阅读说明：本技术 一种淬火油破膜添加剂及含该破膜添加剂的淬火油 (Quenching oil film breaking additive and quenching oil containing same ) 是由 余瀚森 夏佰成 丁林 左永平 聂晓霖 于 2021-10-29 设计创作，主要内容包括：本发明公开了一种淬火油破膜添加剂及包含上述破膜添加剂的淬火油,所述破膜添加剂为不饱和脂肪酸多元醇酯；所述不饱和脂肪酸多元醇酯由含至少一个顺式双键的不饱和脂肪酸与多元醇酯化反应后得到。本发明使用的破膜添加剂在淬火油中以小分子形式存在,只有在淬火过程中,才在工件表面原位发生聚合反应达到破膜的效果,一方面可有效避免高分子破膜添加剂对成品淬火油的粘度影响,另一方面可以维持淬火油更长时间的使用稳定性,从而解决现有采用大分子破膜添加剂对淬火油粘度影响大,且大分子破膜添加剂受热易分解导致分子量下降,从而导致长期使用破膜效果下降的问题。(The invention discloses a quenching oil film breaking additive and quenching oil containing the same, wherein the film breaking additive is unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is obtained by esterification reaction of unsaturated fatty acid containing at least one cis-double bond and polyol. The film breaking additive used in the invention exists in the quenching oil in a micromolecule form, only in the quenching process, the in-situ polymerization reaction is carried out on the surface of a workpiece to achieve the film breaking effect, on one hand, the influence of the macromolecule film breaking additive on the viscosity of the finished quenching oil can be effectively avoided, on the other hand, the use stability of the quenching oil for a longer time can be maintained, and therefore, the problems that the influence of the macromolecule film breaking additive on the viscosity of the quenching oil is large, and the macromolecule film breaking additive is easily decomposed by heating to cause the reduction of molecular weight, so that the reduction of the film breaking effect in long-term use is caused are solved.)

1. The quenching oil film breaking additive is characterized in that: the film breaking additive is unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is obtained by esterification reaction of unsaturated fatty acid containing at least one cis-double bond and polyol.

2. The quenching oil film breaking additive as claimed in claim 1, wherein: mixing unsaturated fatty acid containing at least one cis-double bond with polyhydric alcohol according to the molar ratio of 1:1 of carboxyl and hydroxyl functional groups, and reacting at 120-130 ℃ for 3-5 hours to obtain unsaturated fatty acid polyhydric alcohol ester.

3. The quenching oil film breaking additive as claimed in claim 2, wherein: the molecular weight of the unsaturated fatty acid polyol ester is 300-400.

4. The quenching oil film breaking additive as claimed in claim 2, wherein: the unsaturated fatty acid containing at least one cis-double bond is oleic acid, linoleic acid, linolenic acid or erucic acid.

5. The quenching oil film breaking additive as claimed in claim 2, wherein: the polyol is a polyhydric fatty alcohol containing at least two hydroxyl groups; wherein the polyhydric aliphatic alcohol containing at least two hydroxyl groups is ethylene glycol, glycerol or pentaerythritol.

6. Quenching oil comprising the film breaking additive according to claim 1, characterized in that: the composite material comprises the following components in percentage by weight: 8-10% of a film breaking additive, 88-90% of base oil, 0.8-1% of an antioxidant and 0.8-1% of a brightener.

7. The quenching oil of claim 6, wherein: the antioxidant is a mixture of an organic amine antioxidant and an organic phenol antioxidant in a weight ratio of 1: 1.

8. The quenching oil of claim 7, wherein: the organic phenol antioxidant is 3, 5-di-tert-butyl-4-hydroxyphenyl propionate; the organic amine antioxidant is dinonyl diphenylamine.

Technical Field

The invention relates to a quenching oil film breaking additive and quenching oil containing the film breaking additive.

Background

In order to obtain better hardness, fatigue resistance and long service life of the metal workpiece, the metal workpiece needs to be subjected to heat treatment including a quenching process. Quenching essentially consists of heating the metal above the critical temperature and holding it warm to complete or partial austenization, followed by rapid cooling in a quenching medium to allow bainitic or martensitic transformation to occur. The most widely used quenching media at present are oil-based quenching media based on mineral oil, and the quenching process usually goes through three stages: a vapor film stage, a boiling stage, and a convection stage. In order to increase the cooling capacity of quenching oil and improve the cooling uniformity, a steam film breaking additive needs to be added into the quenching oil to shorten the steam film stage time and improve the cooling speed of the quenching oil.

Patent CN107109503 discloses a film breaking additive prepared by using asphalt as raw material. The kinematic viscosity at 40 ℃ is 15mm²The quenching oil obtained by adding 6% of the film breaking additive into 70N mineral oil/s has a good effect of promoting steam film breaking, but the viscosity of the obtained quenching oil is increased by 15% -25% compared with that of base oil, so that the fluidity of the quenching oil is indirectly influenced, and the quenching cooling effect is further influenced. In addition, because the additives such as PIB1300, PIB2400, petroleum resin and the like which are commonly used in the industry are all high molecular compounds, the additives have similar defects in the use process. In addition, the film breaking effect of the high-molecular film breaking additive is related to the molecular weight, in the using process, quenching oil needs to be in contact with a red hot workpiece with the temperature of more than 850 ℃, and the high-molecular compound inevitably generates under the impact of the high-temperature workpieceThe molecular weight is reduced due to thermal decomposition, and the membrane breaking failure problem can occur after the membrane is used for a period of time.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a quenching oil film breaking additive which does not affect the viscosity of the quenching oil and has longer service stability, and the invention also aims to provide the quenching oil containing the film breaking additive.

The technical scheme is as follows: the quenching oil film breaking additive is unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is obtained by esterification reaction of unsaturated fatty acid containing at least one cis-double bond and polyol.

Mixing unsaturated fatty acid containing at least one cis-double bond with polyhydric alcohol according to the molar ratio of carboxyl to hydroxyl functional groups of 1:1, reacting for 3-5 hours at 120-130 ℃, vacuumizing if necessary according to the reaction activity of raw materials, and removing moisture generated in the reaction process in time to increase the reaction rate;

the unsaturated fatty acid containing at least one cis double bond and polyol generate unsaturated fatty acid polyol ester according to the reaction formula:

wherein the molecular weight of the unsaturated fatty acid polyol ester is 300-400.

Wherein the unsaturated fatty acid containing at least one cis-form double bond is oleic acid, linoleic acid, linolenic acid or erucic acid.

Wherein the polyhydric alcohol is a polyhydric fatty alcohol containing at least two hydroxyl groups.

Wherein the polyhydric aliphatic alcohol containing at least two hydroxyl groups is ethylene glycol, glycerol or pentaerythritol.

The quenching oil containing the film breaking additive comprises the following components in percentage by weight: 8-10% of a film breaking additive, 88-90% of base oil, 0.8-1% of an antioxidant and 0.8-1% of a brightener.

The base oil isOne or more of mineral base oil or synthetic base oil, and has a kinematic viscosity at 40 deg.C of 5-500 mm²The viscosity index is more than or equal to 90 and the flash point is more than or equal to 160 ℃.

Wherein the antioxidant is a mixture of an organic amine antioxidant and an organic phenol antioxidant in a weight ratio of 1: 1. The compound antioxidant can effectively improve the oxidation resistance of the quenching oil and ensure that the service life of the quenching oil is not reduced due to oxidation in the using process.

Wherein the organic phenol antioxidant is 3, 5-di-tert-butyl-4-hydroxyphenyl propionate; the organic amine antioxidant is dinonyl diphenylamine. The brightener is oleoyl sarcosinate.

The steam film breaking additive used in the invention has cis double bonds capable of generating DA addition reaction, so that the steam film breaking additive can generate polymerization reaction in situ on the surface of a workpiece in the quenching process to generate a high molecular film (the reaction condition of the in-situ polymerization reaction is more than 300 ℃), thereby promoting the steam film breaking in the quenching and cooling process.

The reaction formula of the DA addition reaction containing cis double bonds is as follows:

has the advantages that: compared with the prior art, the invention has the remarkable advantages that: the film breaking additive used in the invention exists in the quenching oil in a micromolecule form, only in the quenching process, the in-situ polymerization reaction is carried out on the surface of a workpiece to achieve the film breaking effect, on one hand, the influence of the macromolecule film breaking additive on the viscosity of the finished quenching oil can be effectively avoided, on the other hand, the use stability of the quenching oil for a longer time can be maintained, and therefore, the problems that the influence of the macromolecule film breaking additive on the viscosity of the quenching oil is large, and the macromolecule film breaking additive is easily decomposed by heating to cause the reduction of molecular weight, so that the reduction of the film breaking effect in long-term use is caused are solved; the film breaking additive disclosed by the invention can be suitable for base oil with a wide viscosity range, and can be used for preparing quenching oil with an excellent film breaking effect, wherein the upper characteristic temperature of the quenching oil is higher than 720 ℃ in a GB/T30823 quenching oil cooling characteristic test.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

Example 1

The invention relates to a synthesis method of a quenching oil film breaking additive-ethylene glycol oleate, which comprises the following steps: 282g (1mol) of oleic acid and 31g (0.5mol) of ethylene glycol are added into a three-neck flask provided with a mechanical stirrer and a thermometer, stirring is started, the temperature is raised to 120 ℃, the reaction is carried out for 3h, and the water is removed by vacuum pumping to obtain the brown oily ethylene glycol oleate product.

Example 2

The invention relates to a synthesis method of a quenching oil film breaking additive-glyceryl oleate, which comprises the following steps: 282g (1mol) of oleic acid and 30g (0.3mol) of glycerol are added into a three-neck flask provided with a mechanical stirrer and a thermometer, stirring is started, the temperature is raised to 130 ℃, the reaction is carried out for 4.5h, and the water is removed by vacuum pumping to obtain the brown pasty glyceryl oleate product.

Example 3

The quenching oil containing the film breaking additive ethylene glycol oleate consists of the following components in percentage by weight: 70N mineral oil (kinematic viscosity at 40 ℃ 15 mm)²Viscosity index 95), ethylene glycol oleate, dinonyl diphenylamine 0.5%, 3, 5-di-tert-butyl-4-hydroxyphenyl propionate 0.5% and oleoyl sarcosinate 1%.

The components are stirred at the temperature of 60 ℃ according to the proportion to prepare the quenching oil. For the quenching oil obtained in example 3, kinematic viscosity at 40 ℃, brightness, and cooling characteristic curve at 60 ℃ under a standing condition were measured, and the characteristic temperature and the maximum cooling rate were recorded.

Example 4

The quenching oil containing the film breaking additive glyceryl oleate disclosed by the invention comprises the following components in percentage by weight: 70N mineral oil (kinematic viscosity at 40 ℃ 15 mm)²Viscosity index 95), glycerol oleate 8%, dinonyl diphenylamine 0.5%, 3, 5-di-tert-butyl-4-hydroxyphenyl propionate 0.5% and oleoyl sarcosinate 1%.

The components are stirred at the temperature of 60 ℃ according to the proportion to prepare the quenching oil. For the quenching oil obtained in example 4, kinematic viscosity at 40 ℃, brightness, and cooling characteristic curve at 60 ℃ under a standing condition were measured, and the characteristic temperature and the maximum cooling rate were recorded.

Comparative example 1

Quenching oil consists of the following components in percentage by weight: 70N mineral oil (kinematic viscosity at 40 ℃ 15 mm)²Viscosity index 95), polyisobutylene (PIB1300)8, dinonyldiphenylamine 0.5, 3, 5-di-tert-butyl-4-hydroxyphenyl propionate 0.5 and oleoyl sarcosinate 1%.

The components are stirred at the temperature of 60 ℃ according to the proportion to prepare the quenching oil. For the quenching oil obtained in comparative example 1, kinematic viscosity at 40 ℃, brightness, and cooling characteristic curve at 60 ℃ under a standing condition were measured, and the characteristic temperature and the maximum cooling rate were recorded.

Table 1 shows the comparative test data of the physical and chemical properties and the film breaking effect of the quenching oil of examples 3 to 4 and comparative example 1

As can be seen from Table 1, compared with the quenching oil using polyisobutylene as the film breaking additive, the film breaking additive of the invention can achieve similar film breaking effect, improve the cooling performance of the quenching oil, and simultaneously can significantly reduce the influence on the viscosity of the quenching oil. Meanwhile, the film breaking additive is a micromolecule, so that the problems of molecular weight reduction and film breaking effect reduction caused by thermal cracking at high temperature are solved, and the film breaking additive can be used for better maintaining the stability of viscosity and cooling performance of quenching oil in the using process, so that the consistency and stability of the quality of heat treatment products are ensured. And the brightness test finds that the brightness of the quenched workpiece can be effectively improved by adopting the film breaking additive. The film breaking additive of the invention generates DA addition reaction on the surface of a high-temperature workpiece to form a polymer film, which plays a role in reducing the heat flux density on the surface of the workpiece, thereby promoting the rupture of a steam film in the quenching process.