KR20190046604A - Composite based melamine resin, and oil-water separating materials - Google Patents

Abstract

The present invention relates to oil-water separating materials and a method for producing the same. The oil-water separating materials include a composite in which a zinc oxide particle layer, which forms a micro-nano structure; a magnetic particle layer that is magnetized; and a fatty acid layer that has a low surface energy, are sequentially formed on the surface of a polyurethane matrix having a porous, foamed structure, and thus are not only excellent in durability, but also have an advantage that the average BET specific surface area and the maximum average absorption amount of oil is large. Further, the composite is lipophilic, superhydrophobic, and super-water repellent, is excellent in oil-water separation efficiency, and is magnetic to facilitate position control and recovery of the composite, and thus can be effectively used as oil-absorption-type, oil-water separating materials used for large-scale oil-water separation such as oil removal from the ocean.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane-based composite and a material for water-

The present invention relates to a polyurethane-based composite and a material for water-diluting comprising the same.

Recently, due to environmental problems, attention has been paid to oil-water separating materials for removing pollutants present in the water. Research on the high performance and application of separation materials and diversification of use fields have been actively carried out, .

Conventional water-oil separation methods commonly used include separation of gravity and adsorption. Of these, the gravity separation method is simple in structure due to a small mechanical operation part, and consumables to be replaced as a filter are not used. There are advantages to be able to. However, since the efficiency of separating the oil is low and the water (H ₂ O) content in the separated and discharged oil is high, it is difficult to recycle the oil and the amount of water is increased by mixing with water, there is a problem. In addition, since the oil-water separating capacity is not large, oil can not be effectively separated in a short period of time in the case of a wide range of contamination such as oil leaking into the sea or river.

As an alternative to this, in-depth research is underway on the development of optimal manufacturing processes for the characterization of the separating materials used in the adsorption process and on the technology for producing the separating materials with high functionality by the surface treatment technique.

For example, the plasma surface treatment technique has been developed to improve the performance of a material by changing the surface of a polymer material used as a disk or a filter in an adsorption method. However, since the above techniques require a surface treatment process such as a plasma treatment, the production cost of the material is high, and the performance required for water separation is improved, for example, the physical properties such as the adhesion angle indicating the water affinity of the separation material are improved There is a limit to the degree.

Therefore, it is possible to manufacture a large amount of water in a short time, and it is easy to manufacture the material and to carry out the large-scale oil-water separation work, and is excellent in performance such as water affinity and oil absorption amount for oil- Development of such an excellent separating material is required.

Korean Registered Patent No. 10-0786678

An object of the present invention is to provide a separation material which is easy to manufacture and economical in production of a material and a large area oil separation operation, excellent in water affinity and water absorption capacity for oil separation and excellent in oil separation efficiency.

In order to solve the above problems,

The present invention, in one embodiment,

A polyurethane matrix having a spongy porous structure;

A zinc oxide particle layer formed on the matrix;

A magnetic particle layer formed on the zinc oxide particle layer; And

And a fatty acid layer formed on the magnetic particle layer and containing a fatty acid having 10 to 30 carbon atoms.

In addition, the present invention, in one embodiment,

Immersing a polyurethane matrix having a sponge-like porous structure in a zinc oxide precursor solution, and irradiating microwaves to form a zinc oxide particle layer on the surface of the matrix;

Immersing a polyurethane matrix in which a zinc oxide particle layer is formed on a surface thereof in a solution containing magnetic particles to form a magnetic particle layer on the surface; And

And immersing the polyurethane matrix having the magnetic particle layer on its surface in a solution of 10 to 30 carbon atoms in which the fatty acid is dissolved to form a fatty acid layer on the surface.

Further, in one embodiment, the present invention provides a material for oil-water separation comprising the composite.

Since the composite according to the present invention is manufactured through microwave irradiation, a manufacturing process is simple, and a zinc oxide particle layer forming a micro-nano structure on the surface of a polyurethane matrix having a porous structure on the sea surface, a magnetic particle layer having magnetic properties, A low-energy fatty acid layer is formed successively to provide excellent durability, a large average BET specific surface area, and a maximum average absorption amount for oil. Also, since the complex exhibits lipophilic property, super hydrophobic property and super water repellency, and is excellent in oil separation efficiency and magnetic property, it is easy to control the position of the composite and recover it. Therefore, the oil used for large- And can be usefully used as a material for adsorptive oil and water separation.

Fig. 1 is an SEM photograph of (a) a polyurethane sponge as a non-treated group, (b) the composite prepared in Comparative Example 1, (c) the composite prepared in Example 1, (SEM-EDS) analysis results of the polyurethane sponge and the composite prepared in Comparative Example 1 and Example 1. Fig.
FIG. 2 is a graph showing the results of XRD analysis of a polyurethane sponge as a non-treated group and the composite prepared in Example 1 and Comparative Example 1. FIG.
3 is a graph showing X-ray photoelectron spectroscopy (XPS) results of the polyurethane sponge as a non-treated group and the composite prepared in Example 1. FIG.
4 is a graph showing water contact angle (WCA) results of the polyurethane sponge as a non-treated group and the composite prepared in Example 1 and Comparative Examples 1 and 2. FIG.
5 is a graph showing the results of magnetization measurement of Fe ₃ O ₄ particles as magnetic particles and the composite prepared in Example 1 before and after water separation.
6 is a graph showing the maximum average amount of water absorption according to the number of times of repeated use in oil separation of the composite prepared in Example 1. FIG.
7 is a graph showing the water contact angle (WCA) before and after the evaluation according to the durability evaluation method of the composite prepared in Example 1. Fig.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail.

It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

In the present invention, the terms " comprising " or " having ", and the like, specify that the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for water softening and a method for producing the same.

Recently, due to environmental problems, attention has been paid to oil-water separating materials for removing pollutants present in the water. Research on the high performance and application of separation materials and diversification of use fields have been actively carried out, .

Conventional water-oil separation methods commonly used include separation of specific gravity and adsorption, and development of an optimum manufacturing process for the characteristics of the separation material used in the adsorption system and separation of the high- In-depth research on material manufacturing technology is under way. For example, the plasma surface treatment technique has been developed to improve the performance of a material by changing the surface of a polymer material used as a disk or a filter in an adsorption method. However, since the technologies developed so far require a surface treatment process such as a plasma treatment, the production cost of the material is high, and the performance required for oil separation, for example, properties such as adhesion angle indicating the water affinity of the separation material There is a limit to the degree of improvement.

Accordingly, the present invention provides a polyurethane-based composite, and a material for water softening including the same.

Since the composite according to the present invention is manufactured through microwave irradiation, a manufacturing process is simple, and a zinc oxide particle layer forming a micro-nano structure on the surface of a polyurethane matrix having a porous structure on the sea surface, a magnetic particle layer having magnetic properties, A low-energy fatty acid layer is formed successively to provide excellent durability, a large average BET specific surface area, and a maximum average absorption amount for oil. Also, since the complex exhibits lipophilic property, super hydrophobic property and super water repellency, and is excellent in oil separation efficiency and magnetic property, it is easy to control the position of the composite and recover it. Therefore, the oil used for large- And can be usefully used as a material for adsorptive oil and water separation.

Hereinafter, the present invention will be described in more detail.

Complex

The present invention, in one embodiment, provides a polyurethane-based composite.

Specifically, the composite according to the present invention comprises a polyurethane matrix having a porous structure on the surface of the sea, and is formed on the surface of the polyurethane matrix and aggregated in the form of a flame or a snow to form a micro- And a fatty acid layer formed on the surface of the magnetic particle layer and containing a fatty acid having 10 to 30 carbon atoms, the magnetic particle layer including a zinc particle layer and formed of a magnetic particle layer formed on the zinc oxide particle.

Hereinafter, each component constituting the composite according to the present invention will be described in more detail.

First, the present invention includes a sponge-like polyurethane matrix, such as a polyurethane sponge, which is inexpensive to manufacture and is economical and has high elasticity. Such polyurethane matrices may include open pores and may include open pores having an average size or diameter of 100 to 1,000 mu m. More specifically, the average size of the open pores is in the range of 100 to 800 탆, 100 탆 to 600 탆, 100 탆 to 400 탆, 100 탆 to 200 탆, 500 탆 to 1,000 탆, 200 탆 to 300 탆, 400 占 퐉, 500 占 퐉, or 300 占 퐉 to 600 占 퐉. The present invention includes a sponge-like polyurethane matrix having open pores having a diameter as described above, so that a high elasticity of the composite can be realized, thereby exhibiting an excellent durability.

As one example, when the composite is compressed at 50% or 70% strain at room temperature (21 ± 2 ° C), the stress is 0.0003 to 0.00045 MPa, specifically 0.0003 to 0.00043 MPa, 0.0003 to 0.00039 MPa, 0.0003 to 0.00037 MPa, 0.0003 to 0.00035 MPa, 0.00031 to 0.00033 MPa, 0.00031 to 0.00043 MPa, or 0.00041 to 0.00043 MPa. This is equivalent to a polyurethane sponge which is commercially available in the prior art. The composite according to the present invention has excellent resilience and resistance to forces acting on the outside, so that it has high durability.

Next, the composite according to the present invention comprises a zinc oxide particle layer which is formed on the surface of the polyurethane matrix and in which the zinc oxide particles are densely aggregated, for example, in a flake or snow structure. The composite comprises a zinc oxide particle layer aggregated in a flake or snow structure on the surface of the polyurethane matrix to provide a surface roughness and an average BET specific surface area Thereby increasing the contact area of the oil and increasing the water repellency since a large amount of air pockets can be induced when a liquid containing water comes into contact with the surface.

Next, the composite according to the present invention may include a magnetic particle layer having magnetism on the zinc oxide particle layer, and the magnetic particle layer may have a form that surrounds the entire surface of the zinc oxide particle layer, And may have a shape that partially adsorbs and covers the surface of the particle layer.

At this time, the magnetic particle layer may include magnetic particles. Specifically, the magnetic particle layer may include magnetic particles containing at least one of pure iron oxide having magnetic properties, ferrite, magnetite, and a magnetic substance such as an alloy of these and a divalent metal. As an example, the magnetic particle layer may comprise magnetic particles comprising Fe ₃ O ₄ .

The present invention has an advantage in that position control and collection of the complex are easy by including the magnetic particle layer in the composite. Specifically, when the complex is used for large-scale oil-water separation such as oil removal from the ocean, the complex can be easily moved to a place where the oil floating on the sea surface is located by using a magnet. One complex can be easily recovered.

Next, the complex according to the present invention comprises a fatty acid layer surrounding the zinc oxide particle layer, wherein the fatty acid layer may comprise a fatty acid having 10 to 30 carbon atoms. Specifically, the fatty acid layer is composed of capric acid having 10 carbon atoms, lauric acid having 12 carbon atoms, myristic acid having 14 carbon atoms, palmitic acid having 16 carbon atoms, stearic acid having 18 carbon atoms, arachic acid having 20 carbon atoms, And hexanoic acid. For example, the composite may comprise stearic acid in the fatty acid layer surrounding the zinc oxide particles.

In addition, the average thickness of the fatty acid layer may be such that the surface energy can be sufficiently lowered without lowering the surface roughness of the composite. The average thickness of the fatty acid layer may be 20 nm or less, specifically 15 nm or less, 10 nm or less, 0.5 nm to 10 nm or 2 nm to 8 nm.

Generally, the polyurethane matrix has high affinity to water, so it can not measure the contact angle because it absorbs all the water contacted on the surface when measuring the static water contact angle. However, the composite according to the present invention includes a zinc oxide particle layer formed by aggregating zinc oxide particles on the surface of a polyurethane matrix in a flake or snow structure to maximize the surface roughness, By forming the coating layer with a fatty acid having 10 to 30 carbon atoms having a low energy, it is possible to realize both super hydrophobic and lipophilic properties on the surface of the polyurethane matrix.

As an example, the composite may have a static water contact angle of 150 ° or more, more specifically 150 ° to 170 °, 155 ° to 165 °, 157 ° To 165 °, 157 ° to 162 °, 159 ° to 164 °, or 160 ° to 162 °.

As another example, the composite may have a sliding water contact angle and a shedding water contact angle, each of which exhibits water repellency, of 15 ° or less, and more specifically, the average water slip 5 ° to 13 °, 5 ° to 11 °, 5 ° to 10 °, 3 ° to 9 °, 4 ° to 9 °, 5 ° 6 ° to 8 °, 7 ° to 9 °, or 6 ° to 9 °.

As another example, the composite has a very high affinity for organic materials such as oil, so that it absorbs all of the oil contacted to the surface during the measurement of the average static oil contact angle, And in this case the average static oil contact angle can be regarded as 0 °.

For example, the composite according to the present invention may have an average static water contact angle of 161 +/- 0.5 DEG, an average water slip angle and an average water flow angle of 8 +/- 0.5 DEG and 7 +/- 0.5 DEG, respectively.

Meanwhile, the composite according to the present invention includes a zinc oxide particle layer, a magnetic particle layer and a fatty acid layer on a polyurethane matrix, and has an X-ray photoelectron spectroscopy (XPS) analysis of 1022 ± 0.5 eV, 711 ± 0.5 eV, 533 ± 0.5 eV, 400 Lt; RTI ID = 0.0 > eV < / RTI > and 284.6 + 0.6 eV. X-ray photoelectron spectroscopy (XPS) analysis shows that the peak indicates the bond between the elements contained in the complex, and the intensity of the peak may vary depending on the relative amount between the bonds, which is controlled by controlling the content of the components contained in the complex . The composite of the present invention comprises a zinc oxide particle layer and a fatty acid layer on a polyurethane matrix, the zinc oxide particle layer and the fatty acid layer having a content capable of optimizing the surface roughness and surface energy of the composite, and the 1s bond of the carbon element (C) in the X-ray photoelectron spectroscopy The intensity ratio (Pc / Po) of the peak (Po) of 533 ± 0.5 eV representing the 1s binding energy of the oxygen element (O) to the 284.6 ± 0.6 eV peak representing the energy may be 1 to 3. More specifically, the intensity ratio (Pc / Po) of the peak indicating the 1s binding energy between the carbon element and the oxygen element is 1.3 to 3, 1.5 to 3, 1.8 to 3, 2 to 3, 2.5 to 3, 1 to 2.5, 1 to 2, 1.5 to 2.5, 1.8 to 2.7 or 2.1 to 2.5. The present invention can optimize the surface roughness and the surface energy of the composite by controlling the peak energy ratio of binding energy between the carbon element (C) and the oxygen element (O) within the above range during the X-ray photoelectron spectroscopic analysis of the composite.

Accordingly, the composite according to the present invention is a zinc oxide particle layer in which a zinc oxide particle aggregates in a flake or snow structure on a polyurethane matrix having a porous structure on the sea surface to form a micro-nano structure; A magnetic particle layer magnetized; And a fatty acid layer for lowering the surface energy are sequentially formed to provide excellent durability, a broad average BET specific surface area, a maximum average absorption amount to oil, a lipophilic property, a super hydrophobic property and a super water repellent property, It is possible to control and control the position of the complex by using the method of the present invention. Therefore, it can be effectively used as a material for the separation of water from oil leaking out into the ocean.

Method of making composite

In addition, the present invention, in one embodiment,

Immersing a polyurethane matrix having a sponge-like porous structure in a zinc oxide precursor solution, and irradiating microwaves to form a zinc oxide particle layer on the surface of the matrix;

Immersing a polyurethane matrix in which a zinc oxide particle layer is formed on a surface thereof in a solution containing magnetic particles to form a magnetic particle layer on the surface; And

And immersing the polyurethane matrix having the magnetic particle layer on its surface in a solution of 10 to 30 carbon atoms in which the fatty acid is dissolved to form a fatty acid layer on the surface.

The method for producing a composite according to the present invention is characterized in that a zinc oxide particle layer is formed on the surface of a polyurethane matrix having a porous structure on the sea surface by aggregating the zinc oxide particles into a flake or snow structure, After the particle layer is formed, the zinc oxide particle layer formed on the surface may be coated with a fatty acid to form a fatty acid layer, thereby preparing a composite.

Specifically, the step of forming the zinc oxide particle layer on the surface of the polyurethane matrix comprises immersing the polyurethane matrix in a zinc oxide precursor solution having a pH of 9 to 12 and having a predetermined concentration of zinc ions (Zn ^{2 +} ) dissolved therein, A zinc oxide particle layer in which zinc oxide particles are aggregated in a flake or snow structure having a large surface roughness can be formed on the polyurethane matrix.

In this case, the zinc oxide precursor solution of zinc acetate (Zn (OAc) _2), zinc chloride (ZnCl _2), zinc hydroxide (Zn (OH) _2), zinc nitrate (Zn (NO _{3) 2),} such as the zinc oxide precursor Is dissolved in a concentration of 0.1 M to 2 M, ammonia water is added to the aqueous solution to adjust pH to 9 to 12, and 0.1 M to 2 M, specifically 0.1 M to 1.5 M, 0.1 M to 1.2 M, 0.1 M to 1 M, 0.1 M to 0.6 M, 0.1 M to 0.5 M, 0.1 M to 0.3 M, 0.3 M to 0.5 M, 0.4 M to 0.7 M, 0.5 M to 1 M, 0.7 M to 1 M, 1 M to 1.5 M, 0.8 M to 1.2M or a concentration of zinc ions (Zn ^< ^{2 + &} gt ^; ) of 0.15M to 0.25M may be dissolved. In the present invention, it is possible to uniformly form zinc oxide particles on the surface of the polyurethane matrix by controlling the concentration of zinc ions (Zn ^{2 +} ) present in the zinc oxide precursor solution within the above range, The shape and growth direction of the zinc oxide particles can be controlled and the agglomerate shape of the zinc oxide particles can be controlled in a random radial manner, thereby maximizing the surface roughness of the composite.

In addition, the output of the microwave may be 1,000 W to 1,500 W, specifically 1,000 W to 1,500 W, 1,050 W to 1,300 W, or 1,080 W to 1,200 W, the frequency of the microwave may be 2,000 MHz to 3,000 MHz, May be from 2,200 MHz to 2,600 MHz or from 2,400 MHz to 2,500 MHz.

In addition, the microwave irradiation may include an irradiation step of microwave-treating the polyurethane matrix; And an aging step of leaving a microwave irradiated polyurethane matrix, and the irradiating step and the aging step may be repeated n times (integer of n < = 10).

The execution time of the irradiation step may be 10 to 100 seconds, specifically 10 to 80 seconds, 20 to 80 minutes, 30 to 70 seconds, 40 to 80 seconds, 50 to 70 seconds, 30 to 100 seconds, 50 to 100 Sec, 70 to 100 sec, or 55 to 65 sec.

Also, the aging time is 1 to 60 seconds, specifically 1 to 50 seconds, 1 to 40 seconds, 5 to 40 seconds. 10 to 40 seconds, 20 to 40 seconds, 30 to 60 seconds, 50 to 60 seconds, or 25 to 35 seconds.

As one example, the microwave irradiation may include an irradiating step of microwave-treating the polyurethane matrix for 57 to 62 seconds; And an aging step of leaving the microwave irradiated polyurethane matrix for 27 to 32 seconds, and the irradiation step and the aging step may be repeated twice.

The present invention is capable of uniformly maintaining the temperature of a zinc precursor solution and a polyurethane matrix by repeatedly performing micro-irradiation and aging for a specific time in a polyurethane matrix immersed in a zinc oxide precursor solution, It is possible to control the shape and growth direction of the zinc particles and adjust the agglomeration form of the zinc oxide particles to a flake or a snow structure so that the surface roughness of the composite can be maximized.

In addition, the step of forming the magnetic particle layer may be performed by immersing the polyurethane matrix having the zinc oxide particle layer on the surface thereof in a solution containing magnetic particles for 30 to 100 minutes or for 40 to 70 minutes.

Here, the magnetic particles may include at least one of pure iron oxide having magnetic properties, ferrite, magnetite, and a magnetic substance such as an alloy of these and a bivalent metal. As an example, the magnetic particles may comprise Fe ₃ O ₄ . When particles containing Fe ₃ O ₄ are used as the magnetic particles, the magnetic particles are prepared by adding ammonia water to a mixed solution of an iron precursor such as an iron precursor such as FeCl ₃ having a trivalent oxidation number and FeCl ₂ having a divalent oxidation number, The pH of the solution to which ammonia water is added may be from 11 to 12.

In addition, the concentration of the solution containing the magnetic particles may be 0.1 to 5 g / L, specifically 0.5 to 3 g / L, 0.5 to 1.5 g / L or 0.8 to 1.2 g / L. The present invention can form a magnetic particle layer on the surface of the composite with a thickness sufficient to impart magnetism to the composite by controlling the concentration of the solution containing the magnetic particles within the above range

Further, the step of coating the formed zinc oxide particle layer with a fatty acid to form a fatty acid layer may include immersing the polyurethane matrix having a zinc oxide particle layer on its surface in a fatty acid solution having a concentration of 0.005M to 0.1M or 0.005 to 0.05mM for 1 to 10 minutes And then the fatty acid layer can be formed by dip coating.

At this time, the fatty acid may include a fatty acid having 10 to 30 carbon atoms. Specifically, the fatty acid layer is composed of capric acid having 10 carbon atoms, lauric acid having 12 carbon atoms, myristic acid having 14 carbon atoms, palmitic acid having 16 carbon atoms, stearic acid having 18 carbon atoms, arachic acid having 20 carbon atoms, And hexanoic acid. For example, the composite may include stearic acid in the fatty acid layer surrounding the zinc oxide particle layer.

In addition, the average thickness of the fatty acid layer may be such that the surface energy can be sufficiently lowered without lowering the surface roughness of the composite. Specifically, the average thickness of the fatty acid layer may be 20 nm or less, specifically 15 nm or less, 10 nm or less, 0.5 nm to 10 nm or 2 nm to 8 nm, / RTI > and / or < RTI ID = 0.0 > concentration. ≪ / RTI >

Materials for oil-water separation

Furthermore, the present invention provides, in one embodiment, a material for water drainage comprising a composite according to the present invention.

The material for water softening according to the present invention is characterized in that zinc oxide particles aggregate in a flake or snow structure on a polyurethane matrix having a porous structure on the sea surface to form a zinc oxide particle layer, Can be reused including the complex of the present invention which is not only excellent in durability but also has a wide average BET specific surface area and exhibits lipophilic property, super hydrophobic property and super water repellency, and is excellent in oil separation efficiency.

Specifically, a polyurethane sponge having a porous structure used as a general water-dispersible material can realize super-hydrophobicity through various surface treatments, but does not exhibit water repellency. Therefore, when oil is used in fresh water and / And absorbs a considerable amount of water to be present in the water. However, the oil-water separating material according to the present invention exhibits lipophilicity as well as lipophilic property and super-hydrophobic property, so that when oil flows out into freshwater and / or oceans, only the oil floating on the water surface is selectively absorbed, There is an advantage that the efficiency is excellent and the treatment after the water separation is easy.

As one example, the oil-water separating material exhibits lipophilic, super-hydrophobic, and super-water-repellent properties including the composite according to the present invention. The material is immersed in a reactor and the surface of the material is immersed in a solvent such as hexane (n-hexame), toluene, dichloromethane, vacuum oil, gasoline, soybean oil or diesel ) And water in a volume ratio of 1: 1, the oil is absorbed and passed through the material, but the water remains on the surface without being absorbed by the material. The separation efficiency of water may be 95% or more, specifically 97% or more, based on the volume of water contained in the mixed solution.

As another example, the water-oil separating material includes a composite according to the present invention and is excellent in durability, so that it is possible to use n-hexane, toluene, dichloromethane, vacuum oil, When oil separation and washing are performed 100 times in a mixed solution of gasoline, soybean oil or diesel and water in a volume ratio of 1: 1, The separation efficiency of 70% or more is exhibited, and the separation efficiency of 80% or more can be exhibited for a low viscosity component such as hexane (n-hexane) when the glass is separated by 50 times.

Meanwhile, the maximum average adsorption amount of the water-swellable material according to the present invention may be 20 to 200 g per unit weight (g), and specifically 20 to 180 g, 20 to 160 g, 20 to 140 g, 20 20 to 100 g, 20 to 70 g, 20 to 70 g, 20 to 60 g, 20 to 50 g, 20 to 30 g, 30 to 200 g, 50 to 200 g, 70 to 200 g, 90 to 200 g, 100 to 200 g, , 140 to 200 g, 160 to 200 g, 180 to 200 g, 25 to 150 g, 30 to 110 g, 30 to 90 g, 30 to 70 g, 30 to 60 g, 35 to 90 g, 35 to 70 g, 35 to 60 g, have. The maximum average adsorption amount of the water-swellable material may be influenced by the viscosity of the oil to be adsorbed, and thus adsorbed in the above range depending on the type of oil to be separated.

As an example, when the water-splitting material is subjected to oil-water separation of hexane (viscosity: 13.10 mm 2 / s) mixed with water, the maximum average adsorption amount per unit weight (1 g) is 32.01 ± 0.05 g The maximum average adsorption amount for light oil in the case of oil-water separation of a mixture of light oil (viscosity: 103.99 mm 2 / s) and water may be 80.98 ± 0.05 g per unit weight (1 g).

Furthermore, the material for water softening according to the present invention has an excellent durability.

As an example, since the material for water softening does not cause loss of the zinc oxide particle layer, the magnetic particle layer and the fatty acid layer formed on the surface of the polyurethane sponge, even if surface friction occurs or shape deformation occurs under ultrasonic irradiation or a load of 2,000 gr, The static water contact angle as well as the average slip angle and average water flow angle can be maintained at about 98% or more.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are merely illustrative of the present invention, and the present invention is not limited to the following Examples and Experimental Examples.

Manufacturing example  One

Magnetic particles were prepared by coprecipitation method. Specifically, 0.1 M FeCl ₃ solution (100 ml) was mixed with 0.1 M FeCl ₂ solution (50 ml), ammonia water was added dropwise to the mixed solution, and a precipitate was formed through the reaction shown in the following Formula 1. At this time, the temperature of the mixed solution was 80 ± 5 ° C., the pH was 11 to 12, and the reaction was carried out for 3 hours while maintaining the temperature and the pH:

Fe₃O₄↓ + H₂O (1).[Formula 1] Fe ^{2 +} + Fe ^{3 +} + OH ^-

Fe ₃ O ₄ ↓ + H ₂ O (1).

When the reaction was completed, the temperature of the mixed solution was cooled to room temperature, the solution was filtered, and the filtrate was washed with water and acetone to neutralize the pH. Then, the neutralized filtrate were dried in a 60 ℃ oven for 12 hours, pulverized to a grinder (grinder) to obtain magnetic particles (Fe ₃ O ₄ particles).

Example  One

A polyurethane sponge having a width of 3 cm, a width of 3 cm and a thickness of 3 cm was prepared, and the prepared polyurethane sponge was washed with distilled water and ethanol three times to remove impurities remaining on the surface.

Separately, 25 wt% aqueous ammonia was added dropwise to 100 mL of a 1M aqueous solution of zinc acetate (Zn (OAc) ₂ ) to dissolve all the white zinc acetate precipitated in the aqueous zinc acetate solution. At this time, the pH of the solution was 10.5 ± 0.3. The dissolved aqueous zinc acetate solution was added to the reaction flask and the polyurethane sponge prepared above was immersed in an aqueous solution of zinc acetate. (Output: 1120 ± 20 W, frequency: 2450 ± 10 MHz). At this time, the microwaves were irradiated and the polyurethane sponge irradiated with microwaves was aged to be left standing. This process was repeated three times. Each irradiation step irradiated with microwaves was performed for 60 ± 2 seconds, and each aging step for leaving a polyurethane sponge irradiated with microwave was performed for 30 ± 2 seconds. After completion of the above processes, the temperature of the aqueous zinc acetate solution was cooled to room temperature (20 ± 1 ° C.) for 5 minutes, and the polyurethane sponge immersed in the aqueous zinc acetate solution was taken out, washed with distilled water and air dried. The magnetic particles (Fe ₃ O ₄ particles, 0.1 g) obtained in Production Example 1 were dispersed in ethanol (100 ml), and the dried polyurethane sponge was immersed in the solution. Then, the solution was stirred at room temperature (20 ± 2 ° C) A magnetic particle layer was formed on the surface of the urethane sponge. Complex _{(PU-ZnO-Fe 3 O} 4 washing the immersed polyurethane sponge surface with distilled water for 5 minutes to a solution of stearic acid (100㎖) of a 10mM concentration of dissolving the cleaning polyurethane sponge was taken out by air drying the ethanol damgwotda -SA), and the average thickness of the stearic acid layer on the surface was 8 to 12 nm.

Comparative Example  One

A polyurethane sponge having a width of 3 cm, a width of 3 cm and a thickness of 3 cm was prepared, and the prepared polyurethane sponge was washed with distilled water and ethanol three times to remove impurities remaining on the surface.

Separately, 25 wt% aqueous ammonia was added dropwise to 100 mL of a 1M aqueous solution of zinc acetate (Zn (OAc) ₂ ) to dissolve all the white zinc acetate precipitated in the aqueous zinc acetate solution. At this time, the pH of the solution was 10 to 11. The dissolved aqueous zinc acetate solution was added to the reaction flask and the polyurethane sponge prepared above was immersed in an aqueous solution of zinc acetate. (Output: 1120 ± 20 W, frequency: 2450 ± 10 MHz). At this time, the microwaves were irradiated and the polyurethane sponge irradiated with microwaves was aged to be left standing. This process was repeated three times. Each irradiation step irradiated with microwaves was performed for 60 ± 2 seconds, and each aging step for leaving a polyurethane sponge irradiated with microwave was performed for 30 ± 2 seconds. After the completion of the above-mentioned treatments, the temperature of the aqueous zinc acetate solution was cooled to room temperature (20 占 1 占 폚) for 5 minutes. Thereafter, the polyurethane sponge immersed in the aqueous zinc acetate solution was taken out, washed with distilled water, and naturally dried to prepare a composite (PU-ZnO).

Comparative Example  2

A polyurethane sponge having a width of 3 cm, a width of 3 cm and a thickness of 3 cm was prepared, and the prepared polyurethane sponge was washed with distilled water and ethanol three times to remove impurities remaining on the surface. (PU-SA) was prepared by immersing the polyurethane sponge in 100 ml of a 10 mM concentration of stearic acid solution dissolved in ethanol for 5 minutes and drying it naturally, wherein the average thickness of the stearic acid layer on the surface was 8 to 12 nm .

Experimental Example  One

In order to confirm the surface properties of the composite according to the present invention, the polyurethane sponge, which is a non-treated group, and the composite prepared in Example 1 and Comparative Examples 1 and 2 were subjected to Scanning Electron Microscope- Energy dispersive X-ray spectrometry (SEM-EDS) analysis was performed. The results are shown in FIG.

As shown in FIG. 1, the composite according to the present invention has a micro-nano-type surface structure, and thus has excellent BET surface area.

Specifically, referring to FIG. 1, the composite of Comparative Example 2 in which the polyurethane sponge and the surface thereof were coated with stearic acid (SA) showed smoothness on the surface. On the other hand, in the composite of Comparative Example 1 in which a zinc oxide particle layer was formed on the surface of the polyurethane sponge, it was confirmed that the zinc oxide particles aggregated on the surface with a flame or a snow structure by applying a microwave to the zinc oxide particle layer have. The composite of Example 1 including a fatty acid layer containing stearic acid on the surface of a zinc oxide particle layer formed on a polyurethane sponge by a zinc oxide particle layer in the same manner as the composite of Comparative Example 1 has a carboxyl group of stearic acid And the zinc oxide particles were more self - assembled through the strong coordination bond, and the magnetic particle layer was found to maintain the surface roughness realized by the zinc oxide particle layer. It can also be seen that the carbon element (C), the oxygen element (O), the zinc element (Zn) and the iron element (Fe) are uniformly distributed in the composite of Example 1.

From these results, it can be seen that the composite according to the present invention has a micro-nano structure in which a zinc oxide particle layer is agglomerated into a flake or snow structure on the surface of a sponge porous polyurethane sponge having three-dimensionally open pores, And the surface properties such as the average BET specific surface area are excellent.

Experimental Example  2

X-ray diffraction (XRD) was measured on the polyurethane sponge as a non-treated group and the composite prepared in Example 1 and Comparative Example 1 to confirm the surface composition of the composite according to the present invention. At this time, the measurement of X-ray diffraction pattern to D8 (CuKa radiation, 40 kV, 30 mA) using a, wavelength 1.5406 Å to 0.02 ° / injected at a rate in the 2 θ range of 10-80 ° of sec Bruker Co. (Germany) ≪ / RTI >

X-ray photoelectron spectroscopy (XPS) was measured on the polyurethane sponge and each composite, and the measured results are shown in FIGS. 2 and 3. FIG.

As shown in FIGS. 2 and 3, it can be seen that the composite according to the present invention has a structure in which fatty acid is coated on the surface of the zinc oxide particle layer aggregated on the polyurethane sponge.

Specifically, FIG. 2 is a graph showing the results of XRD analysis of the untreated polyurethane sponge and the composite prepared in Example 1 and Comparative Example 1. In contrast to the untreated polyurethane sponge, in Examples 1 and 2, The composite of Comparative Example 1 was prepared from the zinc oxide particles at a specific angle of 2θ = 32.01 ± 0.5 °, 34.17 ± 0.5 °, 36.20 ± 0.5 °, 47.35 ± 0.5 °, 56.62 ± 0.5 °, 62.92 ± 0.5 °, 66.92 ± 0.5 °, A peak of ± 0.5 ° and 69.09 ± 0.5 ° was confirmed. The composite of Example 1 further includes a Fe ₃ O ₄ particle layer which is magnetic particles on the zinc oxide particle layer and further comprises peaks at 2? = 30.1 ± 0.5 °, 43.1 ± 0.5 ° and 53.5 ± 0.5 ° together with the peak Respectively.

FIG. 3 is a graph showing X-ray photoelectron spectroscopy (XPS) results of the untreated polyurethane sponge and the composite prepared in Example 1. In the polyurethane sponge, 533. + -. 0.5 eV, 400. + -. 0.5 eV, and 284.6. (P) between the carbon element (C) and the oxygen element (O) was found at 0.6 eV, indicating a 1s bond of the carbon element (O), the nitrogen element (N) _C / P ₀ ) was found to be about 0.7 to 0.9. In contrast, the composite of Example 1, like the untreated polyurethane sponge, had carbon atoms at 533 ± 0.5 eV, 400 ± 0.5 eV, and 284.6 ± 0.6 eV, A peak of 1022 ± 5 eV indicating a 2p3 bond of a zinc element (Zn) of zinc oxide together with a peak indicating a 1s bond of oxygen element (O), nitrogen element (N) and oxygen element (O) ) Showed peaks at 724 ± 0.5 eV and 711 ± 0.5 eV indicating 2p1 / 2 and 2p3 / 2 bonds, and carbon Cattle (C) and the peak intensity ratio of carbon element _{(O) ((P C /} P O) is due to the stearic acid was found to be about 2.2 to 2.4.

These results indicate that the composite of the present invention uniformly surrounds the zinc oxide particle layer and the magnetic particle layer on the polyurethane sponge and uniformly surrounds the surface of the zinc oxide particle layer.

Experimental Example  3

The following experiment was conducted to evaluate the physical properties of the composite according to the present invention.

end) Evaluation of affinity to water

The untreated polyurethane sponge and the composites prepared in Example 1 and Comparative Examples 1 and 2 were measured for static water contact angle (static) using a contact angle meter (Model: SmartDrop, manufactured by Femtofab Co. Ltd) WCA), sliding water contact angle (sliding WCA), and shedding water contact angle (shedding WCA) and static oil contact angle were measured. At this time, each measurement was performed by dropping 10 μl of water or oil drop on the surface for each measurement, and repeated three times to derive the average value. The results are shown in Table 1 and FIG.

Water (H ₂ O) Static contact angle Slip angle Flow angle Untreated group Not measurable Not measurable Not measurable Example 1 161 ± 1 ° 8 ± 1 ° 7 ± 1 ° Comparative Example 1 119 ± 1 ° 35 ± 1 ° 30 ± 1 ° Comparative Example 2 92 ± 1 ° 54 ± 1 ° 52 ± 1 °

As shown in Table 1 and Fig. 4, it can be seen that the composite according to the present invention has pyrochrome, water repellency and lipophilic properties on the surface.

Specifically, the composite prepared in Example 1 exhibited a static water contact angle of 160 ° to 162 ° indicating affinity to water, and the water slip angle and water flow angle indicating water repellency were 11 ° or less, specifically, Lt; RTI ID = 0.0 > 6-9 < / RTI > In addition, the composite absorbed all of the oil and was unable to measure the static oil contact angle indicating lipophilicity.

On the other hand, the untreated polyurethane sponge has high affinity for both water and oil, absorbing water or oil falling on the surface during contact angle measurement, so that water or static oil contact angle as well as slip angle and flow angle measurement It was impossible. In addition, the composites prepared in Comparative Examples 1 and 2 each showed a hydrophobic property including a zinc oxide particle layer or a stearic acid layer on the surface, but the degree of the hydrophobicity was low and the static water contact angle was less than 120 °. In addition, the composites of Comparative Examples 1 and 2 were remarkably low in water repellency, so that the slip angle and the flow angle with respect to water were 30 ° or more.

This means that the surface roughness of the composite due to the zinc oxide particle layer must be controlled simultaneously with the surface energy due to the fatty acid in order to realize the superhydrophobicity and water repellency.

Accordingly, the composite according to the present invention has a structure in which a zinc oxide particle layer is formed on a polyurethane sponge in a flake or snow structure, and the surface of the zinc oxide particle layer is surrounded by a fatty acid, whereby the affinity to oil is remarkably high , But the superhydrophobicity and water repellency are excellent.

B) Magnetic properties

Magnetization-Hysteresis (MH) loops were measured at room temperature (25 ± 1 ° C) for the Fe ₃ O ₄ particles as magnetic particles and the composite prepared in Example 1. The magnetization-hysteresis (MH) loop of the composite material was re-measured at room temperature (25 ± 1 ° C.) after the water separation using the composite material of Example 1 was repeated 20 times. The results are shown in FIG. 5 .

5, the composite of Example 1 was found to exhibit a saturation magnetization (M _s ) of about 5 ± 0.02 emu / g, and after about 100 oil water separations using the composite, about 2.5 (M _s ) Saturation magnetization was confirmed to be maintained.

This means that the composite according to the invention exhibits magnetic properties including Fe ₃ O ₄ particles, which are magnetic particles, and that the magnetic properties remain constant after repeated use of the composite.

Experimental Example  4

In order to evaluate the water separation efficiency of the complex according to the present invention, the following experiment was conducted.

The composite (diameter 7 ± 2 cm, height 1 cm) prepared in Example 1 was fixed to a tube having a diameter of 7 cm equipped with a stainless steel mesh as a stopper, and a beaker was prepared under the tube. Then, a solution (30 ml) of oil and water mixed at a volume ratio of 1: 1 was poured into the tube and waited until the oil in the solution passed all through the untreated polyurethane sponge or complex, The oil that is used can be either n-hexame, toluene, dichloromethane, gasoline, vacuum oil, soybean oil or diesel, Emulsions mixed with 1: 1 oil were used. When all of the oil in the solution had been absorbed and passed through the composite, the volume of water remaining on the top without passing through the composite was measured. From the measured results, the separation efficiency of oil and water was derived using the following formula 2, and the maximum average absorption amount of the oil per unit weight of the composite (based on 1 g) was calculated. This procedure was repeated 100 times, and the obtained results are shown in FIG. 6 and Table 2.

[Formula 2]

Oil water separation efficiency (k) = V ₁ / V ₀ X 100

In Equation 2,

V ₁ represents the volume of water remaining on the top of the polyurethane sponge or composite after separation,

V ₀ represents the volume of water contained in the pre-separation mixed solution.

Unit: g / g Hexane toluene Dichloromethane Gasoline Soybean oil Diesel Vacuum oil Room temperature (20 ± 1 ℃) Viscosity 0.32 cP 0.58 cP 0.4 cP 0.6 cP 80 cP - - Maximum average absorption 32.01 + - 0.1 g / g 49.0 + - 0.1 g / g 58.1 + - 0.1 g / g 59.2 ± 0.1 g / g 65.1 + - 0.1 g / g 80.98 + - 0.1 g / g 108.9 ± 0.1 g / g Separation efficiency 99.89% 99.88% 99.87% 99.5% 99.2% 99.0% 98.21%

As shown in FIG. 6 and Table 2, it can be seen that the composite according to the present invention is excellent in oil-water separation efficiency regardless of the kind of oil and can be used repeatedly.

Specifically, it was confirmed that the composite prepared in Example 1 was separated from water at a high efficiency of 98% or more with respect to oils such as hexane, toluene, dichloromethane, gasoline, vacuum oil, soybean oil and light oil. In addition, it was confirmed that the maximum average absorption amount of the composite was about 30 to 110 g / g depending on the type of oil, and the maximum average absorption amount tended to increase with increasing viscosity of the oil at room temperature.

Furthermore, the composite of Example 1 showed that the maximum average amount of absorption of the complex to oil was maintained at 70% or more even when oil-water separation of the mixed solution was repeated 30 times, regardless of the oil component, and n-hexane It was confirmed that the same low viscosity components were retained by 80% or more even when oil separation was performed 50 times or more. This is because the oil that has been absorbed in the pores of the composite in the oil separation is remained and the total absorption amount of the oil absorbed thereafter decreases.

From these results, it can be seen that the composite according to the present invention is excellent in oil-water separation efficiency.

Experimental Example 4

In order to evaluate the durability of the composite according to the present invention, the following experiment was conducted.

Specifically, the composite prepared in Example 1 was subjected to external force by the following three methods, and the water contact angle (WCA) before and after the external force was applied was measured to confirm the change. The results are shown in FIG. 7 :

[Method 1] After immersing the composite in water, ultrasonic irradiation was performed for 30 minutes at room temperature (22 ± 2 ° C) using an ultrasonic grinder, and then the composite was naturally dried and the water contact angle was measured.

[Method 2] The reciprocating motion of 3 times at 1 cm / s was carried out under a load of 2,000 gr per unit area of the composite, and then the water contact angle of the composite was measured.

[Method 3] Both ends of the composite body (3 cm in length, 3 cm in length and 3 cm in length) were held, and the water contact angle of the composite body was measured.

As shown in FIG. 7, the composite according to the present invention is excellent in durability because it has excellent resistance to external force.

Specifically, in the composite prepared in Example 1, loss of the zinc oxide particle layer, the magnetic particle layer and the fatty acid layer formed on the surface of the polyurethane sponge was not generated even when surface friction or shape deformation occurred under ultrasonic irradiation or at a load of 2,000 gr The average static water contact angle as well as the mean slip angle and average water flow angle were maintained at about 98% or more.

From these results, it can be seen that the composite according to the present invention has excellent durability and realizes excellent super-hydrophobic property and water-repellent property even if external force is applied.

Claims (14)

A polyurethane matrix having a spongy porous structure;
A zinc oxide particle layer formed on the matrix;
A magnetic particle layer formed on the zinc oxide particle layer; And
And a fatty acid layer formed on the magnetic particle layer and containing 10 to 30 carbon atoms.
The method according to claim 1,
The complex,
The average static water contact angle is 150 DEG or more,
A composite having a sliding water contact angle of 10 ° or less.
The method according to claim 1,
X-ray photoelectron spectroscopy (XPS) analysis of the complex showed binding peaks at 1022 ± 0.5 eV, 711 ± 0.5 eV, 533 ± 0.5 eV, 400 ± 0.5 eV and 284.6 ± 0.6 eV,
Wherein the ratio (Pc / Po) of the intensity of the 1s binding peak (Pc) of the carbon element to the intensity of the 1s binding peak (Po) of the oxygen element is 1 to 3.
The method according to claim 1,
Wherein the magnetic particles comprise at least one kind of magnetic particles selected from the group consisting of iron oxides, ferrites, magnetites, and alloys of these and bivalent metals.
The method according to claim 1,
The polyurethane matrix comprises open pores,
Wherein the average size of the pores is 100 占 퐉 to 1,000 占 퐉.
The method according to claim 1,
The fatty acid includes at least one selected from the group consisting of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid.
The method according to claim 1,
The average thickness of the fatty acid layer was 20 Nm or less.
Immersing a polyurethane matrix having a sponge-like porous structure in a zinc oxide precursor solution, and irradiating microwaves to form a zinc oxide particle layer on the surface of the matrix;
Immersing a polyurethane matrix in which a zinc oxide particle layer is formed on a surface thereof in a solution containing magnetic particles to form a magnetic particle layer on the surface; And
And immersing a polyurethane matrix having a magnetic particle layer on its surface in a solution of a fatty acid having 10 to 30 carbon atoms dissolved therein to form a fatty acid layer on the surface.
9. The method of claim 8,
Wherein the zinc oxide precursor solution comprises 0.1M to 2M zinc ions (Zn ^< ^{2 + &} gt ^; ).
9. The method of claim 8,
Wherein the output of the microwave is from 1,000 W to 1,500 W.
9. The method of claim 8,
Wherein the frequency of the microwave is from 2,000 MHz to 3,000 MHz.
9. The method of claim 8,
In the microwave irradiation,
An irradiation step of subjecting the polyurethane matrix to microwave treatment for 10 to 100 seconds; And
And an aging step in which the microwave irradiated polyurethane matrix is left for 1 to 60 seconds,
Wherein the irradiation step and the aging step are repeated n times (n < = 10).
A material for water softening including the composite according to claim 1.
14. The method of claim 13,
Wherein the maximum average adsorption amount to oil is 20 to 200 g per unit weight (g).

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