CN107418673B

CN107418673B - Cutting fluid of emulsifying system based on polyisobutenyl succinic anhydride and preparation method and application thereof

Info

Publication number: CN107418673B
Application number: CN201710245621.XA
Authority: CN
Inventors: 侯海燕; 戴恩期; 向晖
Original assignee: Guangzhou Jisheng Lubrication Technology Co Ltd; Guangzhou Mechanical Engineering Research Institute Co Ltd
Current assignee: Guangzhou Guoji Lubrication Technology Co., Ltd; Guangzhou Machinery Research Institute Co., Ltd
Priority date: 2017-04-14
Filing date: 2017-04-14
Publication date: 2020-01-14
Anticipated expiration: 2037-04-14
Also published as: CN107418673A

Abstract

The invention belongs to the field of metal cutting fluid, and discloses a cutting fluid of a novel emulsification system based on polyisobutenyl succinic anhydride, and a preparation method and application thereof. The lubricant comprises base oil, a polyisobutylene succinic anhydride mixture (prepared by mixing polyisobutylene succinic anhydrides with molecular weights of 200, 400 and 1000 in a mass ratio of 2:1: 1), a nonionic surfactant, a PH regulator, a lubricant, an extreme pressure agent, an antirust agent, a corrosion inhibitor and a bactericide. According to the invention, the polybutylene succinate anhydride mixture is used as the main emulsifier of the cutting fluid for the first time, so that the emulsifying system is very stable, smelly bacteria are not easy to grow, the service life of the product is very long, and the working fluid can be used for more than half a year; meanwhile, the antirust oil has excellent performances of rust prevention, lubrication, low foam and the like. The cutting fluid has excellent performance, can be used in a high-speed precise machining center, particularly has outstanding performance in the aspect of nonferrous metal machining, and is mainly used in the aspects of tapping, deep hole drilling and the like of electronic products.

Description

Cutting fluid of emulsifying system based on polyisobutenyl succinic anhydride and preparation method and application thereof

Technical Field

The invention belongs to the field of metal cutting fluid, and particularly relates to cutting fluid of a novel emulsification system based on polyisobutenyl succinic anhydride, and a preparation method and application thereof.

Background

Water-based metal cutting fluids were introduced in the fortieth of the twentieth century and developed rapidly due to their low cost and excellent cooling characteristics. Water-based metal cutting fluids have been developed to date to dominate certain metal working applications. At present, petroleum sulfonate is generally used as an emulsifying system in a water-based metal working fluid system, and the system has the defects of environmental pollution, easy odor generation, low production efficiency, great environmental pollution and the like. At the same time, a wide range of future changes in global environment, health and safety expectations, stricter regulations, etc. have made the metal working fluid industry face many challenges. The complexity of the application requirements of the metalworking fluid industry, the changing chemical supply markets, and the increasingly stringent regulatory expectations have made the market environment more and more severe. Future pressure on the implementation of chemical registration, evaluation, authorization and restrictions will force many lubricating oil manufacturers to change, revise and renew lubricating formulations. Revolutionary through structured, close-fitting and innovative approaches.

At present, the petroleum is gradually exhausted and the environmental protection requirement is more and more strict, the development of water-based metal working fluid based on environment-friendly renewable raw materials is not slow enough. As early as 2012, more and more experts in the industry started looking for new raw materials, a new emulsifying system of succinic anhydride appeared in the foreign metal working fluid market, and in 2015, a lot of research and hot tide using succinic anhydride was raised abroad, and various modified succinic anhydride emulsifiers with various molecular weights were introduced by large-scale global additive companies such as basf, dow chemical, lubon and the like. In 2016, numerous powerful and thick imported products of metal cutting fluids such as Quke, Fulanke, Jiaguduo and the like have launched market occupation of related products. The metal cutting fluid in China is mainly based on the traditional sodium sulfonate system, and the domestic cutting fluid market is as follows: the inventor researches and discovers that the succinic anhydride system has better performance and service life than the traditional petroleum sulfonate system by exchanging with a plurality of experts at home and abroad.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a cutting fluid of a novel emulsification system based on polyisobutenyl succinic anhydride; the cutting fluid replaces petroleum sodium sulfonate and oleic acid as main emulsifiers, is matched with raw materials of a nonionic surfactant, an antirust agent, a corrosion inhibitor and a bactericide, and then the weight composition of the raw materials is reasonably set, so that the emulsified cutting fluid of the novel emulsified system is obtained, the comprehensive performance of the emulsified cutting fluid is greatly improved, and the emulsified cutting fluid has excellent stability, corrosion resistance and rust resistance.

Another object of the present invention is to provide a method for preparing the cutting fluid based on the novel emulsification system of polyisobutenyl succinic anhydride.

Still another object of the present invention is to provide a cutting fluid using the above novel emulsification system based on polyisobutenyl succinic anhydride.

The purpose of the invention is realized by the following technical scheme:

the cutting fluid is prepared from the following raw materials in percentage by weight:

the emulsifier is formed by mixing polyisobutenyl succinic anhydride with the molecular weight of 200, 400 and 1000, and the mass ratio of the polyisobutenyl succinic anhydride to the polyisobutenyl succinic anhydride is 2:1: 1.

The base oil is more than one of naphthenic base oil, paraffin base oil, vegetable oil, modified vegetable oil, vegetable series oleate and poly alpha-olefin;

the nonionic surfactant is sorbitan oleate or fatty alcohol-polyoxyethylene ether; the pH regulator is more than one of alkylamine, triethanolamine, monoethanolamine, diglycolamine and 2-amino-2-methyl-1-propanol; the lubricant is more than one of stearate, fatty acid ester and trimethylolpropane oleate; the extreme pressure agent is a mixture of one of chlorinated paraffin, sulfurized lard and sulfurized vegetable oil fatty acid and modified phosphate; the antirust agent is more than one of boric acid, sebacic acid, trimer acid, dimer acid, organic carboxylate and polyacid; the corrosion inhibitor is more than one of phosphate and sodium metasilicate; the bactericide is more than one of 1, 2-benzisothiazolin-3-one, 2-butyl-1, 2-benzisothiazolin-3-one and 3-iodine-2-propynyl butyl carbamate.

The modified phosphate ester contained in the extreme pressure agent is a mixture generated by reacting more than one of phosphoric acid monomer, alkylamine, triethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol and hydroxyl acrylic ester with phosphoric acid diester and phosphoric acid monoester; the weight percentage of the modified phosphate ester in the cutting fluid raw material is 1-2%.

The modified phosphate ester in the extreme pressure agent also has the function of a corrosion inhibitor in the formula.

The preparation method of the cutting fluid based on the novel polyisobutenyl succinic anhydride emulsifying system comprises the following operation steps: adding the base oil, the emulsifier and the lubricant into a kettle, and stirring for 20-30 minutes at room temperature until the base oil, the emulsifier and the lubricant are uniformly mixed; then sequentially adding a pH regulator, a nonionic surfactant, an antirust agent, a corrosion inhibitor and an extreme pressure agent, and stirring for 30-50 minutes at room temperature until the components are uniformly mixed; and finally, adding the bactericide and water, and stirring for 20-30 minutes until the mixture is transparent to obtain the cutting fluid.

The cutting fluid based on the novel polyisobutenyl succinic anhydride emulsifying system is applied to the field of nonferrous metal processing.

The principle of the invention is as follows:

the emulsion cutting fluid of the traditional system is basically a sulfonate system or an oleic acid system, and the traditional emulsion systems are easy to generate bacteria due to the defects of the system, so that the traditional emulsion systems are easy to smell, short in service life, large in amount of bubbles in the processing process and poor in performance, and a series of processing problems are generated. The water quality of the production water in the north is poor, the water quality is basically normal when 500ppm plus 300 ppm is used, and even reaches 800ppm in some places, the hard water resistance of a sulfonate and oleic acid system is particularly poor, and when the system is used in the places, the product is easy to demulsify to generate a plurality of oil soaps to be ineffective. The present invention addresses these original problems by optimizing the emulsifiability and rust inhibition of the invention through the compounding of a polyisobutylene succinic anhydride emulsifier, while reducing the use of other emulsifiers and lubricants and rust inhibitors. The polyisobutylene succinic anhydride emulsifier is very difficult to use, and if the selected molecular weight is not proper, the polyisobutylene succinic anhydride emulsifier cannot be used as a main emulsifier, and the stability of the cutting fluid is poor, so that the service life is influenced; if the selected proportion is not appropriate, the phenomenon that the emulsification is unstable or the foam is too much and fine to cause difficult defoaming can occur, so that the processing precision is influenced, and the processing cannot be performed even. The polyisobutylene succinic anhydride related by the invention is prepared by compounding polyisobutylene succinic anhydrides with molecular weights of 200, 400 and 1000, the low-molecular polyisobutylene succinic anhydride has good water solubility, the high-molecular polyisobutylene succinic anhydride has good lubricating effect, and the polyisobutylene succinic anhydride is easy to disperse, stable and low-foaming after being matched with each other. The mixed polyisobutene succinic anhydride has good emulsibility, rust resistance and lubricity, and can effectively improve the dispersing ability, rust resistance and lubricating ability of the cutting fluid. The usage amount of the mixed polyisobutene succinic anhydride is 5-12%, and the mixed polyisobutene succinic anhydride used in the invention can improve the antirust capacity, the emulsifying capacity and the lubricating capacity of the cutting fluid, so that the cutting fluid forms a microemulsion with tiny particles after being diluted by a large amount of water, and the hard water resistance is improved.

In addition, modified phosphate is used, which is a mixture of one or more of phosphate diester, phosphate monoester and phosphate monomer, alkylamine, triethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol and hydroxy acrylate, and synthetic phosphate fatting agent comprising long-chain fatty alcohol or fatty alcohol ether, and natural oil containing hydroxyl such as castor oil, rapeseed oil, sunflower seed oil, cottonseed oil, fish oil and lanolin is used. Before phosphorylation, long-chain fatty alcohol or fatty alcohol ether and natural oil containing hydroxyl are modified properly, such as ester exchange reaction, amidation reaction, sulfonation reaction, quaternization reaction, sulfation reaction, halogenation reaction, etherification reaction and the like, more active groups are introduced reasonably or exposed, then phosphorylation reaction is carried out, and the combination is optimized effectively, so that the synthesized phosphate ester has the optimized fat-adding performance.

Through the combined use of a plurality of rust inhibitors, the cutting fluid system has a good protection effect on the corrosion prevention of nonferrous metals such as various aluminum alloys and the like.

Compared with the prior art, the invention has the following outstanding advantages and beneficial effects:

(1) the emulsified cutting fluid has more stable emulsified system, finer formed particles, better infiltration and protection for metal processing, and capability of improving the smoothness of a processed surface, is particularly suitable for high-speed precise processing centers, and particularly has outstanding performance in the aspect of nonferrous metal processing.

(2) The source of the emulsifier polyisobutylene succinic anhydride used in the invention is a renewable raw material, the dependence on sodium petroleum sulfonate is avoided to a great extent, the formed cutting fluid product has long service life, good lubrication and rust prevention and low foam, and the requirement of modern processing center on low-foam products is met

(3) The emulsified cutting fluid has excellent hard water resistance, is particularly suitable for being used in coastal or northern areas with poor water quality (water quality with high hardness or more minerals), and greatly improves the problems of demulsification and oil separation of products and the like.

(4) The emulsifying system of the invention has excellent antibacterial and bacteriostatic properties, and can inhibit the production of bacteria and keep clean production under the condition of adding no or little bactericide.

(5) The implementation of the invention can seize the domestic market, change the market pattern, create the national brand, and is particularly beneficial to the development of the Chinese manufacturing industry.

(6) The implementation of the invention not only improves the service life of the cutting fluid, but also solves a series of difficult winding problems of foam, stimulation and the like, so that the aqueous cutting fluid is safer to use, more environment-friendly and better in performance.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

The polyisobutylene succinic anhydride mixtures used in examples 1-5 below were mixed from polyisobutylene succinic anhydrides having molecular weights of 200, 400 and 1000 in a 2:1:1 mass ratio.

The modified phosphoric acid ester used in the following examples was a mixture obtained by reacting at least one of phosphoric acid monomers, alkylamines, triethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol, and hydroxyacrylate with a phosphoric acid diester and a phosphoric acid monoester.

The following examples were all prepared as follows: adding the base oil, the emulsifier and the lubricant into a kettle, and stirring for 20-30 minutes at room temperature until the base oil, the emulsifier and the lubricant are uniformly mixed; then sequentially adding a pH regulator, a nonionic surfactant, an antirust agent, a corrosion inhibitor and an extreme pressure agent, and stirring for 30-50 minutes at room temperature until the components are uniformly mixed; and finally, adding the bactericide and water, and stirring for 20-30 minutes until the mixture is transparent to obtain the cutting fluid.

Example 1

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 45% of base oil (naphthenic mineral oil), 10% of polyisobutylene succinic anhydride mixture, 4% of nonionic surfactant (sorbitan oleate), 9% of pH regulator (mixture of 5% of triethanolamine, 2% of diglycolamine and 2% of alkylamine), 7% of antirust agent (mixture of polyacid and dimer acid), 6% of lubricant (trimethylolpropane oleate), 6% of extreme pressure agent (mixture of 5% of chlorinated paraffin and 1% of modified phosphate ester), 1% of corrosion inhibitor (phosphate ester), 2% of bactericide (1, 2-benzisothiazolin-3-one) and the balance of water.

Example 2

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 40% of base oil (castor oil), 12% of polyisobutylene succinic anhydride mixture, 5% of nonionic surfactant (fatty alcohol polyoxyethylene ether), 6% of pH regulator (mixture of triethanolamine 1%, monoethanolamine 3% and alkylamine 2%), 2% of lubricant (stearate), 10% of antirust agent (mixture of dimer acid and organic carboxylate), 4% of extreme pressure agent (mixture of 2% of sulfurized vegetable oil fatty acid and 2% of modified phosphate ester), 2% of bactericide (2-butyl-1, 2-benzisothiazolin-3-one) and the balance of water.

Example 3

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 50% of base oil (mixed oil of sunflower seed oil and cottonseed oil), 8% of polyisobutylene succinic anhydride mixture, 3% of nonionic surfactant (fatty alcohol polyoxyethylene ether), 11% of pH regulator (4% of 2-amino-2-methyl-1-propanol, 4% of triethanolamine and 3% of monoethanolamine), 3% of lubricant (trimethylolpropane oleate), 10% of antirust agent (mixture of dimer acid and organic carboxylate), 4% of extreme pressure agent (mixture of 3% of chlorinated paraffin and 1% of modified phosphate ester), 1% of slow release agent (phosphate ester), 3% of bactericide (3-iodine-2-propynyl butyl carbamate) and the balance of water.

Example 4

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 43% of base oil (paraffin-based base oil and poly-alpha-olefin), 12% of polyisobutylene succinic anhydride mixture, 3% of nonionic surfactant (sorbitan oleate), 10% of pH regulator (a mixture of 4% of triethanolamine, 4% of monoethanolamine and 2% of 2-amino-2-methyl-1-propanol), 2% of lubricant (stearate), 8% of antirust agent (dimer acid and sebacic acid), 2% of corrosion inhibitor (sodium metasilicate), 4% of extreme pressure agent (a mixture of 3% of chlorinated paraffin and 1% of modified phosphate ester), 1% of bactericide (2-butyl-1, 2-benzisothiazolin-3-one) and the balance of water.

Example 5

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 30% of base oil (paraffin-based base oil), 12% of polyisobutylene succinic anhydride mixture, 5% of nonionic surfactant (fatty alcohol polyoxyethylene ether), 10% of pH regulator (a mixture of 4% of triethanolamine, 4% of monoethanolamine and 2% of 2-amino-2-methyl-1-propanol), 8% of lubricant (fatty acid ester and trimethylolpropane oleate), 9% of antirust agent (boric acid and dimer acid), 3% of corrosion inhibitor (a mixture of 1% of sodium metasilicate and 2% of phosphate ester), 4% of extreme pressure agent (a mixture of 1.5% of sulfurized lard, 1.5% of sulfurized vegetable oil fatty acid and 1% of modified phosphate ester), 3% of bactericide (triazine derivative) and the balance of water.

Example 6

A cutting fluid based on a novel emulsifying system of polyisobutenyl succinic anhydride; comprises the following raw materials in percentage by weight: 31% of base oil (cycloalkyl base oil), 12% of a 1000-molecular-weight polyisobutylene succinic anhydride mixture, 5% of a nonionic surfactant (a mixture of fatty alcohol polyoxyethylene ethers), 10% of a pH regulator (a mixture of 4% of triethanolamine, 4% of diglycolamine and 2% of 2-amino-2-methyl-1-propanol), 7% of a lubricant (a mixture of 6% of trimethylolpropane oleate and 1% of stearate), 10% of an antirust agent (a mixture of 5% of propionic acid polymer and 5% of dimer acid), 2% of a corrosion inhibitor (a mixture of 1% of sodium metasilicate and 1% of phosphate ester), 4% of an extreme pressure agent (a mixture of 2% of sulfurized vegetable oil fatty acid and 2% of modified phosphate ester), 2% of a bactericide (2-butyl-1, 2-benzisothiazolin-3-one), and the balance of water.

Example 7

42% of base oil (naphthenic mineral oil), 8% of a mixture of polyisobutylene succinic anhydrides with molecular weights of 200 and 400 (mass ratio of 2:1), 5% of nonionic surfactant (sorbitan oleate), 9% of pH regulator (a mixture of 5% of triethanolamine, 2% of diglycolamine and 2% of alkylamine), 7% of antirust agent (a mixture of polyacid and dimer acid), 6% of lubricant (trimethylolpropane oleate), 6% of extreme pressure agent (a mixture of 5% of chlorinated paraffin and 1% of modified phosphate ester), 1% of corrosion inhibitor (phosphate ester), 2% of bactericide (1, 2-benzisothiazolin-3-one) and the balance of water.

Example 8

40% of base oil (naphthenic mineral oil), 8% of polyisobutylene succinic anhydride mixture with molecular weights of 200, 400 and 1000 (mass ratio of 3:3:1), 5% of nonionic surfactant (sorbitan oleate), 9% of pH regulator (mixture of triethanolamine 5%, diglycolamine 2% and alkylamine 2%), 7% of antirust agent (mixture of polyacid and dimer acid), 6% of lubricant (trimethylolpropane oleate), 6% of extreme pressure agent (mixture of chlorinated paraffin 5% and modified phosphate ester 1%), 1% of corrosion inhibitor (phosphate ester), 2% of bactericide (1, 2-benzisothiazolin-3-one) and the balance of water.

The results of the tests on the stability, rust prevention, hard water resistance, defoaming property and the like of the cutting fluids obtained in the above examples are shown in tables 1 and 2.

The conventional example refers to the detection data of example 1 using sodium petroleum sulfonate as the main emulsifier and the other components are unchanged.

TABLE 1 examination of the Properties of the cutting fluids obtained in the conventional examples and examples 1 to 4

TABLE 2 examination of the Properties of the cutting fluids obtained in examples 5 to 8

To summarize: compared with the traditional example, the cutting fluid prepared by the novel emulsifying system has the advantages of more delicate appearance, more stable performance, more excellent comprehensive performance, improved hard water resistance, more effective improvement of the foam amount of the system, and finally achieves the cutting fluid which has excellent performance and can be used in a system for high-speed precision machine tool machining.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims

1. A cutting fluid based on a polyisobutenyl succinic anhydride emulsifying system is characterized in that: the cutting fluid is prepared from the following raw materials in percentage by weight:

the emulsifier is formed by mixing polyisobutenyl succinic anhydride with the molecular weight of 200, 400 and 1000, and the mass ratio of the polyisobutenyl succinic anhydride to the polyisobutenyl succinic anhydride is 2:1: 1;

the lubricant is a fatty acid ester.

2. The cutting fluid of an emulsifying system based on polyisobutenyl succinic anhydride according to claim 1, characterized in that: the base oil is more than one of naphthenic base oil, paraffin base oil, vegetable oil, modified vegetable oil, vegetable series oleate and poly alpha-olefin;

the nonionic surfactant is sorbitan oleate or fatty alcohol-polyoxyethylene ether; the pH regulator is more than one of alkylamine, triethanolamine, monoethanolamine, diglycolamine and 2-amino-2-methyl-1-propanol; the lubricant is more than one of stearate and trimethylolpropane oleate; the extreme pressure agent is a mixture of one of chlorinated paraffin, sulfurized lard and sulfurized vegetable oil fatty acid and modified phosphate; the antirust agent is more than one of boric acid, sebacic acid, organic carboxylate and polyacid; the corrosion inhibitor is more than one of phosphate and sodium metasilicate; the bactericide is more than one of 1, 2-benzisothiazolin-3-one, 2-butyl-1, 2-benzisothiazolin-3-one and 3-iodine-2-propynyl butyl carbamate.

3. The cutting fluid of an emulsifying system based on polyisobutenyl succinic anhydride according to claim 1, characterized in that: the modified phosphate ester contained in the extreme pressure agent is a mixture generated by the reaction of more than one of phosphoric acid monomer, alkylamine, triethanolamine, monoethanolamine, 2-amino-2-methyl-1-propanol and hydroxyl acrylic ester with phosphoric acid diester and phosphoric acid monoester; the weight percentage of the modified phosphate ester in the cutting fluid raw material is 1-2%.

4. Method for preparing a cutting fluid based on an emulsifying system of polyisobutenyl succinic anhydride according to any one of claims 1 to 3, characterized in that it comprises the following operating steps: adding the base oil, the emulsifier and the lubricant into a kettle, and stirring for 20-30 minutes at room temperature until the base oil, the emulsifier and the lubricant are uniformly mixed; then sequentially adding a pH regulator, a nonionic surfactant, an antirust agent, a corrosion inhibitor and an extreme pressure agent, and stirring for 30-50 minutes at room temperature until the components are uniformly mixed; and finally, adding the bactericide and water, and stirring for 20-30 minutes until the mixture is transparent to obtain the cutting fluid.

5. Use of a cutting fluid based on an emulsifying system of polyisobutenyl succinic anhydride according to any one of claims 1 to 3 in the field of nonferrous metal processing.