KR101923181B1 - Surface modification of hydrophobic polymer mesh using hydrophilic surface modifier and method of surface treatment by coating with urethane - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface modification method of a hydrophobic polymeric mesh using a hydrophilic surface modifier and a surface treatment method using urethane coating. More particularly, the present invention relates to a method of surface modification of a hydrophobic polymeric mesh using a hydrophilic surface modifier. Modifying the surface of the hydrophobic polymeric mesh through a dyeing reaction of the hydrophilic modifier by heating the high pressure reactor; And a step of washing and drying the surface of the PET mesh modified with the hydrophilic modifier, and a method for modifying the surface of a hydrophobic polymer mesh using a hydrophilic surface modifier, and a method for modifying a surface of a hydrophobic polymer mesh using a diisocyanate compound, a glycol ether and an ester compound as a diluent, Preparing a coating liquid by mixing a catalyst; And a step of immersing the hydrophobic polymer mesh modified with a hydrophilic modifier in a coating solution and then heat treating the surface of the hydrophobic polymer mesh to form a urethane coating layer on the surface of the hydrophobic polymer mesh. A surface treatment method is provided.
The surface of the hydrophobic polymeric mesh is treated with the hydrophilic surface modifier and the urethane coating by the method of the present invention to reduce the size of the mesh of the hydrophobic polymeric mesh and to suppress the leakage of the cell, It can be used as a culture membrane for culturing microalgae in an actual marine environment by maintaining a high ion permeability by surface treatment with a modifier.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polymer surface modifier and a surface treatment method using the hydrophilic surface modifier,

The present invention relates to a surface modification method of a hydrophobic polymeric mesh using a hydrophilic surface modifier and a surface treatment method using urethane coating. More particularly, the present invention relates to a method for surface treatment of a hydrophobic polymeric mesh using a hydrophilic surface modifier, Surface modification of hydrophobic polymeric meshes and surface treatment by urethane coating.

Today, fossil fuels such as petroleum and coal are the most used fuels as efficient energy, but their limitations are revealed in depletion and environmental pollution. As a result, various researches and developments have been made on alternative energy, but there are limitations such as facility cost, additional environmental destruction, and low energy efficiency.

In this situation, bio-energy field is in the spotlight. In particular, bio-diesel does not need energy using fossil fuel but only solar energy which is infinite resource. It is similar to fossil fuel, so existing distribution system will be used There is an advantage that it can be.

However, in the case of early biodiesel, since edible crops and trees were used, there were many limitations associated with food and environmental problems. In recent years, microalgae have been proposed as raw materials for obtaining biodiesel.

Thus, in order to improve the productivity of biodiesel using microalgae, a lot of research has been conducted on the material of the photobioreactor used for culturing microalgae.

However, in order for the photobioreactor to be used for culturing microalgae in an actual marine environment, the permeability of the nutrients necessary for the growth of the microalgae must be high, the microalgae must not leak, and the strong intensity It is necessary to have microbial growth conditions such as having a microbial growth condition.

However, a photobioreactor for satisfying the micro-algae growth conditions has not yet been developed.

Therefore, in order to improve the productivity of biodiesel, it is necessary to cultivate microalgae in various directions. Therefore, it is urgent to research and develop materials for photobioreactors that can satisfy these conditions.

Korea Patent Publication No. 2015-0108880

It is an object of the present invention to provide a method for regulating cell size of fine algae in an actual marine environment by controlling mesh size of a mesh fabric fabric made of PET, which is one kind of polyester polymer, to suppress cell leakage and maintaining high ion permeability due to hydrophilicity And to provide a surface modification method of a hydrophobic polymeric mesh using a hydrophilic surface modifier and a surface treatment method using urethane coating.

In order to accomplish the above object, the present invention provides an anthracene-sorbitol ethoxylate complex represented by the following general formula (1).

[Chemical Formula 1]

이며, R ₁ to R ₆ are the same or different from each other and represent hydrogen or

Lt;

n is 2 to 10;

The present invention also provides a hydrophilic modifier for a hydrophobic polymeric mesh comprising an anthracene-sorbitol ethoxylate complex according to the following general formula (1) or (2).

[Chemical Formula 1]

이며, R ₁ to R ₆ are the same or different from each other and represent hydrogen or

Lt;

n is 2 to 10;

(2)

n is 2 to 10;

In addition, the present invention provides a method of manufacturing a high pressure reactor, comprising: introducing distilled water, a hydrophilic modifier, and a hydrophobic polymer mesh into a high pressure reactor; Modifying the surface of the hydrophobic polymeric mesh through a dyeing reaction of the hydrophilic modifier by heating the high pressure reactor; And washing and drying the surface of the PET mesh modified with the hydrophilic modifier. The present invention also provides a method for surface modification of a hydrophobic polymeric mesh using a hydrophilic surface modifier.

The present invention also provides a method for preparing a coating composition, comprising: preparing a coating solution by mixing a diisocyanate compound, a glycol ether and an ester compound as a diluent, and a urethane curing catalyst; And a step of immersing the hydrophobic polymer mesh modified with a hydrophilic modifier in a coating solution and then heat treating the surface of the hydrophobic polymer mesh to form a urethane coating layer on the surface of the hydrophobic polymer mesh. A surface treatment method is provided.

The present invention also provides a photobioreactor comprising the hydrophilic modifier.

The present invention also provides a method for culturing microalgae comprising culturing microalgae in the photobioreactor.

The surface of the hydrophobic polymeric mesh is treated with the hydrophilic surface modifier and the urethane coating by the method of the present invention to reduce the size of the mesh of the hydrophobic polymeric mesh and to suppress the leakage of the cell, It can be used as a culture membrane for culturing microalgae in an actual marine environment by maintaining a high ion permeability by surface treatment with a modifier.

Fig. 1 schematically shows a PET mesh surface treatment process; Fig.
2 shows a process for synthesizing an anthracene-sorbitol ethoxylate complex according to Example 1;
3 is a graph showing the results of ¹ H-NMR analysis of the anthracene-sorbitol ethoxylate complex synthesized according to Example 1;
4 is a view showing the result of confirming introduction of a hydrophilic surface modifier according to Experimental Example 1;
FIG. 5 is a graph showing IR spectra of a PET mesh fabric, a PET mesh surface modified only with a hydrophilic modifier according to Comparative Example 1, and a PET mesh surface treated according to Example 2; FIG.
Fig. 6 is a graph showing the results of the comparison between the PET mesh fabric Pristine, the PET mesh which has only undergone surface modification with the hydrophilic modifier according to the comparative example 1, the PET mesh with only the urethane coating according to the comparative example 2, (A), the permeability (b), the ion permeability (c), and the cell permeability (d) of the distilled water;
7 is a graph showing the results of the reproducibility analysis of the surface treatment process of the PET mesh according to Experimental Example 3; And
Fig. 8 is a graph showing the cell culture efficiency in the actual marine environment of the PET mesh fabric Pristine and the PET mesh surface-treated according to Example 2. Fig.

Hereinafter, the surface modification of the hydrophobic polymeric mesh using the hydrophilic surface modifier of the present invention and the surface treatment method using the urethane coating will be described in more detail.

The inventors of the present invention have made researches on a surface modification method of a PET-based mesh fabric, and have found that an anthracene-sorbitol ethoxylate complex having a hydrophilic polymer and a large number of hydroxyl groups (-OH groups) is introduced on the surface of a hydrophobic polymer mesh It is possible to effectively form the urethane coating as well as the surface modification, so that the mesh size of the hydrophobic polymer mesh can be controlled and the cell leakage can be effectively suppressed, thereby completing the present invention.

The present invention provides an anthracene-sorbitol ethoxylate complex represented by the following general formula (1).

[Chemical Formula 1]

이며, R ₁ to R ₆ are the same or different from each other and represent hydrogen or

Lt;

n is 2 to 10;

The anthracene-sorbitol ethoxylate complex may be a compound represented by the following general formula (2), but is not limited thereto.

(2)

n is 2 to 10;

The present invention also provides a hydrophilic modifier for a hydrophobic polymeric mesh comprising an anthracene-sorbitol ethoxylate complex according to the following general formula (1) or (2).

[Chemical Formula 1]

이며, R ₁ to R ₆ are the same or different from each other and represent hydrogen or

Lt;

n is 2 to 10;

(2)

n is 2 to 10;

In addition, the present invention provides a method of manufacturing a high pressure reactor, comprising: introducing distilled water, a hydrophilic modifier, and a hydrophobic polymer mesh into a high pressure reactor; Modifying the surface of the hydrophobic polymeric mesh through a dyeing reaction of the hydrophilic modifier by heating the high pressure reactor; And washing and drying the surface of the PET mesh modified with the hydrophilic modifier. The present invention also provides a method for surface modification of a hydrophobic polymeric mesh using a hydrophilic surface modifier.

The hydrophobic polymer may be selected from the group consisting of polyethyleneterephthalate (PET), polystyrene (PS), polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), polysulfone (PSF) , Polyethylene (PE), polypropylene (PP), and polycarbonate (PC), but the present invention is not limited thereto.

The step of modifying the surface of the hydrophobic polymeric meshes may be performed by heating at 110 to 150 ° C in a high-pressure reactor for 2 to 4 hours, but is not limited thereto.

The present invention also provides a method for preparing a coating composition, comprising: preparing a coating solution by mixing a diisocyanate compound, a glycol ether and an ester compound as a diluent, and a urethane curing catalyst; And a step of immersing the hydrophobic polymer mesh modified with a hydrophilic modifier in a coating solution and then heat treating the surface of the hydrophobic polymer mesh to form a urethane coating layer on the surface of the hydrophobic polymer mesh. A surface treatment method is provided.

Specifically, Fig. 1 schematically shows a PET mesh surface treatment process. Referring to FIG. 1, an anthracene portion of the modifier is present in the hydrophobic polymer mesh in a form in which the hydrophilic polymer mesh is inserted into the hydrophobic polymer mesh using a dyeing process similar method, and a hydrophilic portion, polyethylene glycol, is present on the hydrophobic polymer mesh surface. The polymer mesh surface can be modified with a hydrophilic modifier.

In addition, many hydroxyl groups present on the surface of the hydrophobic polymer mesh can be easily urethane-coated.

The glycol ether compound as the diluent may be selected from the group consisting of diethyleneglycol diethyl ether, diethyleneglycol dibutyl ether, dipropyleneglycol dimethyl ether, dipropyleneglycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethyleneglycol dibutyl ether, ethylene glycol methyl ether, ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate. r acetate).

The diisocyanate compound may be selected from the group consisting of hexamethylene diisocyanate, diphenyl methane diisocyanate, tolunene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, diisocyanate, poly (hexamethylene diisocyanate), and the like, but the present invention is not limited thereto.

The urethane curing catalyst may be, but is not limited to, dibutyltin dilaurate.

The step of forming the urethane coating layer on the surface of the hydrophobic polymer mesh can be performed by immersing the hydrophobic polymer mesh modified with the hydrophilic modifier according to claim 3 in the coating solution and then performing the heat treatment at 80 to 120 ° C for 30 seconds to 1 minute and 30 seconds, But is not limited thereto.

The present invention also provides a photobioreactor comprising the hydrophilic modifier.

The present invention also provides a method for culturing microalgae comprising culturing microalgae in the photobioreactor.

Hereinafter, the surface modification of the PET mesh using the hydrophilic surface modifier of the present invention and the surface treatment method using the urethane coating will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples.

Example 1 Synthesis of Anthracene-sorbitol ethoxylate-Based Compounds (see FIG. 2)

1. Synthesis of Anthracene-9-carbonyl chloride

Anthracene-9-carbonyl chloride was prepared by dissolving 3.5 g of 9-anthracenecarboxylic acid in 100 cm ³ round bottom flask, adding oxalyl chloride solution , 2 M solution in dichloromethane, 1575 cm ³ , dichloromethane 10.0 cm ³ , and 3 drops of anhydrous N, N-dimethylformamide were added and the materials were stirred at room temperature.

The mixture was stirred at room temperature to dissolve all of the solids. When the reaction solution became transparent, the reaction proceeded further for 3 hours. Then, a Dean-Stark trap was installed and the temperature was raised to 80 to 90 ° C to remove unreacted oxalyl chloride and dichloromethane. After further drying, solid yellow anthracene-9-carbonyl chloride was obtained.

2. Synthesis of anthracene-sorbitol ethoxylate complex

6.34 g of sorbitol ethoxylate, 1.97 g of triethylamine (TEA) and 15 cm ³ of dichloromethane (hereinafter referred to as 'DCM') were added to a 100 cm ³ round bottom flask, ≪ / RTI >

Then, the temperature of the reaction vessel was lowered to 0 ° C and anthracene-9-carbonyl chloride dissolved in 10 cm ³ of DCM was added slowly. After 10 minutes of reaction, the temperature of the reaction vessel was raised to room temperature and allowed to react for 16 hours. After the reaction was completed, methanol was added thereto, and the mixture was stirred for 10 minutes and then concentrated.

After stirring, the concentrated organic material was dissolved in a small amount of methanol, the precipitate was removed through a filter, and an organic layer containing the product was separated using chloroform and water.

The organic layer containing the product was dried using magnesium sulfate (MgSO ₄ ) and concentrated to synthesize anthracene-sorbitol ethoxylate complex.

3. Anthracene-Sorbitol ethoxylate complex ^One H-NMR analysis

(2)

The synthesis of anthracene-sorbitol ethoxylate complex was confirmed by ¹ H-NMR (400 MHz, CDCl ₃ ) and ¹ H-NMR analysis was as follows.

^{1 H-NMR (400 MHz,} CDCl 3): δ = 8.45 (s, 2H, Ar-H), 8.08 (d, 4H, Ar-H), 7.95 (d, 4H, Ar-H), 7.52 ~ 7.39 (m, 8H, Ar-H ), 4.73 (d, 4H, An-COOCH 2 CH 2), 3.88 (d, 4H, An-COOCH 2 CH 2), 3.70 ~ 3.40 (m, 74H, CH 2 CH 2 O)

Referring to FIG. 3, an anthracene proton peak (7.3 to 8.5 ppm) and a polyethylene glycol (PEG) proton peak (3.3 to 3.7 ppm) of sorbitol ethoxylate can be identified.

When the number of hydrogen atoms in the polyethylene glycol was set to 74 and the structure of the anthracene-sorbitol ethoxylate complex was confirmed when the repeating unit (n) of the polyethylene glycol (PEG) was 3 to 4, Of anthracene are bonded to each other.

<Example 2> Surface treatment of PET mesh

1. Surface modification of PET mesh by dyeing reaction of hydrophilic modifier

Surface preparation of polyethyleneterephthalate (PET) mesh was carried out using a high pressure reactor (Versoclave type 4, Buchiglas) similar to the dyeing process.

Into the high-pressure reactor, 350 cm ³ of distilled water, 3.03 g of the hydrophilic modifier containing the anthracene-sorbitol ethoxylate complex according to Example 1, and two PET meshes (240 mm x 210 mm) were charged. Thereafter, the temperature was heated to 130 DEG C and the reaction was carried out for 3 hours.

After the reaction, the PET mesh treated with the hydrophilic modifier was removed from the high pressure reactor, washed with distilled water and dried at room temperature.

2. Urethane coating of surface of PET mesh with hydrophilic modifier

3.2 grams of hexamethylene diisocyanate, 8.0 cm &lt; ³ &gt; of propylene glycol monomethyl ether acetate as a diluent, and dibutyltin dilaurate as a urethane curing catalyst were added to a 25 cm ³ vial, 1.0 g was added to prepare a coating solution.

The PET mesh surface-treated with a hydrophilic modifier containing the anthracene-sorbitol ethoxylate complex according to Example 1 was evenly moistened to the coating solution, and then heat-treated at 100 ° C for 1 minute to form a urethane coating through crosslinking After the treatment was completed, it was washed with isopropyl alcohol and distilled water and dried.

&Lt; Comparative Example 1 > A PET mesh surface treatment in which only surface modification with a hydrophilic modifier proceeded

Surface preparation of polyethyleneterephthalate (PET) mesh was carried out using a high pressure reactor (Versoclave type 4, Buchiglas) similar to the dyeing process.

Into the high-pressure reactor, 350 cm ³ of distilled water, 3.03 g of the hydrophilic modifier containing the anthracene-sorbitol ethoxylate complex according to Example 1, and two PET meshes (240 mm x 210 mm) were charged. Thereafter, the temperature was heated to 130 DEG C and the reaction was carried out for 3 hours.

After the reaction, the PET mesh treated with the hydrophilic modifier was taken out of the high pressure reactor, washed with distilled water, and dried at room temperature to perform surface modification of the PET mesh using the dyeing reaction of the hydrophilic modifier.

&Lt; Comparative Example 2 > A PET mesh surface treated with urethane coating using a coating liquid containing a diisocyanate compound

3.2 grams of hexamethylene diisocyanate, 8.0 cm &lt; ³ &gt; of propylene glycol monomethyl ether acetate as a diluent, and dibutyltin dilaurate as a urethane curing catalyst were added to a 25 cm ³ vial, 1.0 g was added to prepare a coating solution.

The PET mesh was evenly soaked in the coating solution and then heat treated at 100 캜 for 1 minute to form a urethane coating by crosslinking. After the treatment, the coating was washed with isopropyl alcohol and distilled water and dried, The urethane coating treatment of the surface of the PET mesh was carried out under the same conditions as in Example 2 above.

Experimental Example 1: Possibility of surface treatment of PET mesh

1. Confirmation of introduction of hydrophilic surface modifier

Two PET meshes were prepared before and after the surface modification in order to confirm the possibility of modifying the PET mesh surface of the hydrophilic modifier comprising anthracene-sorbitol ethoxylate complex.

The two PET meshes before and after the surface modification were subjected to reaction at 130 ° C for 3 hours using a 10 cm ³ seal tube. When the anthracene component was exposed to ultraviolet light having a wavelength of 365 nm, it was confirmed that the anthracene component was introduced into the PET mesh of the modifier through blue fluorescence.

Referring to FIG. 4, ultraviolet light was irradiated onto the surface of the PET mesh before and after the surface modification reaction using a UV lamp. As a result, the surface of the PET mesh shone with blue fluorescence after the surface modification reaction. Since the synthesized surface modifier contains anthracene, it has a characteristic of being fluorescent in ultraviolet light.

 As a result, a hydrophilic modifier including an anthracene-sorbitol ethoxylate complex was introduced on the surface of the PET mesh through a reforming reaction.

2. Check the possibility of urethane coating on the surface of the surface modified PET mesh

Infrared spectroscopy (IR spectroscopy) was used to confirm the possibility of urethane coating of PET meshes surface modified with a hydrophilic modifier containing anthracene-sorbitol ethoxylate complex.

The specimens were prepared using a PET mesh fabric (Referance), a PET mesh (An-sor) which had undergone only surface modification with a hydrophilic modifier comprising an anthracene-sorbitol ethoxylate complex according to Comparative Example 1, and an anthracene- (An-sor-urethane), which has been subjected to surface modification with a hydrophilic modifier including a polyoxyalkylene polyoxyalkylene polyoxyalkylene polyoxyalkylene polyoxyalkylene polyoxyalkylene chain,

FIG. 5 is a graph showing IR spectra of a PET mesh fabric, a PET mesh surface modified only with a hydrophilic modifier according to Comparative Example 1, and a PET mesh surface treated according to Example 2. FIG.

Referring to FIG. 5, in the case of the PET mesh (An-sor) which has undergone surface modification with the hydrophilic modifier according to the PET mesh fabric and the comparative example 1, since the functional groups of the synthesized surface modifier are the same as those of the PET mesh, It can be confirmed that peaks are formed similarly.

On the other hand, in the case of an-sor-urethane in which urethane coating was performed after surface modification with a hydrophilic modifier containing anthracene-sorbitol ethoxylate complex according to Example 2, the -NH peak (3335 cm ^-1 ) Urea-specific C═O peak (1625 cm ^-1 ) and δN-H + -CN peak (1569 cm ^-1 ) were newly observed, confirming that a urethane-bonded coating was formed on the PET mesh surface .

Experimental Example 2 Characterization of Surface-treated PET Mesh

1. Measurement method of distilled water permeability

A PET mesh surface-modified with a hydrophilic modifier containing an anthracene-sorbitol ethoxylate complex is attached to a self-made plastic measuring instrument. Put 200 cm ³ of distilled water inside the plastic measuring instrument and measure the volume of the distilled water permeated through the PET mesh every 5 minutes. The measurement was carried out for one hour, thereby obtaining the volume of distilled water permeated per hour.

2. Measurement of permeability and cell permeability

Collect 5 cm ³ of culture medium containing microalgae before measurement. A PET mesh surface-modified with a hydrophilic modifier comprising an anthracene-sorbitol ethoxylate complex is attached to a plastic measuring instrument.

200 cm ³ of the culture medium containing microalgae was added to the inside of the measuring device and the volume of the culture medium permeated every 30 seconds for 5 minutes was measured and the anthracene-sorbitol ethoxylate complex per hour was measured through the volume of the permeated culture medium The amount of the permeated culture liquid is obtained through the PET mesh surface-modified with the hydrophilic modifier.

Then, collect 5 cm ³ of the permeated culture. Cell permeability is obtained by measuring and comparing the cell concentration of the culture solution collected before and after permeation through a particle size analyzer (Multisizer). The degree of permeability of the titrant cells is 3% or less.

3. Nitrate (NO ₃ ^- ) Measurement of ion permeability coefficient

The measurement is carried out using an aqueous solution of sodium nitrate (NaNO ₃ ) having a concentration of nitrate (NO ₃ ^- ) of 2 g / l. Sodium nitrate (NaNO ₃₎ Distilled water 1000 sodium nitrate per cm ³ to make a solution (NaNO ₃₎ 2.74 g was placed and sufficiently dissolved by stirring. Put 2500 cm ³ of NaNO ₃ solution in a plastic container of 4500 cm ³ .

A PET mesh modified with a hydrophilic modifier containing an anthracene-sorbitol ethoxylate complex was attached to a self-made plastic reactor and 200 cm ³ of distilled water was added to the inside of the measuring device. Then, a plastic reactor equipped with a PET mesh was suspended to form nitrate (NO ₃ ^- ) Measure the permeability.

The solution in the plastic reactor was sampled for 1 minute at a rate of 1 cm ^{3 for} a total of 10 minutes. Ultraviolet-visible spectroscopy was used to measure the absorbance of the solution samples and the concentration of nitrate (NO ₃ ^- ) ions per minute .

The ion permeability coefficient K obtained by substituting the concentration of nitrate (NO ₃ ^- ) ions thus obtained, the measured PET mesh thickness, the area, and the amount of distilled water put into the plastic reactor into the following equation (1) is obtained.

[Equation 1]

(M) / (m ² / min), the area (m ² ) of the semipermeable membrane, the thickness (m) of the semipermeable membrane, , The concentration of ions, and the ion permeability.

4. Experimental analysis

We conducted characterization experiments to confirm the efficiency of the previous process. In this experiment, surface treatment was performed on PET meshes with large mesh size, so that high ion permeability was maintained but cell leakage was suppressed.

Therefore, analysis is also focused on this. In general, the condition of the membrane for efficient cell culture is that water and nutrients should permeate well but not count well.

Fig. 6 is a graph showing the results of the comparison between the PET mesh fabric Pristine, the PET mesh which has only undergone surface modification with the hydrophilic modifier according to the comparative example 1, the PET mesh with only the urethane coating according to the comparative example 2, (B), the ion permeability (c), and the cell permeability (d) of the distilled water.

Specifically, the permeability (see FIGS. 6 (a) and 6 (b)) and the cell permeability (see FIG. 6 (c)) of the distilled water / The introduction of the modifier and the progress of the urethane coating result in a reduction in size.

In addition, in the case of ion permeability, it can be seen that there is no significant difference between the PET mesh subjected to the surface treatment according to Example 2 and the PET fabric (see Fig. 6 (c)). This is because even though the size of the mesh is reduced, the surface treated materials show hydrophilicity and thus have a destructive effect.

In addition, in the case of the PET mesh surface-treated according to Example 2, the cell permeability was found to be 0.3%, and the permeability of distilled water and culture fluid was lowered. However, the membrane used in the actual culture (0.4 × 10 ³ mm / h), which is a sufficient value for cell culture (see Fig. 6 (d)).

As a result, when the surface treatment according to Example 2 was carried out, a very low cell permeability (0.3%) was formed while maintaining a high ion permeability (1.21 × 10 ^-7 m ² / min) inherent in the PET mesh. Thus, it can be confirmed that the PET surface treatment process of Example 2 of the present invention is efficient.

<Experimental Example 3> Reproducibility analysis of the surface treatment process of PET mesh

7 is a graph showing the result of the reproducibility analysis of the surface treatment process of the PET mesh according to Experimental Example 3. Fig.

Referring to FIG. 7, in order to confirm the reproducibility of the above-mentioned process, ion permeability and cell permeability analysis experiments were carried out five times under the same conditions. As a result of experiments up to the fifth stage, the ion permeability was higher than 1.13 × 10 ^-7 m ² / min.

The cell permeability was significantly lower than that of the untreated PET mesh, with an average of 2%, although there were differences in five experiments (see FIG. 7). Therefore, it can be confirmed that the PET mesh surface treatment process according to the second embodiment of the present invention has reproducibility.

<Experimental Example 4> Measurement of cell culture efficiency in an actual marine environment

1. Experimental Method

Three PET meshes subjected to the surface treatment according to Example 2 of the present invention and one PET mesh fabric as a control group were each attached to a plastic measuring instrument. Before injecting the culture medium containing the microalgae into the measuring device, 5 cm ³ is sampled and 500 cm ^{3 is} injected per measuring device.

After 2 weeks, the measuring instrument is withdrawn and 5 cm ³ of the inner culture is collected. The cell concentration of the culture solution collected before and after culturing through a particle analyzer (Multisizer) is measured to confirm the cell culture efficiency for 2 weeks.

2. Experimental analysis

Fig. 8 is a graph showing the cell culture efficiency in the actual marine environment of the PET mesh fabric Pristine and the PET mesh surface-treated according to Example 2. Fig.

Referring to FIG. 8, it can be seen that the number of cells in the case of the PET fabric was reduced by 70% compared with that in 2 weeks. This is the result of cell leaks and necrosis.

On the other hand, although the PET mesh treated with the surface treatment according to Example 2 did not increase much, the number of cells increased by 30 ~ 50% and the efficiency of the PET fabric was more than 4 times higher than that of the PET mesh. As a result, it can be confirmed that the PET mesh surface-treated according to Example 2 suppresses cell leakage and can be used for actual culturing.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is to be understood that various modifications and changes may be made without departing from the scope of the appended claims.

Claims (13)

Anthracene-Sorbitol ethoxylate complex represented by the following formula 1:
[Chemical Formula 1]

The substituents of at least one of R &_lt; ₁ &gt; to R &_lt; ₆ &_gt;

And the remaining substituents are hydrogen, and n is 2 to 10. The method according to claim 1,
The anthracene-sorbitol ethoxylate complex may be prepared by,
An anthracene-sorbitol ethoxylate complex, which is a compound represented by the following formula (2): &lt; EMI ID =
(2)

n is 2 to 10; A hydrophilic modifier for a hydrophobic polymeric mesh comprising an anthracene-sorbitol ethoxylate complex according to the following formula:
[Chemical Formula 1]

The substituents of at least one of R &_lt; ₁ &gt; to R &_lt; ₆ &_gt;

And the remaining substituents are hydrogen, and n is 2 to 10. Introducing distilled water, a hydrophilic modifier according to claim 3, and a hydrophobic polymer mesh into a high-pressure reactor;
Modifying the surface of the hydrophobic polymeric mesh through a dyeing reaction of the hydrophilic modifier by heating the high pressure reactor; And
Washing and drying the mesh surface modified with the hydrophilic modifier;
Wherein the hydrophilic modifier comprises a hydrophilic modifier. The method of claim 4,
The hydrophobic polymer may include,
(PET), polystyrene (PS), polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF), polysulfone (PSF), and polyethylene Wherein the hydrophilic modifying agent is any one selected from the group consisting of PE, polypropylene, and polycarbonate (PC). The method of claim 4,
The step of modifying the hydrophobic polymeric mesh surface comprises:
And heating the solution at 110 to 150 캜 in a high-pressure reactor to conduct the reaction for 2 to 4 hours. Preparing a coating liquid by mixing a diisocyanate compound, a glycol ether and an ester compound as a diluent, and a urethane curing catalyst; And
Forming a urethane coating layer on the surface of the hydrophobic polymer mesh by immersing the hydrophobic polymer mesh modified with the hydrophilic modifier according to claim 3 in a coating solution and then performing heat treatment;
Wherein the surface of the hydrophilic polymer surface modified with the hydrophilic modifier is coated with a urethane coating on the hydrophilic polymer surface. The method of claim 7,
The glycol ether compound, which is the diluent,
Diethyleneglycol diethyl ether, diethyleneglycol dibutyl ether, dipropyleneglycol dimethyl ether, dipropyleneglycol dibutyl ether, triethyleneglycol dibutyl ether, dipropyleneglycol dibutyl ether, Triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethyleneglycol dibutyl ether, ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether, Wherein the solvent is selected from the group consisting of ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate. A surface treatment with a urethane coating to a phase, the hydrophilic polymer mesh surface-modified with a hydrophilic modifier as claimed. The method of claim 7,
The diisocyanate compound,
But are not limited to, hexamethylene diisocyanate, diphenyl methane diisocyanate, tolunene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and poly Wherein the hydrophilic polymer is modified with a hydrophilic modifier selected from the group consisting of hexamethylene diisocyanate and hexamethylene diisocyanate. The method of claim 7,
Characterized in that the urethane curing catalyst is dibutyltin dilaurate. The method according to claim 1, wherein the urethane curing catalyst is a dibutyltin dilaurate. The method of claim 7,
The step of forming the urethane coating layer on the surface of the hydrophobic polymer mesh may include:
A hydrophilic polymer mesh modified with a hydrophilic modifier according to claim 3, wherein the hydrophobic polymer mesh is immersed in a coating liquid and then heat-treated at 80 to 120 ° C for 30 seconds to 1 minute and 30 seconds. A method of surface treatment through coating. A photobioreactor comprising the hydrophilic modifier according to claim 3. A microalgae culture method, comprising culturing a microalgae in a photobioreactor according to claim 12.

Images