KR101607454B1 - Soluble cutting oils comprising core-crosslinked amphiphilic polymer nanoparticles prepared by using nonionic amphiphilic reactive precursors and their preparation method - Google Patents

Abstract

(상기 화학식 1에서,
상기 A는 폴리프로필렌 트리올 또는 글리세롤로서, 상기 B의 이소시아네이트기와 반응하여 우레탄 결합이 형성되고;
상기 B는 디이소시아네이트 화합물로서, 하나의 이소시아이트기는 상기 A의 히드록시기와 반응하여 우레탄 결합이 형성되고, 다른 하나는 상기 C의 히드록시기와 반응하여 우레탄 결합이 형성되거나, 상기 D의 히드록시기와 반응하여 우레탄 결합이 형성되고;
상기 C는 히드록시를 가지는 (메타)아크릴레이트로서, 히드록시기는 상기 B의 이소시아네이트기와 반응하여 우레탄 결합이 형성되고;
상기 D는 폴리에틸렌 글리콜로서, 히드록시기는 상기 B의 이소시아네이트기와 반응하여 우레탄 결합이 형성됨.)The present invention provides a water-soluble cutting oil comprising a polymer nanoparticle prepared by core cross-linking a nonionic amphipathic reactive precursor represented by the following formula (1) by a radical polymerization reaction.
[Chemical Formula 1]

(In the formula 1,
Wherein A is a polypropylene triol or glycerol, which reacts with the isocyanate group of B to form a urethane bond;
Wherein B is a diisocyanate compound, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other is to react with the hydroxyl group of C to form a urethane bond or to react with the hydroxyl group of D To form a urethane bond;
Wherein C is a (meth) acrylate having a hydroxy, the hydroxy group reacts with the isocyanate group of the B to form a urethane bond;
D is polyethylene glycol, and the hydroxyl group reacts with the isocyanate group of B to form a urethane bond.)

Description

[0001] The present invention relates to a water-soluble cutting oil comprising core-crosslinked amphiphilic polymer nanoparticles using a nonionic amphipathic reactive precursor,

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to cutting oils that are used in metal processing, and more particularly, to cutting oils used in metal working, and more particularly to a cutting oil additive for improving cutting performance, .

A cutting oil (or cutting oil) is a lubricating oil used to cool a cutting tool to lubricate a cutting tool to increase the service life of the tool, to improve the characteristics of the machined surface, and to clean the machined surface when machining a metal material. It also cleans the residue such as scraps and fine powder.

The ingredients of cutting oil are divided into base oil and additive. The base oil is mainly composed of C ₁₅ -C ₃₅ saturated hydrocarbons and is divided into paraffinic, naphthenic and aromatic based on the arrangement and bonding state of the carbon atoms. The paraffinic base oils are arranged in a chain of carbon atoms, saturated with carbon atoms by hydrogen atoms, have a high viscosity index and pour point, are thermally and chemically stable, and are excellent in oxidation stability. The naphthenic base oil has an excellent low temperature fluidity with the carbon atoms being arranged in a ring shape by the hydrogen atoms and having a carbon atom saturation. It has a boiling point higher than that of the paraffinic base oil of the same carbon number, a specific gravity and a medium viscosity index. The aromatic base oil is similar in structure to the naphthenic base oil, but is unsaturated with benzene rings and condensed rings and has excellent shear stability and thermal stability. The viscosity index and pour point depend on the length of the chain.

Cutting oil was initially used mainly as a base oil, but various additives are added to the base oil in order to improve the physical properties such as emulsifiers, anti-welding agents, oil agents, antifoaming agents, antioxidants, corrosion inhibitors, extreme pressure additives and preservatives.

The cutting oil is classified into insoluble cutting oils and soluble cutting oils depending on whether they are mixed with water or not. Non-water-soluble cutting oil is used mainly in the past because of its excellent cutting ability and corrosion resistance. However, The use of environmentally friendly water-soluble cutting oil is increasing.

Water has a large specific heat and has many advantages in terms of thermal conductivity and environment. However, in the case of water-soluble cutting oil, the metalworking ability is lower than that of the non-water-soluble tanning agent. Various additives (fatty acids, esters, amines, surfactants, ethylene oxide-propylene oxide copolymers) are used to increase lubricity.

In the water-soluble cutting oil, surfactant, which is a lubricant additive, is adsorbed on the metal surface to form a lubricating layer, thereby exhibiting lubrication performance. However, when shear stress acts on the metal, the adsorption ability of the surfactant or amphiphilic polymer adsorbed on the metal surface is deteriorated, resulting in the destruction of the structure, resulting in a reduction in the processing capacity. In recent years, an ethylene oxide-propylene oxide block copolymer (EO-PO block copolymer), which is an amphipathic polymer instead of a surfactant, has been used mainly since it has the same interfacial performance, but it is proprietary to some companies, There is a problem that it is expensive in terms of price. Therefore, it is required to develop a new cutting oil additive which is simple in manufacturing process and cost-effective while maintaining the lubricating property.

The present invention provides a new type of lubricant additive capable of exhibiting superior lubrication performance over conventional ethylene oxide-propylene oxide block copolymers or surfactants, while providing a chemically and physically robust structure that does not cause coagulation or precipitation during metal working The purpose of this study was to develop an additive having superior performance to conventional water-soluble cutting oil by preparing core crosslinked amphipathic polymer nanoparticles and using it as an additive.

In order to achieve the above object, the present invention provides a water-soluble cutting oil comprising polymer nanoparticles prepared by core cross-linking a nonionic amphipathic reactive precursor represented by the following formula (1) by radical polymerization.

[Chemical Formula 1]

(In the formula 1,

Wherein A is a polypropylene triol or glycerol, which reacts with the isocyanate group of B to form a urethane bond;

Wherein B is a diisocyanate compound, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other is to react with the hydroxyl group of C to form a urethane bond or to react with the hydroxyl group of D To form a urethane bond;

Wherein C is acrylate or methacrylate having hydroxy, the hydroxy group reacts with the isocyanate group of B to form a urethane bond;

D is polyethylene glycol, and the hydroxyl group reacts with the isocyanate group of B to form a urethane bond.)

The present invention also relates to a water-soluble (water-soluble) polymer comprising a nonionic amphiphilic reactive precursor represented by the structure of Formula 1 and a polymeric nanoparticle obtained by radical crosslinking of a methyl (meth) acrylate or ethyl Provide cutting oil.

On the other hand, in order to make the core of the amphiphilic polymer nanoparticles more rigid, the present invention provides a method for preparing core crosslinked amphiphilic polymer nanoparticles by polymerizing the nonionic amphiphilic reactive precursor represented by the structure of the above formula (1) A water-soluble cutting oil comprising a core-crosslinked amphiphilic polymer nanoparticle in which an acrylic polymer is formed in a core by adding an acrylate-based monomer together with an initiator to the nanoparticle solution and further polymerizing the monomer.

The nonionic amphiphilic reactive precursor according to the present invention is dispersed in water as in conventional amphiphilic block copolymers to form nanoparticles such as micelles and can easily be converted into amphiphilic polymer nanoparticles in which the core moiety is crosslinked have.

The core crosslinked amphiphilic polymer nanoparticles prepared according to the present invention are prepared by radical polymerization of nonionic amphipathic reactive precursors, and general surfactant micelles are not permanent structures and easily destroyed by external conditions such as temperature and pressure In the case of the core crosslinked amphiphilic polymer nanoparticles of the present invention, since the associative structure such as micelle is chemically permanently fixed, the structure is not destroyed by external conditions and can be effectively used as an additive exhibiting excellent lubrication performance .

Figure 1 is a diagram of a nonionic amphiphilic reactive precursor according to the present invention.
Figure 2 is a photograph of a core cross-linked polymeric nanoparticle solution produced by the radical polymerization of a non-ionic amphiphilic reactive precursor according to an embodiment of the present invention.

The present invention provides a coolant additive having an excellent lubricating property.

The cutting oil additive of the present invention is core crosslinked amphiphilic polymer nanoparticles, wherein the nanoparticles are prepared by radical polymerization of a nonionic amphipathic reactive precursor having both a hydrophobic segment and a hydrophilic segment as shown in the following formula (1).

The nonionic amphipathic reactive precursor according to the present invention has a structure in which four kinds of substances A, B, C and D are chemically bonded as shown in the following formula (1), and a hydrophobic segment (A portion) and a hydrophilic segment (C portion) or methacrylate (C portion) which is present at the same time.

[Chemical Formula 1]

FIG. 1 is a diagram showing a bonding structure between the materials of Formula 1. FIG.

Referring to FIG. 1,

A is a substance having a hydrophobic segment, which is a polypropylene triol or glycerol, and each of the hydroxyl groups reacts with an isocyanate group to form a urethane bond. The average molecular weight of the polypropylene triols is preferably 260 to 2,000, more preferably 1,000.

B is a diisocyanate material that acts as a mediator between A and C, A and D. One isocyanate group forms a urethane bond with the hydroxyl group of the above A, and another isocyanate group forms a urethane bond with the above hydroxyl group of the above C or D. The diisocyanate may be any material used for urethane synthesis such as toluene diisocyanate (TDI), isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolylidine diisocyanate have.

Wherein C is an acrylate or methacrylate having a hydroxy group, and the hydroxy group forms a urethane bond with the isocyanate group of the B. In the production of the polymer nanoparticles of the present invention, the double bond of acrylate or methacrylate is polymerized by a known polymerization initiator such as potassium persulfate, azobisbutyronitrile, etc., so that the core of the nanoparticles is crosslinked.

D is a hydrophilic segment for water dispersibility, polyethylene glycol is used, and a hydroxy group forms a urethane bond with the isocyanate group of the above B. The average molecular weight of the polyethylene glycol is preferably 600 to 15,000.

Representative materials of A, B, C, and D applicable to the present invention are shown in Table 1 below.

matter constitutional formula Chemical name


A

Glycerol

m = 1 to 50, n = 0 to 50, p = 0 to 50 Polypropylene triol















B

,

2,4-toluene diisocyanate,

2-6-toluene diisocyanate

Isophorone diisocyanate

Methylene diisocyanate

4,4'-methylene diphenyl diisocyanate

Hexamethylene diisocyanate

Xylene diisocyanate

Tolidine diisocyanate


C

,

Hydroxyethyl methacrylate, hydroxyethyl acrylate

,

Hydroxymethyl methacrylate, hydroxymethyl acrylate
D

n = 10 to 350 Polyethylene glycol

The synthesis of the nonionic amphipathic reactive precursor having the structure represented by Formula 1 is performed through the following process.

Synthesis of nonionic amphipathic reactive precursors

Step 1:

(Polyisobutylene) having a hydrophobic segment, a substance A (polypropylene triol) having three or more hydroxyl groups and a substance B (diisocyanate) having two or more isocyanate groups at a reaction molar ratio of 1: 3, For a period of time to form a urethane bond between A and B.

Step 2:

A substance C (hydroxy (meth) acrylic monomer) having a hydroxy group is added to the compound obtained in the first step and reacted at 50 to 55 ° C to form a urethane bond between B and C. The reaction molar ratio of the compound of the first step to the substance C is 1: 2.

Step 3:

A material D having a hydrophilic segment and a hydroxyl group, preferably polyethylene oxide having a molecular weight of 600 to 15,000, is added to the resultant mixture obtained in the second step at a molar ratio of 1 and stirred to form a urethane bond between B and D, Core crosslinking A precursor of amphiphilic polymer nanoparticles is synthesized.

The present inventors have synthesized nonionic amphipathic reactive precursors by variously controlling the molecular weight of polypropylene triols, and named the precursor as NARO with the abbreviation Nonionic Amphiphilic Reactive Oigomer. Table 2 shows the name of the precursor compound according to the molecular weight of the polypropylene triol.

Compound name Polypropylene triol (g / mol) Polyethylene oxide (g / mol) NARO 260 260 1500 NARO 700 700 1500 NARO 1000 1000 1500

Preparation of Core Crosslinked Amphiphilic Polymer Nanoparticles

The core crosslinked amphiphilic polymer nanoparticles according to the present invention are prepared through radical polymerization using the nonionic amphiphilic reactive precursor (NARO). Since the nonionic amphipathic reactive precursor according to the present invention has both hydrophilic and hydrophobic properties, it is dispersed in water to form a micellar structure, while acrylic groups at both ends are sequentially radically polymerized and crosslinked by an initiator to form core-form nanoparticles do.

The size of the nanoparticles produced according to the present invention can be variously adjusted by combining the molecular weight of the polypropylene triol or the molecular weight of the polyethylene glycol used,

10 g of the prepared nonionic amphiphilic reactive precursor (NARO) was dissolved in water together with 1-3 wt% of potassium persulfate or azobisisobutyronitrile as a polymerization initiator, At 300 rpm for about 6 to 12 hours. The names of the core crosslinking amphiphilic polymer nanoparticles prepared by the above reaction are shown in Table 3 below.

Example Compound name Precursor Example 1 CCP 260 NARO 260 Example 2 CCP 700 NARO 700 Example 3 CCP 1000 NARO 1000 Example 4 Core-shell 260 NARO 260 Example 5 Core-shell 700 NARO 700 Example 6 Core-shell 1000 NARO 1000 Example 7 NARO-co-MMA 260 NARO 260 Example 8 NARO-co-MMA 700 NARO 700 Example 9 NARO-co-MMA 1000 NARO 1000

* In the above compound names, NARO means a nonionic amphoteric reactive precursor and named as CCP, core-shell and NARO-co-MMA according to the polymerization method.

Example 1. Preparation of Core Crosslinked Amphiphilic Polymer Nanoparticles CCP 260

10 g of the synthesized nonionic amphoteric reactive precursor NARO 260 is dissolved in an oven set at 70 ° C and dissolved in 70 to 80 g of water.

1 to 3 wt% of potassium persulfate, which is a water-soluble initiator, is added to the precursor solution and is prepared by radical polymerization in an oil bath set at 60 to 70 ° C for 6 to 12 hours. In the case of the nanoparticles prepared under the above conditions, the amount of the initiator was adjusted to 1 to 3 wt% in order to control the degree of polymerization.

Example 2. Preparation of Core Crosslinked Amphiphilic Polymer Nanoparticle CCP 700

10 g of the previously synthesized nonionic amphoteric reactive precursor NARO 700 is dissolved in an oven set at 70 ° C. and dissolved in 70 to 80 g of water.

1 to 3 wt% of potassium persulfate, which is a water-soluble initiator, is added to the precursor solution and is prepared by radical polymerization in an oil bath set at 60 to 70 ° C for 6 to 12 hours. In the case of the nanoparticles prepared under the above conditions, the amount of the initiator was adjusted to 1 to 3 wt% in order to control the degree of polymerization.

Example 3 Preparation of core crosslinked ampholytic polymer nanoparticles CCP 1000

10 g of the previously synthesized nonionic amphoteric reactive precursor NARO 1000 is dissolved in an oven set at 70 ° C and dissolved in 70 to 80 g of water.

1 to 3 wt% of potassium persulfate, which is a water-soluble initiator, is added to the precursor solution and is prepared by radical polymerization in an oil bath set at 60 to 70 ° C for 6 to 12 hours. In the case of the nanoparticles prepared under the above conditions, the amount of the initiator was adjusted to 1 to 3 wt% in order to control the degree of polymerization.

Example 4. Preparation of Core-shell amphiphilic polymer nanoparticles Core-shell 260

In order to prepare nanoparticles having more firmer core than the core crosslinked amphiphilic polymer nanoparticles prepared in Examples 1, 2 and 3, nanoparticles were prepared by polymerizing methyl methacrylate, which is an acrylic monomer, in the core.

Acrylic monomers (methylmethacrylate, ethylmethacrylate) are hydrophobic. They enter the core crosslinked amphipathic polymer dispersed in water due to water, and are polymerized by the initiator. Azobisisobutyronitrile was used as an initiator for the preparation of core-shell nanoparticles, and the amount thereof was adjusted to 1 to 3 wt% based on the concentration of CCP nanoparticles dispersed in water.

The initiator was dissolved in 1 to 3 g of acetone and mixed with methyl methacrylate. At this time, the amount of methyl methacrylate was adjusted to 0.5 to 1.5 by weight with respect to the concentration of NARO nanoparticles dispersed in water.

The mixture of the initiator and the monomer (methylmethacrylate) mixed solution in 100 g of the CCP 260 nanoparticles prepared in Example 1 was added in five steps and the mixture was reacted in an oil bath set at 60 to 70 ° C for 6 to 12 hours .

Example 5: Preparation of Core-shell amphiphilic polymer nanoparticle core-shell 700

Azobisisobutyronitrile was used as an initiator for the preparation of core-shell nanoparticles, and the amount thereof was adjusted to 1 to 3 wt% based on the concentration of CCP nanoparticles dispersed in water.

The initiator was dissolved in 1 to 3 g of acetone and mixed with methyl methacrylate. The amount of methyl methacrylate was adjusted to 0.5 to 1.5 by weight with respect to the concentration of CCP nanoparticles dispersed in water.

The mixture of the initiator and the monomer (methylmethacrylate) mixed solution in 100 g of the CCP 700 nanoparticles prepared in Example 2 was added in five steps and reacted in an oil bath set at 60 to 70 ° C for 6 to 12 hours .

Example 6. Preparation of Core-shell amphiphilic polymer nanoparticles Core-shell 1000

For the production of core-shell nanoparticles, azobisisobutylonitrile was used as an initiator, and the amount thereof was adjusted to 1 to 3 wt% with respect to the concentration of NARO nanoparticles dispersed in water.

The initiator was dissolved in 1 to 3 g of acetone and mixed with methyl methacrylate. The amount of methyl methacrylate was adjusted to 0.5 to 1.5 by weight with respect to the concentration of CCP nanoparticles dispersed in water.

The mixture of the initiator and the monomer (methylmethacrylate) mixed solution in 100 g of the CCP 1000 nanoparticles prepared in Example 3 was added in five steps and reacted in an oil bath set at 60 to 70 ° C for 6 to 12 hours .

Example 7. Preparation of core crosslinked ampholytic polymer nanoparticles NARO-co-MMA 260

NARO-co-MMA 260 nanoparticles were prepared by copolymerization of a nonionic amphiphilic reactive precursor and methyl methacrylate, an acrylic monomer.

10 g of the synthesized nonionic amphoteric reactive precursor NARO 260 was dissolved in an oven set at 70 ° C, and then an initiator and methyl methacrylate were added thereto and mixed. At this time, azobisisobutylonitrile was used as an initiator. The amount of the initiator was 1 to 3 wt% based on the amount of the precursor, and the amount of methyl methacrylate was 1: 0.5 to 1.5 by weight based on the amount of the precursor.

The initiator, monomer and precursor mixture solution was added to 100 g of water at intervals of 60 to 75 minutes in five steps. To increase the degree of polymerization in the fifth step, potassium persulfate, a water-soluble initiator, was added at 60 to 70 ° C for 12 to 20 Lt; / RTI >

Example 8. Preparation of Core Crosslinked Amphiphilic Polymer Nanoparticles NARO-co-MMA 700

10 g of the synthesized nonionic amphoteric reactive precursor NARO 700 was dissolved in an oven set at 70 ° C, and then an initiator and methyl methacrylate were added thereto and mixed. At this time, azobisisobutylonitrile was used as an initiator. The amount of the initiator was 1 to 3 wt% based on the amount of the precursor, and the amount of methyl methacrylate was 1: 0.5 to 1.5 by weight based on the amount of the precursor.

The initiator, monomer and precursor mixture solution was added to 100 g of water at intervals of 60 to 75 minutes in five steps. To increase the degree of polymerization in the fifth step, potassium persulfate, a water-soluble initiator, was added at 60 to 70 ° C for 12 to 20 Lt; / RTI >

Example 9. Preparation of Core Crosslinked Amphiphilic Polymer Nanoparticles NARO-co-MMA 1000

10 g of the synthesized nonionic amphiphilic reactive precursor NARO 1000 was dissolved in an oven set at 70 ° C, and then an initiator and methyl methacrylate were added thereto and mixed. At this time, azobisisobutylonitrile was used as an initiator. The amount of the initiator was 1 to 3 wt% based on the amount of the precursor, and the amount of methyl methacrylate was 1: 0.5 to 1.5 by weight with respect to the amount of the precursor.

The initiator, monomer and precursor mixture solution was added to 100 g of water at intervals of 60 to 75 minutes in five steps. To increase the degree of polymerization in the fifth step, potassium persulfate, a water-soluble initiator, was added at 60 to 70 ° C for 12 to 20 Lt; / RTI >

Comparative Example 1. Amphiphilic block copolymer (EO-PO)

As an example of the above example, an amphiphilic block copolymer having two hydroxyl groups at a molecular end group having a molecular weight of 2,400 was used.

Experimental Example 1. Measurement of particle size

DLS (Dynamic Light Scattering) was used to measure the particle size of the core crosslinked amphiphilic polymer nanoparticles prepared according to the above Examples, and is shown in Table 4 below.

Example Compound name Particle Size (nm) Example 1 CCP 260 27.29 Example 2 CCP 700 15.18 Example 3 CCP 1000 17.67 Example 4 Core-shell 260 27.43 Example 5 Core-shell 700 24.21 Example 6 Core-shell 1000 20.72 Example 7 NARO-co-MMA 260 18.11 Example 8 NARO-co-MMA 700 15.87 Example 9 NARO-co-MMA 1000 47.22 Comparative Example 1 EO-PO 3.2

Experimental Example 2. Surface tension measurement

In order to measure the surface tension of various nanoparticles synthesized in the above Examples and the surface tension of Comparative Example 1, analysis was performed under the following conditions. The concentration of the nanoparticles prepared above and the concentration of the EO-PO block copolymer were adjusted to 5%, and the solution was measured using a Sigma 702ET surface tension tester. The measured values are shown in Table 5 below.

Example Compound name density Surface tension (dyne / cm) Example 1 CCP 260 5% 52.2 Example 2 CCP 700 5% 42.2 Example 3 CCP 1000 5% 41.0 Example 4 Core-shell 260 5% 41.8 Example 5 Core-shell 700 5% 42.0 Example 6 Core-shell 1000 5% 43.1 Example 7 NARO-co-MMA 260 5% 43.4 Example 8 NARO-co-MMA 700 5% 41.6 Example 9 NARO-co-MMA 1000 5% 36.8 Comparative Example 1 EO-PO 5% 39.3

In water-soluble cutting oil, the surface tension must be low in order to improve the wettability and coolability during processing. As shown in Table 5, it was confirmed that the surface tension of the core crosslinked amphiphilic polymer nanoparticles prepared according to the present invention is lower than that of Comparative Example 1 which is a conventional additive in some samples.

Experimental Example 3. Micro Tapping Torque Machine Test [

In order to confirm the processability of the nanoparticles prepared in the present invention, tests were conducted using a Micro Tapping Torque Test Machine. The measured values are shown in Table 6 below. The concentration of all the samples was equal to 5%. The specimen used in the test was S45C (SM45C in KS standard), the speed was 400 rpm, and the torque was 400 N / m.

Example Compound name density Max (Ncm) Example 1 CCP 260 5% 186.0 Example 2 CCP 700 5% 178.5 Example 3 CCP 1000 5% 184.0 Example 4 Core-shell 260 5% 203.0 Example 5 Core-shell 700 5% 195.0 Example 6 Core-shell 1000 5% 193.5 Example 7 NARO-co-MMA 260 5% 162.0 Example 8 NARO-co-MMA 700 5% 157.0 Example 9 NARO-co-MMA 1000 5% 147.0 Comparative Example 1 EO-PO 5% 171.0

The lower the torque value measured in Table 6, the lower the friction and resistance to the device, and at the same time the lubricity and the extreme pressure property are improved. It can be seen that the core crosslinked amphiphilic polymer nanoparticles prepared in Examples 7 to 9 of the present invention exhibit far lower torque values than those of Comparative Example 1 which is a conventional lubricant additive.

EXPERIMENTAL EXAMPLE 4. Product Application Evaluation (SAMSOL S-401)

Samples (Examples 7 to 9) showing the same or higher level of results in the evaluation of surface tension and workability among the core-crosslinked amphiphilic polymer nanoparticles prepared according to the above Examples were selected, and a commercially available SAMSOL S-401 lubricant Surface tension and workability were evaluated by using core crosslinked amphipathic polymer nanoparticles prepared as an additive instead of additives of SAMHWA OIL INDUSTRY CO., LTD., Korea.

The core crosslinked amphiphilic polymer nanoparticles prepared by the above example were added in an amount of 3% instead of the EO-PO block copolymer used as an additive to SAMSOL S-401 The surface tension results are shown in Table 7, and the workability evaluation in 8.

Example product name Compound name Concentration (% v / v) Surface tension (dyne / cm) Example 7 SAMSOL S-401 NARO-co-MMA 260 3% 42.1 Example 8 SAMSOL S-401 NARO-co-MMA 700 3% 39.2 Example 9 SAMSOL S-401 NARO-co-MMA 1000 3% 38.5 Comparative Example 1 SAMSOL S-401 EO-PO 3% 41.2

Example product name Compound name density Max (Ncm) Example 7 SAMSOL S-401 NARO-co-MMA 260 3% 132.0 Example 8 SAMSOL S-401 NARO-co-MMA 700 3% 125.0 Example 9 SAMSOL S-401 NARO-co-MMA 1000 3% 119.0 Comparative Example 1 SAMSOL S-401 EO-PO 3% 146.0

As shown in Tables 7 and 8, the core crosslinked amphiphilic polymer nanoparticles prepared by the present invention exhibited equivalent or superior physical properties in the evaluation of surface tension and workability as compared with Comparative Example 1, which is a conventional additive .

Claims (11)

1. A water-soluble cutting oil, comprising polymer nanoparticles prepared by core crosslinking a nonionic amphipathic reactive precursor represented by the following formula (1) by radical polymerization.
[Chemical Formula 1]

(In the formula 1,
Wherein A is a polypropylene triol or glycerol, which reacts with the isocyanate group of B to form a urethane bond;
Wherein B is a diisocyanate compound, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other is to react with the hydroxyl group of C to form a urethane bond or to react with the hydroxyl group of D To form a urethane bond;
Wherein C is a (meth) acrylate having a hydroxy, the hydroxy group reacts with the isocyanate group of the B to form a urethane bond;
D is polyethylene glycol, and the hydroxyl group reacts with the isocyanate group of B to form a urethane bond.)
The method according to claim 1,
Nonionic amphiphilic reactive precursor
Wherein the polypropylene triol has a weight average molecular weight of 260 to 2,000,
Wherein the polyethylene glycol has a weight average molecular weight of 600 to 15,000.
A water - soluble cutting oil containing core - crosslinked polymer nanoparticles.
The method according to claim 1,
Nonionic amphiphilic reactive precursor
Wherein the diisocyanate compound is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate and tolylidine diisocyanate,
Wherein the hydroxy-containing (meth) acrylate is hydroxyethyl (meth) acrylate or hydroxymethyl (meth) acrylate.
A water - soluble cutting oil containing core - crosslinked polymer nanoparticles.
A nonionic amphiphilic reactive precursor represented by the following formula (1)
A water-soluble cutting oil agent comprising polymer nanoparticles obtained by core crosslinking methyl (meth) acrylate or ethyl (meth) acrylate monomer by radical polymerization.
[Chemical Formula 1]

(In the formula 1,
Wherein A is a polypropylene triol or glycerol, which reacts with the isocyanate group of B to form a urethane bond;
Wherein B is a diisocyanate compound, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other is to react with the hydroxyl group of C to form a urethane bond or to react with the hydroxyl group of D To form a urethane bond;
Wherein C is a (meth) acrylate having a hydroxy, the hydroxy group reacts with the isocyanate group of the B to form a urethane bond;
D is polyethylene glycol, and the hydroxyl group reacts with the isocyanate group of B to form a urethane bond.)
5. The method of claim 4,
Wherein the methyl (meth) acrylate or ethyl (meth) acrylate monomer is reacted in an amount of 50 to 150 parts by weight per 100 parts by weight of the nonionic amphoteric reactive precursor.
A water - soluble cutting oil containing core - crosslinked polymer nanoparticles.
The method according to claim 4 or 5,
Nonionic amphiphilic reactive precursor
Wherein the polypropylene triol has a weight average molecular weight of 260 to 2,000,
Wherein the polyethylene glycol has a weight average molecular weight of 600 to 15,000.
A water - soluble cutting oil containing core - crosslinked polymer nanoparticles.
The method according to claim 4 or 5,
Nonionic amphiphilic reactive precursor
Wherein the diisocyanate compound is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate and tolylidine diisocyanate,
Wherein the hydroxy-containing (meth) acrylate is hydroxyethyl (meth) acrylate or hydroxymethyl (meth) acrylate.
A water - soluble cutting oil containing core - crosslinked polymer nanoparticles.
Reacting a nonionic amphipathic reactive precursor represented by the following formula (1) to produce a core crosslinked polymer nanoparticle;
(Meth) acrylate or ethyl (meth) acrylate monomer is mixed with the initiator and reacted with the polymer nanoparticle dispersion to produce polymer nanoparticles containing the (meth) acrylate polymer in the core;
And mixing the polymer nanoparticles with a cutting oil.
A method for producing water-soluble cutting oil.
[Chemical Formula 1]

(In the formula 1,
Wherein A is a polypropylene triol or glycerol, which reacts with the isocyanate group of B to form a urethane bond;
Wherein B is a diisocyanate compound, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other is to react with the hydroxyl group of C to form a urethane bond or to react with the hydroxyl group of D To form a urethane bond;
Wherein C is a (meth) acrylate having a hydroxy, the hydroxy group reacts with the isocyanate group of the B to form a urethane bond;
D is polyethylene glycol, and the hydroxyl group reacts with the isocyanate group of B to form a urethane bond.)
9. The method of claim 8,
Wherein the methyl (meth) acrylate or ethyl (meth) acrylate monomer is added in an amount of 50 to 150 parts by weight based on 100 parts by weight of the nonionic amphoteric reactive precursor.
A method for producing water-soluble cutting oil.
10. The method according to claim 8 or 9,
Nonionic amphiphilic reactive precursor
Wherein the polypropylene triol has a weight average molecular weight of 260 to 2,000,
Wherein the polyethylene glycol has a weight average molecular weight of 600 to 15,000.
A method for producing water-soluble cutting oil.
10. The method according to claim 8 or 9,
Nonionic amphiphilic reactive precursor
Wherein the diisocyanate compound is at least one selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate and tolylidine diisocyanate,
Wherein the hydroxy-containing (meth) acrylate is hydroxyethyl (meth) acrylate or hydroxymethyl (meth) acrylate.
A method for producing water-soluble cutting oil.

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