KR20180092224A - acrylamide nanogel antifoaming agent and its manufacturing method - Google Patents

Abstract

A method for manufacturing an acrylamide nanogel antifoaming agent of the present invention manufactures an acrylamide nanogel antifoaming agent by using a miniemulsion method through a silicon polymer, and according to the present invention, the acrylamide nanogel antifoaming agent is manufactured by using the miniemulsion method through the silicon polymer, and thus after centrifugal separation in cutting oil using the acrylamide nanogel antifoaming agent, antifoaming properties are maintained to obtain a remarkable effect of preventing the decrease in wear resistance and thermo-absorption and reusing the acrylamide nanogel antifoaming agent.

Description

[0001] The present invention relates to an acrylamide nanofiber antifoaming agent and its manufacturing method,

The present invention relates to an acrylamide nano gel antifoaming agent and a method of preparing the same, and more particularly, to a method of manufacturing an antifoaming agent of acrylamide nano gel by using a mini emulsion method through a silicone polymer, The present invention relates to an acrylic foam nano gel antifoaming agent and a method for producing the same, which can maintain the antifoaming property even after centrifugal separation in a cutting oil and prevent the abrasion and heat absorbing effect from being reduced.

Generally used cutting oil is regenerated and used.

However, a defoaming agent or a polymer type defoaming agent is used for the cutting oil, and the defoaming agent or the polymer type defoaming agent is removed at the time of centrifuging.

Particularly, among the cutting oil agents, semiconductor cutting oil is often recycled because it is expensive compared to a metal working cutting oil, and is mainly recycled through a two-stage centrifuge at a temperature of 70 ° C or lower.

The antifoaming agent disclosed in the prior art publication No. 10-2012-0095351 contains a bisamide dispersed in a polyether compound and contains a bisamide content of 0.01 to 10 wt% based on the weight of the bisamide and the polyether compound %, The content of the polyether compound is 90 to 99.99% by weight, and the mode value in the particle size distribution based on the volume of the bisamide is 0.1 to 5 占 퐉.

As another prior art, the polymeric antifoam composition of Patent Application Laid-Open No. 10-2004-0061165 and the production method thereof are obtained by polymerizing an acrylate monomer, a chain transfer agent, a radical reaction initiator and a solvent and have a number- 8000, and a weight average molecular weight of 10,000 to 30,000.

However, in the above conventional techniques, the defoaming agent is removed from the cutting oil when the defoaming agent using the defoaming agent or the polymer type defoaming agent is used, and the defoaming property is lowered. Thus, the wear of the boundary friction between the surface and the surface during re- So that defects of the workpieces are generated.

The present invention relates to an acrylic-based nano-gel defoaming agent and a method for producing the same, wherein the acrylic-modified nano-gel defoaming agent is produced by using a mini-emulsion method through a silicone polomer, The present invention also provides an antifoaming agent for an acrylic-modified nano gel and a method for producing the antifoaming agent, wherein the antifoaming agent is retained even after centrifuging to prevent the wear and the heat absorbing effect from being reduced.

The present invention relates to a method for producing an acrylamide nano gel defoamer for producing a polyacrylamide nanogel defoamer using a miniemulsion method through a silicon polerer,

Preparing a mixed solution by adding water-soluble acrylamide and bis-acrylamide to methylene chloride; Sonicating the mixed solution on an ice bath; Heating the mixed liquid obtained by sonication at a temperature of 50 to 70 ° C for 13 to 15 hours; Centrifuging the heated mixture through a centrifuge to obtain a resultant product; .

The present invention relates to a process for producing an acrylic-modified nano gel defoamer by using a mini-emulsion method through a silicone polomer, so that the defoamer is retained even after centrifugation in a cutting oil using the acrylamide nano gel defoamer, And the heat absorbing effect can be prevented from being reduced and reused.

1 is a conceptual diagram of the present invention
2 is a conceptual diagram showing the chemical structure and characteristics of silicon
Fig. 3 is a conceptual diagram showing the constructions of the silicone rubber
4 is a conceptual diagram showing the characteristics of the silicone resin
5 is a conceptual diagram of the direct method in the synthesis method of the silicone polymer of the present invention
FIG. 6 is a conceptual diagram showing the coalescence of a polymer colloid through an emulsion polymerization reaction
Fig. 7 is a schematic diagram illustrating the synthesis of the present invention through the miniemulsion method of the present invention
FIG. 8 is a photograph of the encapsulation of magnetite synthesized through the mini-emulsion method of the present invention using a transmission electron microscope (TEM)
FIG. 9 is a conceptual diagram of manufacturing a polyacrylamide nano-gel using the mini-emulsion method of the present invention
10 is a flow chart of a polyacrylamide nanogel production process using the mini-emulsion method of the present invention
11 is a comparative chart comparing the amount of foam after centrifugation using UI-30, PDMS-S, UP-35-MMA and UP-35-MAA among the acrylamide nano gel defoamer of the present invention

The present invention relates to a method for producing an acrylamide nano gel defoamer for producing a polyacrylamide nanogel defoamer using a miniemulsion method through a silicon polerer,

Preparing a mixed solution by adding water-soluble acrylamide and bis-acrylamide to methylene chloride; Sonicating the mixed solution on an ice bath; Heating the mixed liquid obtained by sonication at a temperature of 50 to 70 ° C for 13 to 15 hours; Centrifuging the heated mixture through a centrifuge to obtain a resultant product; .

In addition, the silicone polymer is synthesized and used in a synthesis process by a direct method, separating methylchlorosilane using a distillation tower having a high separation function, and then performing a distillation process.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

Fig. 1 is a conceptual view of the present invention, Fig. 2 is a conceptual diagram showing the chemical structure and characteristics of silicon, Fig. 3 is a conceptual view showing the characteristics of silicone rubber, Fig. 4 is a conceptual view showing the characteristics of silicone resin, FIG. 6 is a conceptual diagram showing the coalescence of polymer colloids through emulsion polymerization, FIG. 7 is a schematic diagram synthesized through the mini-emulsion method of the present invention, and FIG. 8 is a schematic view of a mini-emulsion method of the present invention FIG. 9 is a conceptual view of manufacturing a polyacrylamide nano-gel using the mini-emulsion method of the present invention, and FIG. 10 is a schematic view of an embodiment of the present invention. FIG. FIG. 11 is a flow chart of the preparation of a polyacrylamide nano gel using mini-emulsion method, and FIG. 11 is a graph showing the results of the production of polyacrylamide nano-gel using UI-30, PDMS-S, UP-35-MMA and UP- After centrifugation it is also compared to a comparison of the amount of foam.

More specifically, the present invention relates to an acrylic-based nano-gel defoaming agent and a method for producing the same, which comprises preparing an acrylic-modified nano-gel defoaming agent by using a mini-emulsion method through a silicone polymer, It is possible to maintain the defoaming property even after the centrifugal separation in the cutting oil using the gel defoaming agent, thereby preventing the abrasion prevention and the heat absorbing effect from being reduced and reusing it.

The miniemulsion method coalesces monomer droplets by Ostwald ripening. The miniemulsion method is used for nano-dispersion of dyes, synthesis of condensation polymers, and blending of nano-sized particles. At this time, the number of droplets is changed by the coalescence of the monomer droplet.

And a common surfactant called ultra-hydrophobe is dissolved in the monomer droplets, and the co-surfactant is used in combination with hexadecane, cetyl alcohol, ), Polyester, and isocyanate system, and the monomer is polymerized in the monomer droplet so that the interval II does not exist.

The polyacrylamide nanogel antifoaming agent is a nanostructured antifoaming agent, and a polyacrylamide nanogel antifoaming agent is prepared using the miniemulsion method.

The method for preparing a polyacrylamide nanogel defoamer using the miniemulsion method is a method in which water-soluble acrylamide and bis-acrylamide are introduced into methylene chloride, Lt; / RTI > Sonicating the mixed solution on an ice bath; Heating the mixed liquid obtained by sonication at a temperature of 50 to 70 ° C for 13 to 15 hours; Centrifuging the heated mixture through a centrifuge to obtain a resultant product; .

The resultant is to be used after washing and hanging and drying.

The polyacrylamide nanogel is prepared by coalescence of an N, N'-methylenebisacrylamide cross-linking monomer and an acrylamide monomer by a chemical reaction, Ammonium persulfate and tetramethylethylenediamine (TEMED) are used for fusion.

The acrylamide nano gel antifoaming agent is a cutting oil agent. The cutting oil agent is an emulsion agent used to assist in the processing of metal through an electric tool, a cutting tool, and a metal workpiece in the process of metal working.

The cutting oil agent is classified into a non-water-soluble cutting oil agent, which is mainly used for lubricating, and a water-soluble cutting oil agent, which is mainly used for cooling.

The cutting oil may be added with an additive to improve the efficiency of metal working. As a conventional cutting oil, Dyna, Yushiro, etc. are used.

When such a cutting oil agent is used, a lubrication action, a cooling action, and a semi-welded action occur.

The lubricating action penetrates between the face and the face to reduce the boundary friction to prevent the wear and reduce the cutting power. The cooling action absorbs the heat generated during the work, thereby preventing the abrasion due to heat and preventing the expansion of the metal workpiece And the semi-welded action is to prevent defects in the workpieces generated in the cutting edge generated in the cutting edge at the time of cutting through the cutting tool. At this time, the cutting edge is a tip of the cutting edge of the cutting tool, and the constituent cutting edge is a part of the chip is processed and hardened in the cutting process and welded to the cutting edge of the cutting tool.

That is, by using the cutting oil, abrasion and abrasion are reduced by reducing the friction between the cutting tool and the metal workpiece, the surface is prevented from being corroded, the generated heat is cooled to prevent deformation due to heat, By washing the water, the surface properties of the processed surface are improved.

The method of applying the cutting oil is classified into an overflow type and an open type.

At this time, the flooding formula is to continuously use the low-pressure pump to pour the cutting oil on the cutting surface, and the mist type uses a high-speed air flow and a cutting oil in a mist spraying manner.

The cutting oil agent is divided into E, G, G, B and C depending on the degree of containing the detergent, rust inhibitor / pH adjuster, DI water, rust inhibitor additive, CA, lubricant, preservative, BTA, wetting agent, The ratio of each cutting oil is shown in the table below.

E G end I All detergent 74% (37 mL) 74% (37 mL) 70% (35 mL) 70% (35 mL) 70% (mL) Rust inhibitor / PH regulator 16% (8 mL) 16% (8 mL) 16% (8 mL) 12% (6 mL) 12% (6 mL) DI-Water 6% (3 mL) 6% (3 mL) 6% (3 mL) 6% (3 mL) 6% (3 mL) Anti-rust additives 2% (1 mL) 2% (1 mL) 3% (1.5 mL) 4% (2 mL) 4% (2 mL) CA 2% (1 mL) - 1% (0.5 mL) 1% (0.5 mL) 3% (1.5 mL) slush - - 3% (1.5 mL) 6% (3 mL) 3% (1.5 mL) antiseptic - 2% (1 mL) 1% (0.5 mL) 1% (0.5 mL) 1% (0.5 mL) BTA - - 0.08 g 0.08 g 0.08 g Wetting agent - - One drop One drop One drop Bubble sheep 4.6 mL 4.3 mL 3.7 mL 3.0 mL 3.5 mL

Compared with the acrylamide nano gel antifoaming agent, there are conventional antifoaming agents and polymer type antifoaming agents.

The conventional antifoaming agent uses 720 or SJ as a sample to be used, and the performance of each sample is shown in the following table.

Defoamer density Bubble volume (ml) E G I SJ 0.10% 1.6 1.2 1.1 0.20% 1.5 1.2 0.8 0.30% 0.7 0.6 0.6 0.40% 0.6 0.6 0.6 0.50% 0.6 0.6 0.4 720 0.10% 1.8 2.2 1.5 0.20% 1.7 1.5 1.3 0.30% 1.5 1.3 1.3 0.40% 1.5 1.2 1.1 0.50% 1.5 1.0 1.0

The polymeric defoaming agent used was 2500, 2700, PDMS-M, PDMS-B or PDMS-S, and the performance of each sample was as shown in the following table.

sample Bubble volume (ml) end I All none 3.8 3.1 3.6 2500 1.5 1.7 2.0 2700 2.5 2.0 2.4 PDMS-M 2.7 2.4 2.7 PDMS-B 2.8 2.6 2.1 PDMS-S 2.6 2.8 3.9

UP-40, UP-39, UP-30, PA-30, PAm-20, PAm-30, PAm-60, 2700b, 2500h, 2500g, 2700a, 2700e, 2700f, UP-29, UP-28, UP-35-MAA, UP-35-MMA, PDMS-M, PDMS-B or PDMS-S are used.

sample Bubble volume (ml) (1 mL) (4 mL) (8 mL) Minimum value PAm-10 3.9 3.2 3.2 3.2 PAm-20 3.6 3.5 3.1 3.1 PAm-30 3.7 3.3 3.0 3.0 PAm-60 3.1 3.9 4.1 3.1 2700b 7.8 6.8 7.3 6.8 2500h 6.3 4.8 5.5 4.8 2500g 4.3 3.8 3.6 3.6 2700a 7.3 7.5 7.5 7.3 2700e 7.0 8.0 7.3 7.0 2700f 7.8 7.3 7.3 7.3 UP-40 4.2 3.7 1.2 1.2 UP-39 7.5 6.5 5.5 5.5 UP-30 4.2 4.2 2.6 2.6 UP-29 5.7 5.3 4.9 4.9 UP-28 5.8 5.3 5.3 5.3 UP35-MAA 3.9 4.3 4.5 3.9 UP35-MMA 3.9 3.9 3.3 3.3 PDMS-M 5.5 7.5 7.5 5.5 PDMS-B 8.5 7.5 7.0 7.0 PDMS-S 3.3 3.9 3.4 3.3

When using conventional antifoaming agent for cutting oil, compare the amount of foam after centrifuging with a centrifuge as shown in the following table.

sample Amount of foam after centrifugation (ml) 0 times 1 time Episode 2 720 1.3 1.9 2.6 SJ 0.6 1.1 1.6 Dyna 1.2 1.4 2.0 Yushiro 1.2 1.3 2.0

When the acrylamide nano gel defoamer of the present invention is used, the amount of foam after centrifugal separation by a centrifuge is shown in the following table.

sample Amount of foam after centrifugation (ml) (1 mL) (4 mL) (8 mL) 0 times 1 time Episode 2 0 times 1 time Episode 2 0 times 1 time Episode 2 PAm-10 3.9 5.0 4.7 3.2 3.8 4.4 3.2 3.7 4.2 PAm-20 3.6 5.0 5.2 3.5 4.3 5.6 3.1 4.0 5.3 PAm-30 3.7 4.8 4.5 3.3 4.0 3.9 3.0 3.5 4.2 PAm-60 3.1 5.1 4.4 3.9 4.2 4.3 4.1 4.2 4.4 2700b 7.8 8.0 8.0 6.8 7.0 7.0 7.3 7.0 7.0 2500h 6.3 7.0 7.0 4.8 7.0 7.5 5.5 7.0 7.0 2500g 4.3 4.6 4.3 3.8 4.9 4.9 3.6 5.8 5.3 2700a 7.3 6.2 6.3 7.5 7.2 8.0 7.5 7.7 8.0 2700e 7.0 7.5 7.5 8.0 7.0 7.0 7.3 6.8 7.0 2700f 7.8 7.4 7.4 7.3 7.8 8.0 7.3 7.3 8.0 UP-40 4.2 6.2 5.7 3.7 5.9 6.1 1.2 4.0 4.2 UP-39 7.5 7.8 7.9 6.5 7.4 7.6 5.5 7.3 8.0 UP-30 4.2 3.8 3.9 4.2 3.6 4.2 2.6 3.7 4.7 UP-29 5.7 7.0 7.0 5.3 6.5 7.0 4.9 6.2 6.3 UP-28 5.8 7.0 7.5 5.3 4.5 6.1 5.3 4.4 6.2 UP-35-MAA 3.9 4.0 3.9 4.3 4.3 4.3 4.5 3.1 3.0 UP-35-MMA 3.9 5.9 4.1 3.9 4.7 4.0 3.3 3.7 3.3 PDSM-M 5.5 5.8 4.2 7.5 7.3 7.7 7.5 7.3 7.2 PDSM-B 8.5 7.3 8.0 7.5 6.8 6.5 7.0 6.8 7.7 PDSM-S 3.3 5.3 5.2 3.9 4.7 4.5 3.4 4.3 4.2

When the measured values were compared, it was found that the nanoparticulate defoamer of the present invention was used and that the cutting oil using UI-30, UI-30, PDMS-S, UP-35-MMA or UP- It is appropriate to use UI-30, PDMS-S, UP-35-MMA, or UP-35-MAA in the present invention.

The silicone polymer is a compound in which silicon is polymerized by chemical bonding, and is a silicone oil, a silicone rubber, or a silicone resin.

The silicone oil has a chain-like molecular structure bonded to a siloxane structure. Since the siloxane structure is independent of each molecule, the silicone oil can move freely with respect to each other, thereby having fluidity, i.e., a liquid property.

The silicone rubber is bonded in a network structure so that the molecular chains can not mutually move and the fluidity disappears. However, as the degree of freedom of the molecule increases, the silicone rubber becomes elastic and has the property of rubber.

The silicone resin is bonded in a network structure by initially selecting a crosslinkable structural unit at an extremely high crosslinking density. As the cross-linking density increases, the degree of freedom of the molecule decreases and the elasticity is also reduced, resulting in hardness.

Since the chemical nature of silicon has both inorganic and organic properties in the molecular structure, silicon (Si) and oxygen (O) contained in the silicon molecules have a large difference in electronegativity, It is stable against enemy and strong against heat and acid.

Therefore, the silicon is practical when used at a high temperature.

Describing the physical properties of silicon, silicone oil has a low surface tension due to a small attractive force between molecules, has a property of being thin and wide on the surface of an object, has a low solidifying point and low temperature resistance, and silicone rubber has a low solidifying point Cold resistance is good.

However, when the silicone oil is used, the pressure of the friction surface becomes high and the oil film can not be preserved, which is not suitable as a lubricant between metals used in the present invention.

The synthesis of the silicone polymer is carried out by a direct synthesis process, in which methylchlorosilane is separated using a distillation column having a high separation function and then subjected to a distillation process.

Among the methylchlorosilanes, dimethyldichlorosilane ((CH3) 2SiCl2) has two functional groups capable of two-dimensional growth.

The dimethyldichlorosilane reacts with water to form silanols, and the silanol is polymerized to form a linear siloxane, and potassium hydroxide is used as a catalyst to form a cyclic 2-methyl form. The tetrahedron is again made of linear silicone rubber using potassium hydroxide as a catalyst.

When crosslinking the silicone rubber, copolymerizing with the organic material, imparting adhesiveness, imparting oil resistance, etc., silanes having a unique organic group such as aminopropyl or trifluoropropyl, that is, a special monomer And the specific monomer is produced by a technique of organic synthetic chemistry.

The silicone antifoaming agent can be classified according to major components, solvent type, and amount of addition, as shown in the following table.

 main ingredient Features and Usability Addition amount Solvent type receptivity
Organic Polymers and Organometallic Compounds Water-soluble, emulsion paint system, aqueous RMPC Especially excellent for Alkyd Emulsion System 0.1-1.0 Water, BA Non-silicone polymer Suitable for matte, silk emulsion paints, suitable for interior paint 0.2-0.8 water Modified polysiloxane Suitable for water-based paint and water-based pigment concentrating system, transparency Superior air-mixing inhibition effect in case of tackifier, dispersion and pumping 0.1-0.3 - Solvent type Non-silicon compound Excellent transparency, suitable for polyurethane, acid hardening, NLRCAR, unsaturated resin type, woodworking paint and alkyd system 0.1-1.0 Xylene Non-silicone polymer HIGH SOLID Suitable for NC lockers, two-component urethane, COLDEPOXY, unsaturated resin systems 0.1-0.7 Mineral Spirit Non-silicone polymer Suitable for surface active effects, polyurethane, alkyd paint systems, and baked alkyd systems 0.5-2.0 Xylene Silicone-based polymer 2-pack PU (especially CURTAIN COAT). STOVINGENAMEL Heavy oil, suitable for alkyd system 0.1-1.0 Xylene, MPA, EA, BA Silicone-type polymer Suitable for 2-pack PU, NC, system, OIL Free Polyester and Sobu Acryl 0.1-0.5 Alkyl Benzene MPA Silicone-type polymer Suitable for natural dry type acrylic, vinyl, CR polymer, alkyd base construction paint, airless spray painting system 0.1-1.0 Cyclohexanone Alkyl Silicone-type polymer Polyurethane, unsaturated resin, acid hardening, NC lacquer, especially Curtain coating Excellent anti-tearing effect 0.1-1.0 Xylene, MPA, EA, BA Silicone-type polymer Suitable for architectural paints, natural dry acrylic, Vinyl, CR Polymer, alkyd base construction paint, airless spray painting system 0.5-1.0 Diisobutyl-Ketone Silicone-type polymer Excellent Compatibility, Polyurethane, Unsaturated Polyester System Suitable for paint, roller, airless spray coating 0.1-1.5 Alkyl Benzene MPA, Xylene Silicone-type polymer Suitable for natural drying type construction paint, 2-component Epoxy Urethane brush, roller, airless spray coating 0.1-0.7 Diisobutyl-Ketone Fluorine silicon It is suitable for high gloss, quick drying, Type Sparay and Brush coating Especially excellent compatibility with wood coating paint, excellent in two-component urethane-curing type, NC locker system 0.1-0.4 Cyclohexanone Non-silicone polymer Unsaturated Polyester (Musical Instrument, Instrument) Unsaturated UV System, Znc Steorate and Extra Extention Pigment System, Transparency Requirement System 0.1-1.0 Alkyl Benzene Mineral Spirit Silicone-type polymer  UV Curing System of Acrylate Oligomer System 0.5-1.0 2-Ethy Hexyl Acrlate Silicone-type polymer  Non-solvent Epoxy System (especially flooring) Excellent surface smoothness 0.5-1.5 Alkyl Benzene MPA  Xylene 1% max  Ideal for ink-only defoamers, aromatic solvents, and food-related packaging printing  EA, nBA, 2M1MEA

The silicone antifoaming agent is an oil-based antifoaming agent, a solvent-based antifoaming agent, an emulsion-type antifoaming agent, or an oil-compound-type antifoaming agent and is not molecularly associated with a molecule having water, a polar atom, a hydrocarbon or a hydrocarbon group, It has a somewhat cool property and is suitable for the present invention.

The silicone defoamer is chemically inert and stable, has no reactivity with a foamable material, has excellent heat resistance, is physiologically harmless, and can be used for food, fermentation and the like.

The oil type defoaming agent has an oil content of 100% and is excellent in heat resistance, and is used when it is difficult to mix foreign substances such as water and solvent.

The emulsion type antifoaming agent uses an emulsifier as a silicone antifoaming agent.

The oil compound type antifoaming agent is a compound in which fine powder silica is dispersed.

Accordingly, the present invention relates to a process for producing an acrylic-modified nano gel defoamer by using a mini-emulsion method through a silicone polomer, so that the defoamer is retained even after centrifugation in the cutting oil using the acrylic- And the effect of preventing the heat absorbing action is prevented from being reduced and reused.

Claims (3)

A method for producing an acrylamide nano gel defoamer for producing a polyacrylamide nanogel defoamer using a miniemulsion method through a silicon polerer,
Preparing a mixed solution by adding water-soluble acrylamide and bis-acrylamide to methylene chloride; Sonicating the mixed solution on an ice bath; Heating the mixed liquid obtained by sonication at a temperature of 50 to 70 ° C for 13 to 15 hours; Centrifuging the heated mixture through a centrifuge to obtain a resultant product; A method for producing an acrylic-modified nano gel defoaming agent The method according to claim 1, wherein the silicone polymer is synthesized and used in a synthetic process by a direct method, separating methylchlorosilane using a distillation tower having a high separation function, and then carrying out a distillation process. Manufacturing method of nanogel defoamer An acrylic-modified nano-gel defoaming agent produced by the method of any one of claims 1 to 2

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