CN107418673A - A kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride and its preparation method and application - Google Patents

A kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride and its preparation method and application Download PDF

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Publication number
CN107418673A
CN107418673A CN201710245621.XA CN201710245621A CN107418673A CN 107418673 A CN107418673 A CN 107418673A CN 201710245621 A CN201710245621 A CN 201710245621A CN 107418673 A CN107418673 A CN 107418673A
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Prior art keywords
succinic anhydride
cutting fluid
agent
polyisobutenyl succinic
system based
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CN107418673B (en
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侯海燕
戴恩期
向晖
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Guangzhou Guoji Lubrication Technology Co., Ltd
Guangzhou Machinery Research Institute Co., Ltd
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Guangzhou Jisheng Lubrication Technology Co Ltd
Guangzhou Mechanical Engineering Research Institute Co Ltd
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    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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Abstract

The invention belongs to metalworking fluid field, discloses a kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride and its preparation method and application.The present invention includes base oil, polyisobutylene succinic anhydride mixture (mass ratio 2:1:1 molecular weight be 200,400 and 1000 polyisobutenyl succinic anhydride mix), nonionic surfactant, PH conditioning agents, lubricant, extreme pressure agent, antirust agent, corrosion inhibiter, bactericide.Polybutene mixture of succinic anhydride is used for the primary emulsion of cutting fluid first in the present invention, not only make it that this emulsification system is highly stable, is not easy smelly long bacterium, and make it that life of product is very long, work liquid energy uses more than half a year；There is the performances such as excellent antirust, lubrication, low bubble simultaneously.The cutting fluid superior performance, can be used for the machining center of high speed and precision, especially be had outstanding performance in terms of non-ferrous metals processing, be mainly used in the tapping, depth drill etc. of electronic product.

Description

A kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride and its Preparation method and application
Technical field
The invention belongs to metalworking fluid field, more particularly to a kind of novel emulsion based on polyisobutenyl succinic anhydride Cutting fluid of system and its preparation method and application.
Background technology
Aqueous cutting fluid was come out in nineteen forties, due to its cheap cost and excellent cooling characteristics And rapidly developed.It is developed so far, aqueous cutting fluid is in leading position in some metal processing sectors.Mesh Before, water-based metal working fluid system is usually using petroleum sulfonate as emulsification system, and the system is present not environmentally, easily hair It is smelly, low production efficiency, the defects of waiting big for environment pollution.At the same time global environment, health and safety are expected, tightened up prison A series of changes of pipe etc. these future directions so that metal working fluid industry, be faced with many challenges.Metal working fluid row The complexity of industry application demand, the change and increasingly strict supervision in chemicals supply market are expected, and make market environment more next It is severeer.And future《Registration, assessment, mandate and the limitation of chemicals》The pressure of implementation, many OIL IN LUBRICATING OIL PRODUCTIONs will be promoted Business changes, revises and updated lubricating formulations.Structuring, work closely and innovate by way of changed.
In today that the gradual exhaustion of oil, environmental requirement are increasingly stricter, develop based on environmentally friendly renewable raw materials Water-based metal working fluid is very urgent.Early in 2012, there is the expert in more and more industries to start sight to throw Searching to new raw material, there is the new emulsification system of succinic anhydride in external metal working fluid market, 2015, external It is large-scale a burst of research and the upsurge using succinic anhydride, such as BASF, DOW Chemical, Lu Borun etc. the whole world have just been started Additive company simultaneously be proposed each molecular weight, the succinic anhydride emulsifying agent of various modifications.Kui Ke, Fu Lan in 2016 Gram, numerous fully reinforced imported products of the metalworking fluid such as Castrol are proposed Related product and seize market one after another.And I The metalworking fluid of state is still based on traditional sodium sulfonate system, and domestic cutting fluid market：Medium-to-high grade Water Soluble Cutting The share for cutting liquid-based this 60-70% is occupied by Anti-oxygen Additives From Foreign Lubricating Oil Package company, and especially high-end market is monopolized by imported product substantially, is led to Cross and exchanged with some experts both domestic and external, the present inventor, which studies, finds that succinic anhydride system has than traditional mahogany acid salt system Better performance and life-span.
The content of the invention
In order to overcome shortcoming and defect present in prior art, primary and foremost purpose of the invention is to provide one kind based on poly- The cutting fluid of the novel emulsion system of isobutenyl succinic anhydride；The cutting fluid substitutes petroleum sodium sulfonate and oleic acid and decided emulsification Agent, nonionic surfactant, antirust agent, corrosion inhibiter, bactericide these raw materials are equipped with, then pass through and the weight of each raw material is formed Rationally set, the emulsion cutting fluid of obtained novel emulsion system, its combination property greatly improves, and has excellent stabilization Property, anti-corrosive properties and rust-preventing characteristic.
Another object of the present invention is to provide a kind of above-mentioned novel emulsion system based on polyisobutenyl succinic anhydride Cutting fluid preparation method.
It is still another object of the present invention to provide a kind of above-mentioned novel emulsion system based on polyisobutenyl succinic anhydride Cutting fluid application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride, the cutting fluid by it is following by weight The raw material of percentage is prepared：
The emulsifying agent is mixed by the polyisobutenyl succinic anhydride that molecular weight is 200,400 and 1000, three Between mass ratio be 2:1:1.
The base oil is naphthenic base oils, paraffin base oil, vegetable oil, modified vegetable oil, department of botany's oleate One or more of with poly alpha olefin；
The nonionic surfactant is sorbitan monooleate or AEO；The pH adjusting agent It is one or more of alkylamine, triethanolamine, MEA, diglycolamine and 2-amino-2-methyl-1-propanol；The profit Lubrication prescription is one or more of stearate, fatty acid ester and tricarboxymethyl propane oleate；The extreme pressure agent be chlorinated paraffin, One kind of sulfurized lard and sulfurized plant oil, the mixture with modified phosphate；The antirust agent is boric acid, certain herbaceous plants with big flowers two One or more of acid, trimer acid, dimeric dibasic acid, organic carboxylate and more polyacids；The corrosion inhibiter is phosphate and sodium metasilicate One or more of；The bactericide be 1,2- benzisothiazole-3-ketones, 2- butyl -1,2- benzisothiazole-3-ketones and One or more of IPBC.
The modified phosphate contained in the extreme pressure agent be from phosphorus acid monomer, alkylamine, triethanolamine, MEA, One or more of 2-amino-2-methyl-1-propanol and hydroxy acrylate, generated with phosphate diester, phosphate monoester reaction Mixture；Percentage by weight of the modified phosphate herein in cutting fluid raw material is 1-2%.
Modified phosphate in the extreme pressure agent also has the function that corrosion inhibiter in the formula.
The preparation method of the cutting fluid of the above-mentioned novel emulsion system based on polyisobutenyl succinic anhydride, including following behaviour Make step：Base oil, emulsifying agent and lubricant are added in kettle, stir 20-30 minutes at room temperature to well mixed；Then successively PH adjusting agent, nonionic surfactant, antirust agent, corrosion inhibiter and extreme pressure agent are added, stirs 30-50 minutes at room temperature to mixing Uniformly；Bactericide and water are eventually adding, stirring 20-30 minutes can obtain cutting fluid to transparent.
The cutting fluid of the above-mentioned novel emulsion system based on polyisobutenyl succinic anhydride is in non-ferrous metals processing field Application.
The present invention principle be：
The emulsion cutting fluid of traditional system, sulfonate systems alone or Oleic Acid System are substantially, these traditional emulsified bodies System, because the defects of system itself, it is particularly easy to grow bacterium, thus easily smelly, short life, and steep more, property in process Energy is poor and produces a series of processing problems.The industrial water in the north, water quality inferiority, 300-500ppm are calculated normally substantially, some ground Side is even as high as 800ppm, and the resistance to hard water of sulfonate and Oleic Acid System is particularly poor, is used in these places, product is easy Demulsification produces many oil soaps and failed.Currently invention addresses these it is original the problem of, pass through a kind of polyisobutylene succinic anhydride breast The compounding of agent, to optimize the emulsibility of the invention and rust-preventing characteristic, while reduce other emulsifying agents and lubricant and antirust agent Use.And used for this emulsifying agent of polyisobutylene succinic anhydride it is very difficult, if select molecular weight do not conform to It is suitable, it may appear that can not to be used as primary emulsion, and cause cutting fluid stability poor, so as to influence service life；If from Proportioning it is improper, then occur, otherwise emulsification is unstable, or foam very it is more it is very tiny cause to be not easy to defoam, so as to Machining accuracy is influenceed, or even can not be used for processing.Polyisobutylene succinic anhydride of the present invention be from molecular weight be 200, 400 and 1000 polyisobutylene succinic anhydride compounding forms, and low molecular polyisobutenyl succinic anhydride has good water solubility, The polyisobutenyl succinic anhydride of HMW has good lubricant effect, make it that the emulsification system is easily scattered after interworking, stable, And low bubble.The mixing polyisobutylene succinic anhydride has good emulsibility and rust-preventing characteristic, lubricity, can effectively improve cutting fluid Dispersibility and antirust ability, lubricating ability.The usage amount of the mixing polyisobutylene succinic anhydride is 5%~12%, is used as this Mixing polyisobutylene succinic anhydride used in invention can improve the antirust ability of cutting fluid, emulsifying capacity, lubricating ability, make Cutting fluid forms the minimum microemulsion of particle, improves resistance to hard water ability after being diluted with a large amount of water.
Used modified phosphate in addition, modified phosphate be preferentially from phosphate diester, phosphate monoester and phosphorus acid monomer, Alkylamine, triethanolamine, MEA, one or more of mixing of 2-amino-2-methyl-1-propanol, hydroxy acrylate Thing, using long-chain fatty alcohol or fatty alcohol ether, hydroxyl natural oil for example castor oil, rapeseed oil, sunflower oil, cottonseed oil, The synthetic phosphoric acid ester fatting agent such as fish oil and lanolin.Before phosphorylation reaction, to long-chain fatty alcohol or fatty alcohol ether, hydroxyl Natural oil carry out appropriate modification, such as ester exchange reaction, amidation process, sulfonating reaction, quaterisation, sulfuric acid Change reaction, halogenation and etherification reaction etc., reasonably introduce more active groups or the more active groups of exposure, then enter Row phosphorylation reaction, effectively optimum organization make the phosphate of synthesis have the fatliquoring function optimized.
By being used in combination for a variety of antirust agent, make the cutting liquid system of the present invention to non-ferrous metals such as various aluminium alloys Anticorrosion has a good protective effect.
The present invention has the advantages of following prominent and beneficial effect compared with prior art：
(1) emulsification system of emulsion cutting fluid of the invention is more stable, and the particle of formation is thinner, the infiltration to intermetallic composite coating It is more excellent with protecting, the finish of finished surface can be improved, especially suitable for the machining center of high speed and precision, especially in non-ferrous metal Had outstanding performance in terms of processing.
(2) emulsifying agent polyisobutylene succinic anhydride source used in the present invention is renewable raw materials, is largely put The dependence to petroleum sodium sulfonate has been taken off, and the cutting fluid life of product length formed, lubricating and antirust is good, and foam is low, meets the modern times Needs of the machining center to low froth pulp
(3) the hard water resistance superior performance of emulsion cutting fluid of the invention, it is poor to be especially suitable for use in coastal or northern water quality The area of (water quality that hardness is high or mineral matter is more), the problems such as greatly improving demulsification condensate oil of product etc..
(4) bacteriostasis property of resistance to bacterium of emulsification system of the invention is superior, in the case of being not added with or lacking adding of germicide, can suppress The production of bacterium, keep clean manufacturing.
(5) implementation of the invention, domestic market can be seized, changes the market structure, create one's own national brand, Development manufacturing to China is particularly advantageous.
(6) implementation of the invention had both improved the life-span of cutting fluid, and it is a series of unreasonable to solve foam, stimulation etc. again Problem so that aqueous cutting fluid is more environmentally friendly using safer, while performance is more excellent.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The polyisobutylene succinic anhydride mixture used in example 1 below -5 be by mass ratio be 2:1:1 molecular weight Polyisobutenyl succinic anhydride for 200,400 and 1000 mixes.
Modified phosphate used in following examples be by phosphorus acid monomer, alkylamine, triethanolamine, MEA, One or more of 2-amino-2-methyl-1-propanol and hydroxy acrylate, generated with phosphate diester, phosphate monoester reaction Mixture.
Following examples are to prepare cutting fluid according to following steps：Base oil, emulsifying agent and lubricant are added in kettle, 20-30 minutes are stirred at room temperature to well mixed；Then pH adjusting agent, nonionic surfactant, antirust agent, slow is sequentially added Agent and extreme pressure agent are lost, stirs 30-50 minutes at room temperature to well mixed；Bactericide and water are eventually adding, stirring 20-30 minutes are extremely It is transparent to can obtain cutting fluid.
Embodiment 1
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (naphthenic mineral oil) 45%, polyisobutylene succinic anhydride mixture 10%, nonionic surfactant (lose Water sorbitan oleate) 4%, pH adjusting agent (mixture of triethanolamine 5%, diglycolamine 2% and alkylamine 2%) 9%, prevent Rust agent (mixture of more polyacids and dimeric dibasic acid) 7%, lubricant (tricarboxymethyl propane oleate) 6%, extreme pressure agent (chlorinated paraffin 5% and the mixture of modified phosphate 1%) 6%, corrosion inhibiter (phosphate) 1%, bactericide (1,2- benzisothiazole -3- Ketone) 2% and excess water.
Embodiment 2
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (castor oil) 40%, polyisobutylene succinic anhydride mixture 12%, nonionic surfactant (poly alkyl alcohol Oxygen vinethene) 5%, pH adjusting agent (mixture of triethanolamine 1%, MEA 3% and alkylamine 2%) 6%, lubricant (stearate) 2%, antirust agent (mixture of dimeric dibasic acid and organic carboxylate) 10%, extreme pressure agent (sulfurized plant oil 2% and the mixture of modified phosphate 2%) 4%, bactericide (2- butyl-BIT) 2% and surplus Water.
Embodiment 3
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (miscella of sunflower oil and cottonseed oil) 50%, polyisobutylene succinic anhydride mixture 8%, nonionic table Face activating agent (AEO) 3%, pH adjusting agent (2-amino-2-methyl-1-propanol 4%, the and of triethanolamine 4% The mixture of MEA 3%) 11%, lubricant (tricarboxymethyl propane oleate) 3%, antirust agent (dimeric dibasic acid and organic carboxylic The mixture of hydrochlorate) 10%, extreme pressure agent (mixture of chlorinated paraffin 3% and modified phosphate 1%) 4%, sustained release agent (phosphoric acid Ester) 1%, bactericide (IPBC) 3% and excess water.
Embodiment 4
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (paraffin base oil and poly alpha olefin) 43%, polyisobutylene succinic anhydride mixture 12%, non-ionic surface Activating agent (sorbitan monooleate) 3%, pH adjusting agent (triethanolamine 4%, MEA 4% and 2- amino-2-methyls- The mixture of 1- propyl alcohol 2%) 10%, lubricant (stearate) 2%, antirust agent (dimeric dibasic acid and decanedioic acid) 8%, corrosion inhibiter (sodium metasilicate) 2%, extreme pressure agent (mixture of chlorinated paraffin 3% and modified phosphate 1%) 4%, bactericide (2- butyl -1, 2- benzisothiazole-3-ketones) 1% and excess water.
Embodiment 5
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (paraffin base oil) 30%, polyisobutylene succinic anhydride mixture 12%, nonionic surfactant (fat Fat alcohol APEO) 5%, pH adjusting agent (triethanolamine 4%, MEA 4% and 2-amino-2-methyl-1-propanol 2% Mixture) 10%, lubricant (fatty acid ester and tricarboxymethyl propane oleate) 8%, antirust agent (boric acid and dimeric dibasic acid) 9%, corrosion inhibiter (mixture of sodium metasilicate 1% and phosphate 2%) 3%, extreme pressure agent (sulfurized lard 1.5%, vulcanized vegetable oil The mixture of aliphatic acid 1.5% and modified phosphate 1%) 4%, bactericide (pyrrolotriazine derivatives) 3% and excess water.
Embodiment 6
A kind of cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride；Including following percentage by weight Raw material：Base oil (naphthenic base oils) 31%, the polyisobutylene succinic anhydride mixture 12% of 1000 molecular weight, nonionic table Face activating agent (mixture of AEO) 5%, pH adjusting agent (triethanolamine 4%, diglycolamine 4% and 2- ammonia The mixture of base -2- methyl isophthalic acids-propyl alcohol 2%) 10%, lubricant be (tricarboxymethyl propane oleate 6% and stearate 1% Mixture) 7%, antirust agent (mixture of propionic acid polymer 5% and dimeric dibasic acid 5%) 10%, the corrosion inhibiter (He of sodium metasilicate 1% The mixture of phosphate 1%) 2%, extreme pressure agent (mixture of sulfurized plant oil 2% and modified phosphate 2%) 4%, Bactericide (2- butyl -1,2- benzisothiazole-3-ketones) 2% and excess water.
Embodiment 7
Polyisobutylene succinic anhydride mixture (the quality of the molecular weight of base oil (naphthenic mineral oil) 42%, 200 and 400 Ratio 2:1) 8%, nonionic surfactant (sorbitan monooleate) 5%, pH adjusting agent (triethanolamine 5%, diethylene glycol (DEG) The mixture of amine 2% and alkylamine 2%) 9%, antirust agent (mixture of more polyacids and dimeric dibasic acid) 7%, lubricant (three hydroxyl first Base propane oleate) 6%, extreme pressure agent (mixture of chlorinated paraffin 5% and modified phosphate 1%) 6%, corrosion inhibiter (phosphate) 1%, bactericide (BIT) 2% and excess water.
Embodiment 8
Base oil (naphthenic mineral oil) 40%, the polyisobutylene succinic anhydride mixture of 200,400 and 1000 molecular weight (mass ratio 3:3:1) 8%, nonionic surfactant (sorbitan monooleate) 5%, pH adjusting agent (triethanolamine 5%th, the mixture of diglycolamine 2% and alkylamine 2%) 9%, antirust agent (mixture of more polyacids and dimeric dibasic acid) 7%, lubrication Agent (tricarboxymethyl propane oleate) 6%, extreme pressure agent (mixture of chlorinated paraffin 5% and modified phosphate 1%) 6%, inhibition Agent (phosphate) 1%, bactericide (BIT) 2% and excess water.
Stability, rust-preventing characteristic, hard water resistance property, the detection of defoaming etc., knot are done to cutting fluid obtained by above-described embodiment Fruit is as shown in Table 1 and Table 2.
Inspection in the case that conventional case refers to do primary emulsion with petroleum sodium sulfonate in embodiment 1, and other components are constant Survey data.
The performance detection of the conventional case of table 1 and embodiment 1-4 gained cutting fluids
The performance detection of cutting fluid obtained by the embodiment 5-8 of table 2
Summarize：By the contrast of above example and conventional case as can be seen that using novel emulsion system institute of the invention Obtained cutting fluid, there is finer and smoother outward appearance, more stable performance, more excellent combination property, hard water resistance performance raising, more have The foam volume of improvement system is imitated, is finally reached a superior performance, the cutting that can be used in the system of high-speed precise machine tool processing Liquid.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (5)

  1. A kind of 1. cutting fluid of the novel emulsion system based on polyisobutenyl succinic anhydride, it is characterised in that：The cutting fluid by Following raw materials are prepared：
    The emulsifying agent is mixed by the polyisobutenyl succinic anhydride that molecular weight is 200,400 and 1000, between three Mass ratio be 2:1:1.
  2. 2. a kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride according to claim 1, its It is characterised by：The base oil is naphthenic base oils, paraffin base oil, vegetable oil, modified vegetable oil, department of botany's oleate One or more of with poly alpha olefin；
    The nonionic surfactant is sorbitan monooleate or AEO；The pH adjusting agent is alkane One or more of base amine, triethanolamine, MEA, diglycolamine and 2-amino-2-methyl-1-propanol；The lubricant It is one or more of stearate, fatty acid ester and tricarboxymethyl propane oleate；The extreme pressure agent is chlorinated paraffin, vulcanization One kind of lard and sulfurized plant oil, the mixture with modified phosphate；The antirust agent is boric acid, SA, three One or more of polyacids, dimeric dibasic acid, organic carboxylate and more polyacids；The corrosion inhibiter is one in phosphate and sodium metasilicate More than kind；The bactericide is that 1,2- benzisothiazole-3-ketones, 2- butyl -1,2- benzisothiazole-3-ketones and 3- are iodo- One or more of 2-propynyl butyl carbamate.
  3. 3. a kind of cutting fluid of novel emulsion system based on polyisobutenyl succinic anhydride according to claim 1, its It is characterised by：The modified phosphate contained in the extreme pressure agent is phosphorus acid monomer, alkylamine, triethanolamine, MEA, 2- ammonia Base -2- methyl isophthalic acids-one or more of propyl alcohol and hydroxy acrylate, with phosphate diester, the mixing of phosphate monoester reaction generation Thing；Percentage by weight of the modified phosphate herein in cutting fluid raw material is 1%-2%.
  4. 4. a kind of novel emulsion system based on polyisobutenyl succinic anhydride according to claim any one of 1-3 is cut Cut the preparation method of liquid, it is characterised in that including following operating procedure：Base oil, emulsifying agent and lubricant are added in kettle, room Temperature lower stirring 20-30 minutes are to well mixed；Then pH adjusting agent, nonionic surfactant, antirust agent, inhibition are sequentially added Agent and extreme pressure agent, 30-50 minutes are stirred at room temperature to well mixed；It is eventually adding bactericide and water, stirring 20-30 minutes are to saturating It is bright to can obtain cutting fluid.
  5. 5. a kind of novel emulsion system based on polyisobutenyl succinic anhydride according to claim any one of 1-3 is cut Cut application of the liquid in non-ferrous metals processing field.
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CN112500914A (en) * 2020-10-30 2021-03-16 湖北嘉士力化学科技有限公司 Metal cutting fluid based on maleated rosin ethanolamine and preparation method thereof
WO2023050579A1 (en) * 2021-09-30 2023-04-06 安美科技股份有限公司 Aluminum alloy cutting fluid and preparation method therefor
CN117186972A (en) * 2023-08-08 2023-12-08 河南减碳科技有限公司 Solid-liquid double-form metal cutting fluid and preparation method thereof

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CN110591668A (en) * 2019-09-28 2019-12-20 中国石油集团川庆钻探工程有限公司钻井液技术服务公司 Extreme pressure lubricant and preparation method thereof
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