WO2023071900A1 - Quenching oil membrane breaking additive and quenching oil containing membrane breaking additive - Google Patents

Quenching oil membrane breaking additive and quenching oil containing membrane breaking additive Download PDF

Info

Publication number
WO2023071900A1
WO2023071900A1 PCT/CN2022/126321 CN2022126321W WO2023071900A1 WO 2023071900 A1 WO2023071900 A1 WO 2023071900A1 CN 2022126321 W CN2022126321 W CN 2022126321W WO 2023071900 A1 WO2023071900 A1 WO 2023071900A1
Authority
WO
WIPO (PCT)
Prior art keywords
quenching oil
membrane breaking
breaking additive
membrane
unsaturated fatty
Prior art date
Application number
PCT/CN2022/126321
Other languages
French (fr)
Chinese (zh)
Inventor
余瀚森
夏佰成
丁林
左永平
聂晓霖
Original Assignee
南京科润工业介质股份有限公司
南京科润新材料技术有限公司
南京科润工业技术有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 南京科润工业介质股份有限公司, 南京科润新材料技术有限公司, 南京科润工业技术有限公司 filed Critical 南京科润工业介质股份有限公司
Publication of WO2023071900A1 publication Critical patent/WO2023071900A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/58—Esters of straight chain acids with eighteen carbon atoms in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
    • C21D1/58—Oils

Definitions

  • the invention relates to a quenching oil membrane-breaking additive, and also relates to a quenching oil containing the above-mentioned membrane-breaking additive.
  • Quenching is essentially to heat the metal above the critical temperature and keep it warm to make it fully or partially austenitized, and then rapidly cool it in a quenching medium to transform it into bainite or martensite.
  • the most widely used quenching medium is oil-based quenching medium based on mineral oil.
  • the quenching process usually goes through three stages: steam film stage, boiling stage and convection stage.
  • steam film stage boiling stage
  • convection stage In order to increase the cooling capacity of the quenching oil and improve the uniformity of cooling, it is necessary to add a steam film breaking additive to the quenching oil to shorten the time of the steam film stage and increase the cooling speed of the quenching oil.
  • Patent CN107109503 discloses a membrane-breaking additive prepared from asphalt. Using 70N mineral oil with a kinematic viscosity of 15mm 2 /s at 40°C, the quenching oil obtained after adding 6% of the film-breaking additive has a good effect of promoting the rupture of the steam film, but the viscosity of the obtained quenching oil is lower than that of the base oil There is a 15% to 25% increase in viscosity, which indirectly affects the fluidity of the quenching oil, thereby affecting the effect of quenching and cooling. In addition, commonly used film-breaking additives such as PIB1300, PIB2400, and petroleum resins in the industry have similar disadvantages during use because the additives are all polymer compounds.
  • the film-breaking effect of such polymer membrane-breaking additives is related to its molecular weight.
  • the quenching oil needs to be in contact with red-hot workpieces with temperatures above 850°C.
  • Polymer compounds cannot be used under the impact of high-temperature workpieces. It is avoided that thermal decomposition will lead to a decrease in molecular weight, and then membrane rupture failure will occur after a period of use.
  • the purpose of the present invention is to provide a kind of quenching oil membrane-breaking additive that does not affect the viscosity of the quenching oil and has longer service stability.
  • Another purpose of the present invention is to provide the quenching oil comprising the above-mentioned membrane-breaking additive.
  • the quenching oil membrane-breaking additive described in the present invention is an unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is composed of an unsaturated fatty acid containing at least one cis double bond and a polyol It is obtained by esterification reaction.
  • the unsaturated fatty acid containing at least one cis-type double bond and the polyol are mixed according to the molar ratio of carboxyl and hydroxyl functional groups at 1:1, and reacted at 120-130°C for 3-5 hours. Vacuum to remove the moisture generated during the reaction in time to increase the reaction rate;
  • the molecular weight of unsaturated fatty acid polyol ester is 300-400.
  • the unsaturated fatty acid containing at least one cis double bond is oleic acid, linoleic acid, linolenic acid or erucic acid.
  • the polyhydric alcohol is polyhydric fatty alcohol containing at least two hydroxyl groups.
  • the polyhydric fatty alcohol containing at least two hydroxyl groups is ethylene glycol, glycerol or pentaerythritol.
  • the quenching oil containing the above membrane-breaking additive is composed of the following components in weight percent: 8-10% of membrane-breaking additive, 88-90% of base oil, 0.8-1% of antioxidant and 0.8-1% of brightener.
  • the base oil is a mixture of one or more of mineral base oils or synthetic base oils, with a kinematic viscosity of 5-500mm 2 /s at 40°C, a viscosity index ⁇ 90, and a flash point ⁇ 160°C.
  • 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 anti-oxidation performance of the quenching oil, and ensure that the life of the quenching oil will not be reduced due to oxidation during use.
  • the organic phenolic antioxidant is 3,5-di-tert-butyl-4-hydroxyphenylpropionate; the organic amine antioxidant is dinonyldiphenylamine.
  • the brightener is oleoyl sarcosinate.
  • the steam film rupture additive that the present invention uses has the cis-type double bond that can take place DA addition reaction, so it can generate macromolecule film (the reaction condition of in-situ polymerization reaction is 300°C or higher), so as to promote the rupture of the steam film during the quenching and cooling process.
  • the significant advantage of the present invention is that: the membrane-breaking additive used in the present invention exists in the form of small molecules in the quenching oil, and only in the quenching process, the in-situ polymerization reaction occurs on the surface of the workpiece to reach The effect of membrane breaking, on the one hand, can effectively avoid the influence of the polymer membrane breaking additive on the viscosity of the finished quenching oil;
  • the viscosity of the oil has a great influence, and the macromolecular membrane-breaking additive is easily decomposed by heat, resulting in a decrease in molecular weight, which leads to the problem of a decrease in the membrane-breaking effect of long-term use;
  • the membrane-breaking additive of the present invention can be applied to base oils with a wide viscosity range, and can be prepared according to GB /T 30823 Quenching oil with excellent film breaking effect in the quenching oil cooling characteristic test, whose upper characteristic temperature is higher than 720°C.
  • the synthesis of the quenching oil film-breaking additive of the present invention-ethylene glycol ester of oleate is specifically: add oleic acid 282g (1mol) in the there-necked flask that mechanical stirrer and thermometer are housed, ethylene glycol 31g (0.5mol), open Stir, heat up to 120°C, react for 3 hours, remove water in a vacuum, and obtain a brown oily ethylene glycol oleate product.
  • the synthesis of the quenching oil membrane breaking additive-glyceryl oleate of the present invention is specifically: add oleic acid 282g (1mol) in the there-necked flask equipped with mechanical stirrer and thermometer, glycerol 30g (0.3mol), start stirring, Raise the temperature to 130°C, react for 4.5 hours, remove the moisture by vacuuming, and obtain a brown paste product of glycerol oleate.
  • the quenching oil of the present invention containing ethylene glycol oleate, a membrane-breaking additive consists of the following components in weight percent: 90% of 70N mineral oil (40°C kinematic viscosity 15 mm 2 /s, viscosity index 95), ethylene glycol oleate %, 0.5% dinonyl diphenylamine, 0.5% 3,5-di-tert-butyl-4-hydroxyphenyl propionate and 1% oleoyl sarcosinate.
  • the present invention contains the quenching oil of membrane breaking additive glycerol oleate, is made up of following weight percentage components:
  • a quenching oil consisting of the following components in weight percent: 90% of 70N mineral oil (kinematic viscosity of 15mm 2 /s at 40°C, viscosity index of 95), 8% of polyisobutylene (PIB1300), 0.5% of dinonyl diphenylamine, 3 , 5-di-tert-butyl-4-hydroxyphenylpropionate 0.5% and oleoyl sarcosinate 1%.
  • Table 1 is the inspection data of the comparison of physical and chemical properties and membrane breaking effect of the quenching oil of Examples 3 to 4 and Comparative Example 1
  • the membrane-breaking additive of the present invention can achieve a similar membrane-breaking effect and improve the cooling performance of the quenching oil, while significantly reducing the impact on the viscosity of the quenching oil itself .
  • the membrane-breaking additive itself is a small molecule, there is no problem that the molecular weight will decrease due to thermal cracking at high temperature, and the membrane-breaking effect will decrease.
  • Using the membrane-breaking additive of the present invention can better maintain the viscosity of the quenching oil during use. And the stability of cooling performance, so as to ensure the consistency and stability of heat treatment product quality.
  • the use of the film-breaking additive of the present invention can also effectively improve the brightness of the quenched workpiece.
  • the film-breaking additive of the present invention undergoes DA addition reaction on the surface of high-temperature workpieces to form a polymer film, which can reduce the heat flux on the surface of the workpiece, thereby promoting the rupture of the steam film during the quenching process.
  • the film-breaking additive of the present invention can effectively improve the cooling process of quenching oil
  • the upper characteristic temperature (the higher the upper characteristic temperature, the faster the membrane can be broken), the cooling speed and cooling uniformity of the quenching oil can be improved, and the quenching oil with an upper characteristic temperature greater than 720 ° C can be prepared by using the membrane breaking additive of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Lubricants (AREA)

Abstract

Disclosed are a quenching oil membrane breaking additive and quenching oil containing the membrane breaking additive. The membrane breaking additive is an unsaturated fatty acid polyol ester; and the unsaturated fatty acid polyol ester is obtained after carrying out an esterification reaction on polyol and an unsaturated fatty acid containing at least one cis-double bond. In the present invention, the membrane breaking additive used exists in quenching oil as small molecules. Only during a quenching process, a polymerization reaction occurs in situ on a surface of a workpiece to achieve a membrane breaking effect. In one aspect, the impact of a macromolecular membrane breaking additive on the viscosity of the finished quenching oil may be effectively avoided, and in another aspect, usage stability of the quenching oil may be maintained for a longer period of time, thereby solving the existing problem that macromolecular membrane breaking additives have a great impact on the viscosity of quenching oil, and the relative molecular weight is reduced due to a macromolecular membrane breaking additive being easily decomposed after being heated, thereby leading to reduced membrane breaking effects after long-term use.

Description

一种淬火油破膜添加剂及含该破膜添加剂的淬火油A kind of quenching oil film breaking additive and quenching oil containing the film breaking additive 技术领域technical field
本发明涉及一种淬火油破膜添加剂，还涉及包含上述破膜添加剂的淬火油。The invention relates to a quenching oil membrane-breaking additive, and also relates to a quenching oil containing the above-mentioned membrane-breaking additive.
背景技术Background technique
为使金属工件获得更好的硬度、抗疲劳性能以及长使用寿命，需要将金属工件进行包括淬火工序在内的热处理。淬火本质上是将金属加热到临界温度以上并保温，使其完全或部分奥氏体化，然后在淬火介质中快速冷却，使其发生贝氏体或马氏体转换。目前使用最为广泛的淬火介质是以矿物油为基础的油基淬火介质，淬火过程通常会经历三个阶段：蒸汽膜阶段、沸腾阶段和对流阶段。为增加淬火油冷却能力，提高冷却均匀性，需要在淬火油中添加蒸汽膜破膜添加剂以缩短蒸汽膜阶段时间，提高淬火油冷却速度。In order to obtain better hardness, fatigue resistance and long service life of metal workpieces, it is necessary to carry out heat treatment including quenching process on metal workpieces. Quenching is essentially to heat the metal above the critical temperature and keep it warm to make it fully or partially austenitized, and then rapidly cool it in a quenching medium to transform it into bainite or martensite. The most widely used quenching medium is oil-based quenching medium based on mineral oil. The quenching process usually goes through three stages: steam film stage, boiling stage and convection stage. In order to increase the cooling capacity of the quenching oil and improve the uniformity of cooling, it is necessary to add a steam film breaking additive to the quenching oil to shorten the time of the steam film stage and increase the cooling speed of the quenching oil.
专利CN107109503公开了一种以沥青为原料制备而成的破膜添加剂。采用40℃运动粘度为15mm 2/s的70N矿物油，添加6％该破膜添加剂后所得到的淬火油有很好的促进蒸汽膜破裂的效果，但得到的淬火油粘度相比于基础油有15％～25％的粘度增加，从而间接影响淬火油的流动性，进而影响淬火冷却效果。除此之外，业内常用的PIB1300、PIB2400、石油树脂等破膜添加剂，因添加剂均为高分子化合物，因此在使用过程中均有类似弊端。除此之外，此类高分子破膜添加剂的破膜效果与其分子量大小相关，使用过程中，淬火油需要与温度高达850℃以上的红热工件接触，高分子化合物在高温工件冲击下不可避免的会发生热分解导致分子量下降，进而使用一段时间后会发生破膜失效问题。 Patent CN107109503 discloses a membrane-breaking additive prepared from asphalt. Using 70N mineral oil with a kinematic viscosity of 15mm 2 /s at 40°C, the quenching oil obtained after adding 6% of the film-breaking additive has a good effect of promoting the rupture of the steam film, but the viscosity of the obtained quenching oil is lower than that of the base oil There is a 15% to 25% increase in viscosity, which indirectly affects the fluidity of the quenching oil, thereby affecting the effect of quenching and cooling. In addition, commonly used film-breaking additives such as PIB1300, PIB2400, and petroleum resins in the industry have similar disadvantages during use because the additives are all polymer compounds. In addition, the film-breaking effect of such polymer membrane-breaking additives is related to its molecular weight. During use, the quenching oil needs to be in contact with red-hot workpieces with temperatures above 850°C. Polymer compounds cannot be used under the impact of high-temperature workpieces. It is avoided that thermal decomposition will lead to a decrease in molecular weight, and then membrane rupture failure will occur after a period of use.
发明内容Contents of the invention
发明目的：本发明的目的是提供一种不影响淬火油粘度同时具有更长时间使用稳定性的淬火油破膜添加剂，本发明另一目的是提供包含上述破膜添加剂的淬火油。Purpose of the invention: the purpose of the present invention is to provide a kind of quenching oil membrane-breaking additive that does not affect the viscosity of the quenching oil and has longer service stability. Another purpose of the present invention is to provide the quenching oil comprising the above-mentioned membrane-breaking additive.
技术方案：本发明所述的淬火油破膜添加剂，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发生酯化反应而得到。Technical solution: the quenching oil membrane-breaking additive described in the present invention, the membrane-breaking additive is an unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is composed of an unsaturated fatty acid containing at least one cis double bond and a polyol It is obtained by esterification reaction.
其中，将含至少一个顺式双键的不饱和脂肪酸与多元醇按羧基和羟基官能团的摩尔比1:1混合，于120～130℃反应3～5小时，视原料反应活性，必要时可抽真空，将反应过程中产生的水分及时去除，以增加反应速率；Among them, the unsaturated fatty acid containing at least one cis-type double bond and the polyol are mixed according to the molar ratio of carboxyl and hydroxyl functional groups at 1:1, and reacted at 120-130°C for 3-5 hours. Vacuum to remove the moisture generated during the reaction in time to increase the reaction rate;
含至少一个顺式双键的不饱和脂肪酸与多元醇生成不饱和脂肪酸多元醇酯的反应式为：The reaction formula that the unsaturated fatty acid that contains at least one cis double bond and polyalcohol generates unsaturated fatty acid polyalcohol ester is:
Figure PCTCN2022126321-appb-000001
Figure PCTCN2022126321-appb-000001
其中，不饱和脂肪酸多元醇酯的分子量为300～400。Wherein, the molecular weight of unsaturated fatty acid polyol ester is 300-400.
其中，至少含一个顺式双键的不饱和脂肪酸为油酸、亚油酸、亚麻酸或芥酸。Wherein, the unsaturated fatty acid containing at least one cis double bond is oleic acid, linoleic acid, linolenic acid or erucic acid.
其中，多元醇为至少含两个羟基的多元脂肪醇。Wherein, the polyhydric alcohol is polyhydric fatty alcohol containing at least two hydroxyl groups.
其中，至少含两个羟基的多元脂肪醇为乙二醇、丙三醇或季戊四醇。Wherein, the polyhydric fatty alcohol containing at least two hydroxyl groups is ethylene glycol, glycerol or pentaerythritol.
包含上述破膜添加剂的淬火油，由如下重量百分比的组分组成：破膜添加剂8～10％、基础油88～90％、抗氧剂0.8～1％以及光亮剂0.8～1％。The quenching oil containing the above membrane-breaking additive is composed of the following components in weight percent: 8-10% of membrane-breaking additive, 88-90% of base oil, 0.8-1% of antioxidant and 0.8-1% of brightener.
基础油为矿物基础油或合成基础油中的一种或多种组成的混合物，其40℃运动粘度在5～500mm 2/s，粘度指数≥90，闪点≥160℃。 The base oil is a mixture of one or more of mineral base oils or synthetic base oils, with a kinematic viscosity of 5-500mm 2 /s at 40°C, a viscosity index ≥ 90, and a flash point ≥ 160°C.
其中，所述抗氧剂为有机胺类抗氧剂和有机酚类抗氧剂按重量比1:1的混合物。复配抗氧剂能够有效提高淬火油的抗氧化性能，保证淬火油在使用过程中不会因为氧化而导致寿命降低。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 anti-oxidation performance of the quenching oil, and ensure that the life of the quenching oil will not be reduced due to oxidation during use.
其中，所述有机酚类抗氧剂为3，5-二叔丁基-4-羟基苯基丙酸酯；有机胺类抗氧剂为二壬基二苯胺。所述光亮剂为油酰肌氨酸盐。Wherein, the organic phenolic antioxidant is 3,5-di-tert-butyl-4-hydroxyphenylpropionate; the organic amine antioxidant is dinonyldiphenylamine. The brightener is oleoyl sarcosinate.
本发明使用的蒸汽膜破膜添加剂具有可发生DA加成反应的顺式双键，因此其可以在淬火过程中在工件表面原位发生聚合反应生成高分子薄膜(原位聚合反应的反应条件为300℃以上)，从而达到促进淬火冷却过程中的蒸汽膜破裂。The steam film rupture additive that the present invention uses has the cis-type double bond that can take place DA addition reaction, so it can generate macromolecule film (the reaction condition of in-situ polymerization reaction is 300°C or higher), so as to promote the rupture of the steam film during the quenching and cooling process.
含顺式双键的DA加成反应的反应式为：The reaction formula of DA addition reaction with cis double bond is:
Figure PCTCN2022126321-appb-000002
Figure PCTCN2022126321-appb-000002
有益效果：与现有技术相比，本发明的显著优点在于：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；本发明破膜添加剂能够适用于粘度范围广的基础油，均能够制备得到按照GB/T 30823淬火油冷却特性测试中上特性温度高于720℃的具有优异破膜效果的淬火油。Beneficial effects: Compared with the prior art, the significant advantage of the present invention is that: the membrane-breaking additive used in the present invention exists in the form of small molecules in the quenching oil, and only in the quenching process, the in-situ polymerization reaction occurs on the surface of the workpiece to reach The effect of membrane breaking, on the one hand, can effectively avoid the influence of the polymer membrane breaking additive on the viscosity of the finished quenching oil; The viscosity of the oil has a great influence, and the macromolecular membrane-breaking additive is easily decomposed by heat, resulting in a decrease in molecular weight, which leads to the problem of a decrease in the membrane-breaking effect of long-term use; the membrane-breaking additive of the present invention can be applied to base oils with a wide viscosity range, and can be prepared according to GB /T 30823 Quenching oil with excellent film breaking effect in the quenching oil cooling characteristic test, whose upper characteristic temperature is higher than 720°C.
具体实施方式Detailed ways
下面结合具体实施例对本发明技术方案作进一步阐述。The technical solutions of the present invention will be further elaborated below in conjunction with specific embodiments.
实施例1Example 1
本发明淬火油破膜添加剂-油酸乙二醇酯的合成，具体为：在装有机械搅拌器和温度计的三口烧瓶中加入油酸282g(1mol)，乙二醇31g(0.5mol)，开启搅拌，升温至120℃，反应3h，抽真空除去水分，得褐色油状油酸乙二醇酯产物。The synthesis of the quenching oil film-breaking additive of the present invention-ethylene glycol ester of oleate is specifically: add oleic acid 282g (1mol) in the there-necked flask that mechanical stirrer and thermometer are housed, ethylene glycol 31g (0.5mol), open Stir, heat up to 120°C, react for 3 hours, remove water in a vacuum, and obtain a brown oily ethylene glycol oleate product.
实施例2Example 2
本发明淬火油破膜添加剂-油酸甘油酯的合成，具体为：在装有机械搅拌器和温度计的三口烧瓶中加入油酸282g(1mol)，丙三醇30g(0.3mol)，开启搅拌，升温至130℃，反应4.5h，抽真空除去水分，得褐色膏状油酸甘油酯产物。The synthesis of the quenching oil membrane breaking additive-glyceryl oleate of the present invention is specifically: add oleic acid 282g (1mol) in the there-necked flask equipped with mechanical stirrer and thermometer, glycerol 30g (0.3mol), start stirring, Raise the temperature to 130°C, react for 4.5 hours, remove the moisture by vacuuming, and obtain a brown paste product of glycerol oleate.
实施例3Example 3
本发明含破膜添加剂油酸乙二醇酯的淬火油，由如下重量百分比组分组成：70N矿物油(40℃运动粘度15mm 2/s，粘度指数95)90％、油酸乙二醇酯％、二壬基二苯胺0.5％、3，5-二叔丁基-4-羟基苯基丙酸酯0.5％以及油酰肌氨酸盐1％。 The quenching oil of the present invention containing ethylene glycol oleate, a membrane-breaking additive, consists of the following components in weight percent: 90% of 70N mineral oil (40°C kinematic viscosity 15 mm 2 /s, viscosity index 95), ethylene glycol oleate %, 0.5% dinonyl diphenylamine, 0.5% 3,5-di-tert-butyl-4-hydroxyphenyl propionate and 1% oleoyl sarcosinate.
将组分按照上述比例在60℃下进行搅拌，制备淬火油。针对实施例3所制得的淬火油，测定40℃运动粘度、光亮性和60℃静置条件下的冷却特性曲线，记录上特性温度和最大冷速。Stir the components according to the above ratio at 60°C to prepare quenching oil. For the quenching oil prepared in Example 3, measure the kinematic viscosity at 40°C, the brightness and the cooling characteristic curve under the condition of standing at 60°C, and record the characteristic temperature and maximum cooling rate.
实施例4Example 4
本发明含破膜添加剂油酸甘油酯的淬火油，由如下重量百分比组分组成：The present invention contains the quenching oil of membrane breaking additive glycerol oleate, is made up of following weight percentage components:
70N矿物油(40℃运动粘度15mm 2/s，粘度指数95)90％、油酸甘油酯8％、二壬基二苯胺0.5％、3，5-二叔丁基-4-羟基苯基丙酸酯0.5％以及油酰肌氨酸盐1％。 70N mineral oil (40°C kinematic viscosity 15mm 2 /s, viscosity index 95) 90%, glyceryl oleate 8%, dinonyl diphenylamine 0.5%, 3,5-di-tert-butyl-4-hydroxyphenylpropyl Ester 0.5% and Oleoyl Sarcosinate 1%.
将组分按照上述比例在60℃下进行搅拌，制备淬火油。针对实施例4所制得的淬火油，测定40℃运动粘度、光亮性和60℃静置条件下的冷却特性曲线，记录上特性温度和最大冷速。Stir the components according to the above ratio at 60°C to prepare quenching oil. For the quenching oil prepared in Example 4, measure the kinematic viscosity at 40°C, the brightness and the cooling characteristic curve under the condition of standing at 60°C, and record the characteristic temperature and maximum cooling rate.
对比实施例1Comparative Example 1
一种淬火油，由如下重量百分比组分组成：70N矿物油(40℃运动粘度15mm 2/s，粘度指数95)90％、聚异丁烯(PIB1300)8％、二壬基二苯胺0.5％、3，5-二叔丁基-4-羟基苯基丙酸酯0.5％以及油酰肌氨酸盐1％。 A quenching oil consisting of the following components in weight percent: 90% of 70N mineral oil (kinematic viscosity of 15mm 2 /s at 40°C, viscosity index of 95), 8% of polyisobutylene (PIB1300), 0.5% of dinonyl diphenylamine, 3 , 5-di-tert-butyl-4-hydroxyphenylpropionate 0.5% and oleoyl sarcosinate 1%.
将组分按照上述比例在60℃下进行搅拌，制备淬火油。针对对比实施例1所制得的淬火油，测定40℃运动粘度、光亮性和60℃静置条件下的冷却特性曲线，记录上特性温度和最大冷速。Stir the components according to the above ratio at 60°C to prepare quenching oil. For the quenching oil prepared in Comparative Example 1, the kinematic viscosity at 40°C, the brightness and the cooling characteristic curve under the condition of standing at 60°C were measured, and the characteristic temperature and maximum cooling rate were recorded.
表1为实施例3～4与对比实施例1淬火油的理化性能和破膜效果对比的检验数据Table 1 is the inspection data of the comparison of physical and chemical properties and membrane breaking effect of the quenching oil of Examples 3 to 4 and Comparative Example 1
Figure PCTCN2022126321-appb-000003
Figure PCTCN2022126321-appb-000003
Figure PCTCN2022126321-appb-000004
Figure PCTCN2022126321-appb-000004
通过表1可知，相比于采用聚异丁烯作为破膜添加剂的淬火油，采用本发明破膜添加剂在达到相似破膜效果，提高淬火油冷却性能的同时，可以显著降低对淬火油本身粘度的影响。同时由于破膜添加剂本身是小分子，不存在由于在高温下发生热裂解而导致分子量下降，破膜效果下降的问题，用本发明破膜添加剂可使淬火油在使用过程中更好的维持粘度和冷却性能的稳定，从而保证热处理产品质量的一致性和稳定性。并且，光亮性测试发现，采用本发明破膜添加剂还可以有效改善淬火工件的光亮性。本发明破膜添加剂在高温工件表面发生DA加成反应成高分子膜，起到降低工件表面热流密度的作用，从而促进淬火过程中蒸汽膜的破裂，本发明破膜添加剂有效提高淬火油冷却过程中的上特性温度(上特性温度越高，能够越快破膜)，提高淬火油冷却速度和冷却均匀性，利用本发明破膜添加剂可制备上特性温度大于720℃的淬火油。It can be seen from Table 1 that compared with the quenching oil using polyisobutylene as the membrane-breaking additive, the membrane-breaking additive of the present invention can achieve a similar membrane-breaking effect and improve the cooling performance of the quenching oil, while significantly reducing the impact on the viscosity of the quenching oil itself . At the same time, because the membrane-breaking additive itself is a small molecule, there is no problem that the molecular weight will decrease due to thermal cracking at high temperature, and the membrane-breaking effect will decrease. Using the membrane-breaking additive of the present invention can better maintain the viscosity of the quenching oil during use. And the stability of cooling performance, so as to ensure the consistency and stability of heat treatment product quality. Moreover, it is found from the brightness test that the use of the film-breaking additive of the present invention can also effectively improve the brightness of the quenched workpiece. The film-breaking additive of the present invention undergoes DA addition reaction on the surface of high-temperature workpieces to form a polymer film, which can reduce the heat flux on the surface of the workpiece, thereby promoting the rupture of the steam film during the quenching process. The film-breaking additive of the present invention can effectively improve the cooling process of quenching oil The upper characteristic temperature (the higher the upper characteristic temperature, the faster the membrane can be broken), the cooling speed and cooling uniformity of the quenching oil can be improved, and the quenching oil with an upper characteristic temperature greater than 720 ° C can be prepared by using the membrane breaking additive of the present invention.

Claims (8)

  1. 一种淬火油破膜添加剂，其特征在于：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。A quenching oil membrane breaking additive, characterized in that: the membrane breaking additive is an unsaturated fatty acid polyol ester; the unsaturated fatty acid polyol ester is esterified by an unsaturated fatty acid containing at least one cis double bond and a polyhydric alcohol obtained after the reaction.
  2. 根据权利要求1所述的淬火油破膜添加剂，其特征在于：将含至少一个顺式双键的不饱和脂肪酸与多元醇按羧基和羟基官能团的摩尔比1:1混合，于120～130℃反应3～5小时得到不饱和脂肪酸多元醇酯。The quenching oil membrane breaking additive according to claim 1, characterized in that: the unsaturated fatty acid containing at least one cis double bond and the polyhydric alcohol are mixed according to the molar ratio of carboxyl and hydroxyl functional groups of 1:1, and the mixture is heated at 120-130°C React for 3-5 hours to obtain unsaturated fatty acid polyol ester.
  3. 根据权利要求2所述的淬火油破膜添加剂，其特征在于：所述不饱和脂肪酸多元醇酯的分子量为300～400。The quenching oil membrane breaking additive according to claim 2, characterized in that: the molecular weight of the unsaturated fatty acid polyol ester is 300-400.
  4. 根据权利要求2所述的淬火油破膜添加剂，其特征在于：至少含一个顺式双键的不饱和脂肪酸为油酸、亚油酸、亚麻酸或芥酸。The membrane breaking additive for quenching oil according to claim 2, characterized in that: the unsaturated fatty acid containing at least one cis double bond is oleic acid, linoleic acid, linolenic acid or erucic acid.
  5. 根据权利要求2所述的淬火油破膜添加剂，其特征在于：所述多元醇为至少含两个羟基的多元脂肪醇；其中，至少含两个羟基的多元脂肪醇为乙二醇、丙三醇或季戊四醇。The quenching oil membrane breaking additive according to claim 2, characterized in that: the polyhydric alcohol is a polyhydric fatty alcohol containing at least two hydroxyl groups; wherein, the polyhydric fatty alcohol containing at least two hydroxyl groups is ethylene glycol, glycerin alcohol or pentaerythritol.
  6. 包含权利要求1所述的破膜添加剂的淬火油，其特征在于：由如下重量百分比的组分组成：破膜添加剂8～10％、基础油88～90％、抗氧剂0.8～1％以及光亮剂0.8～1％。The quenching oil comprising the membrane-breaking additive according to claim 1 is characterized in that: it is composed of the following components in weight percentage: 8-10% of membrane-breaking additive, 88-90% of base oil, 0.8-1% of antioxidant and Brightener 0.8-1%.
  7. 根据权利要求6所述的淬火油，其特征在于：所述抗氧剂为有机胺类抗氧剂和有机酚类抗氧剂按重量比1:1的混合物。The quenching oil according to claim 6, characterized in that: the antioxidant is a mixture of an organic amine antioxidant and an organic phenol antioxidant in a weight ratio of 1:1.
  8. 根据权利要求7所述的淬火油，其特征在于：所述有机酚类抗氧剂为3，5-二叔丁基-4-羟基苯基丙酸酯；有机胺类抗氧剂为二壬基二苯胺。The quenching oil according to claim 7, characterized in that: the organic phenolic antioxidant is 3,5-di-tert-butyl-4-hydroxyphenyl propionate; the organic amine antioxidant is dinonyl diphenylamine.
PCT/CN2022/126321 2021-10-29 2022-10-20 Quenching oil membrane breaking additive and quenching oil containing membrane breaking additive WO2023071900A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111270866.0 2021-10-29
CN202111270866.0A CN113845425B (en) 2021-10-29 2021-10-29 Quenching oil film breaking additive and quenching oil containing same

Publications (1)

Publication Number Publication Date
WO2023071900A1 true WO2023071900A1 (en) 2023-05-04

Family

ID=78983461

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/126321 WO2023071900A1 (en) 2021-10-29 2022-10-20 Quenching oil membrane breaking additive and quenching oil containing membrane breaking additive

Country Status (2)

Country Link
CN (1) CN113845425B (en)
WO (1) WO2023071900A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845425B (en) * 2021-10-29 2023-12-15 南京科润工业介质股份有限公司 Quenching oil film breaking additive and quenching oil containing same
CN114657341B (en) * 2022-04-14 2023-06-20 西华大学 Engine crankshaft quenching equipment and method for hydrogen energy hybrid commercial vehicle

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140261926A1 (en) * 2012-12-10 2014-09-18 A. & A. Fratelli Parodi S.P.A. Synthetic Quenching Fluid Composition
CN109722511A (en) * 2019-02-20 2019-05-07 张丹 A kind of high-performance quenching oil
CN111471842A (en) * 2020-04-10 2020-07-31 南京科润工业介质股份有限公司 Over-speed bright quenching oil with stable cooling speed
CN112604002A (en) * 2020-07-12 2021-04-06 苏州裕泰医药科技有限公司 Disulfide-bond bridged docetaxel-fatty acid prodrug and self-assembled nanoparticles thereof
CN113845425A (en) * 2021-10-29 2021-12-28 南京科润工业介质股份有限公司 Quenching oil film breaking additive and quenching oil containing same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3379215B2 (en) * 1994-03-18 2003-02-24 三菱化学株式会社 Emulsifier for ice creams and method for producing ice creams using the same
JPH115988A (en) * 1997-06-19 1999-01-12 Cosmo Sogo Kenkyusho:Kk Flame-retardant polyester-based lubricating oil composition
US7470381B2 (en) * 2003-07-25 2008-12-30 Rohmax Additives Gmbh Functional fluid and the use thereof
JP5930981B2 (en) * 2013-02-06 2016-06-08 出光興産株式会社 Heat treated oil composition
CN104480264A (en) * 2014-12-01 2015-04-01 昌利锻造有限公司 Bright quenching oil and preparation method thereof
CN105821187A (en) * 2016-04-28 2016-08-03 昌利锻造有限公司 Low-volatility quenching oil
CN110655970A (en) * 2019-10-21 2020-01-07 中国石油化工股份有限公司 Biodegradable transformer oil and preparation method thereof
CN111304418A (en) * 2020-03-18 2020-06-19 马鞍山金泉工业介质科技有限公司 Easily-cleaned bright quenching oil special for bearing and preparation method thereof
CN113061693B (en) * 2021-03-19 2022-02-22 广东剑鑫科技股份有限公司 Rapid and stable overspeed bright quenching oil and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140261926A1 (en) * 2012-12-10 2014-09-18 A. & A. Fratelli Parodi S.P.A. Synthetic Quenching Fluid Composition
CN109722511A (en) * 2019-02-20 2019-05-07 张丹 A kind of high-performance quenching oil
CN111471842A (en) * 2020-04-10 2020-07-31 南京科润工业介质股份有限公司 Over-speed bright quenching oil with stable cooling speed
CN112604002A (en) * 2020-07-12 2021-04-06 苏州裕泰医药科技有限公司 Disulfide-bond bridged docetaxel-fatty acid prodrug and self-assembled nanoparticles thereof
CN113845425A (en) * 2021-10-29 2021-12-28 南京科润工业介质股份有限公司 Quenching oil film breaking additive and quenching oil containing same

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
DATABASE Registry CAS; 16 November 1984 (1984-11-16), ANONYMOUS : "9,12-Octadecadienoic ac id (9Z,12Z)-, 2,3-dihy droxypropyl ester", XP093062277, Database accession no. 2277-28-3 *
DATABASE Registry CAS; 16 November 1984 (1984-11-16), ANONYMOUS : "9-Octadecenoic acid (9 Z)-, 2,3-dihydroxypr opyl ester", XP093062275, Database accession no. 111-03-5 *
DATABASE Registry CAS; 16 November 1984 (1984-11-16), ANONYMOUS : "9-Octadecenoic acid (9 Z)-, 2-hydroxy-1-(hy droxymethyl)ethyl e ster", XP093062280, Database accession no. 3443-84-3 *
DATABASE Registry CAS; 16 November 1984 (1984-11-16), ANONYMOUS : "9-Octadecenoic acid (9 Z)-, 2-hydroxyethyl e ster", XP093062284, Database accession no. 4500-01-0 *
DATABASE Registry CAS; 16 November 1984 (1984-11-16), ANONYMOUS : "9-Octadecenoic acid (9 Z)-, 3-hydroxy-2,2-bi s(hydroxymethyl)pr opyl ester", XP093062286, Database accession no. 10332-32-8 *
DATABASE Registry CAS; 27 January 1989 (1989-01-27), ANONYMOUS : "9,12-Octadecadienoic ac id (9Z,12Z)-, 2-hydro xyethyl ester ", XP093062292, Database accession no. 118675-23-3 *
DATABASE Regsitry CAS; 4 August 1985 (1985-08-04), ANONYMOUS : "9,12-Octadecadienoic ac id (9Z,12Z)-, 3-hydroxy-2,2-bis(hy droxymethyl)propyl ester (9CI) ", XP093062291, Database accession no. 97488-56-7 *
LIU, YE ET AL.: "Effect of Additives on the Performance of Fast Bright Quenching Oil", HOT WORKING TECHNOLOGY, vol. 43, no. 4, 28 February 2014 (2014-02-28), pages 190 - 192, XP009545336, ISSN: 1001-3814 *

Also Published As

Publication number Publication date
CN113845425B (en) 2023-12-15
CN113845425A (en) 2021-12-28

Similar Documents

Publication Publication Date Title
WO2023071900A1 (en) Quenching oil membrane breaking additive and quenching oil containing membrane breaking additive
JP6152502B2 (en) Fullerene derivatives and lubricants
US2353192A (en) Stabilized fuel oil composition and method thereof
WO2022001515A1 (en) Preparation method for cardanol modified polyamine curing agent having high anticorrosive performance
JP2019514912A (en) Benzotriazole derivative, method for producing the same and application
US4174461A (en) Stabilized perfluoropolyether fluids
CN111909525A (en) High-temperature-resistant silicon rubber containing phenyl and preparation method thereof
CN111393996B (en) Polymerized rosin mixed ester and preparation method and application thereof
CN111471842A (en) Over-speed bright quenching oil with stable cooling speed
JP3567279B2 (en) Lubricant composition containing polymeric antioxidant
EP2055763A1 (en) Lubricating oil composition
US4036773A (en) Lubricant compositions containing carboxylic acid esters of hindered hydroquinones
US20140274846A1 (en) Stabilized fluids for industrial applications
JP2007502887A (en) Complex polyol esters with improved performance
CN107652424A (en) Dimeric dibasic acid neopentyl glycol complex ester and preparation method thereof
JP2005513201A (en) Quenching oil composition
CN111592864A (en) High-boiling-point cooling liquid
Hung et al. Synthesis biolubricant from rubber seed oil
JP2000072715A (en) Polyhydric alcohol ester compound and lubricating oil composition containing the same
CN109181811B (en) High-viscosity high-temperature-resistant trimesic acid synthetic ester base oil and preparation method thereof
CN116478754B (en) Ester type transformer oil composition with high hydrolytic stability
CN110157517B (en) Nano titanium oxide antiwear additive and method for preparing nano titanium oxide
JPH0352996A (en) Oiliness improver of mill clean rolling oil
CN112280612A (en) High-performance transformer oil and preparation method thereof
JPS63195273A (en) Metal-containing composition for inhibiting oxidation of metallic material at high temperature and production thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22885778

Country of ref document: EP

Kind code of ref document: A1