in succinimide is ≥1.8%.
The fast bright quenching oil according to claim 1, wherein the antioxidant is a mixture of a phenolic antioxidant and an amine antioxidant; wherein the phenolic antioxidant is a shielding phenol 2. 6-di-tert-butyl-p-cresol or polymer phenol type antioxidant; amine type antioxidant is one of alkyldiphenylamine, alkylphenyl-α-naphthylamine or octylbutyldiphenylamine.
The fast bright quenching oil according to claim 8, wherein the mixing mass ratio of the phenolic antioxidant and the amine antioxidant is 1:1.5-3.
The method for preparing fast bright quenching oil according to claim 1, characterized in that it specifically comprises the following steps:

(1) Mix the refrigerant, antioxidant and part of the base oil according to the formula, stir evenly, add the auxiliary dispersant of the formula to the mixture, heat up to 70~80℃, keep for 2.5~3h;

(2) Add all the remaining base oil, cool the material to 40~50°C, add the formulated amount of surfactant and continue to stir for 1~1.5h, cool to room temperature and then fill the equipment.