WO2023071900A1 - Additif de rupture de membrane d'huile de trempe et huile de trempe contenant l'additif de rupture de membrane - Google Patents

Additif de rupture de membrane d'huile de trempe et huile de trempe contenant l'additif de rupture de membrane Download PDF

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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
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WO
WIPO (PCT)
Prior art keywords
quenching oil
membrane breaking
breaking additive
membrane
unsaturated fatty
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PCT/CN2022/126321
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English (en)
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
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Publication of WO2023071900A1 publication Critical patent/WO2023071900A1/fr

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    • 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.

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  • 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

L'invention concerne un additif de rupture de membrane d'une huile de trempe et une huile de trempe contenant l'additif de rupture de membrane. L'additif de rupture de membrane est un ester de polyol d'acide gras insaturé ; et l'ester de polyol d'acide gras insaturé est obtenu après la mise en œuvre d'une réaction d'estérification sur un polyol et un acide gras insaturé contenant au moins une liaison cis-double. Dans la présente invention, l'additif de rupture de membrane utilisé existe dans l'huile de trempe sous forme de petites molécules. Seulement pendant un processus de trempe, une réaction de polymérisation se produit in situ sur la surface d'une pièce à travailler pour obtenir un effet de rupture de membrane. Selon un aspect de l'invention, l'impact d'un additif de rupture de membrane macromoléculaire sur la viscosité de l'huile de trempe finie peut être évité de manière efficace, et dans un autre aspect, la stabilité d'utilisation de l'huile de trempe peut être maintenue pendant une période de temps plus longue, ce qui permet de résoudre le problème existant selon lequel des additifs de rupture de membrane macromoléculaire ont un impact important sur la viscosité de l'huile de trempe, et le poids moléculaire relatif est réduit en raison d'un additif de rupture de membrane macromoléculaire qui est facilement décomposé après chauffage, ce qui conduit à des effets de rupture de membrane réduits après utilisation à long terme.
PCT/CN2022/126321 2021-10-29 2022-10-20 Additif de rupture de membrane d'huile de trempe et huile de trempe contenant l'additif de rupture de membrane WO2023071900A1 (fr)

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CN202111270866.0 2021-10-29
CN202111270866.0A CN113845425B (zh) 2021-10-29 2021-10-29 一种淬火油破膜添加剂及含该破膜添加剂的淬火油

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CN113845425B (zh) * 2021-10-29 2023-12-15 南京科润工业介质股份有限公司 一种淬火油破膜添加剂及含该破膜添加剂的淬火油
CN114657341B (zh) * 2022-04-14 2023-06-20 西华大学 一种氢能混合动力商用车发动机曲轴淬火设备及方法

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 (zh) * 2019-02-20 2019-05-07 张丹 一种高性能淬火油
CN111471842A (zh) * 2020-04-10 2020-07-31 南京科润工业介质股份有限公司 一种冷速稳定的超速光亮淬火油
CN112604002A (zh) * 2020-07-12 2021-04-06 苏州裕泰医药科技有限公司 二硫键桥连的多西他赛-脂肪酸前药及其自组装纳米粒
CN113845425A (zh) * 2021-10-29 2021-12-28 南京科润工业介质股份有限公司 一种淬火油破膜添加剂及含该破膜添加剂的淬火油

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3379215B2 (ja) * 1994-03-18 2003-02-24 三菱化学株式会社 アイスクリーム類用乳化剤及びそれを用いたアイスクリーム類の製造方法
JPH115988A (ja) * 1997-06-19 1999-01-12 Cosmo Sogo Kenkyusho:Kk 難燃性ポリオールエステル系潤滑油組成物
US7470381B2 (en) * 2003-07-25 2008-12-30 Rohmax Additives Gmbh Functional fluid and the use thereof
JP5930981B2 (ja) * 2013-02-06 2016-06-08 出光興産株式会社 熱処理油組成物
CN104480264A (zh) * 2014-12-01 2015-04-01 昌利锻造有限公司 一种光亮淬火油及其制备方法
CN105821187A (zh) * 2016-04-28 2016-08-03 昌利锻造有限公司 一种低挥发淬火油
CN110655970A (zh) * 2019-10-21 2020-01-07 中国石油化工股份有限公司 一种可生物降解变压器油及其制备方法
CN111304418A (zh) * 2020-03-18 2020-06-19 马鞍山金泉工业介质科技有限公司 一种轴承专用易清洗光亮性淬火油及其制备方法
CN113061693B (zh) * 2021-03-19 2022-02-22 广东剑鑫科技股份有限公司 一种迅速稳定的超速光亮淬火油及其制备方法

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 (zh) * 2019-02-20 2019-05-07 张丹 一种高性能淬火油
CN111471842A (zh) * 2020-04-10 2020-07-31 南京科润工业介质股份有限公司 一种冷速稳定的超速光亮淬火油
CN112604002A (zh) * 2020-07-12 2021-04-06 苏州裕泰医药科技有限公司 二硫键桥连的多西他赛-脂肪酸前药及其自组装纳米粒
CN113845425A (zh) * 2021-10-29 2021-12-28 南京科润工业介质股份有限公司 一种淬火油破膜添加剂及含该破膜添加剂的淬火油

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 *

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