KR101744343B1

KR101744343B1 - Metal-complex polymer film for air cleaning filter and method for manufacturing same

Info

Publication number: KR101744343B1
Application number: KR1020150067789A
Authority: KR
Inventors: 이승호; 최성호; 김운중
Original assignee: 한남대학교 산학협력단
Priority date: 2015-05-15
Filing date: 2015-05-15
Publication date: 2017-06-07
Also published as: KR20160134166A

Abstract

The present invention relates to a metal complex type polymer membrane for an air purification filter and a method of manufacturing the same. More particularly, the present invention relates to a polymer membrane and a diazonium salt having at least one functional group selected from the group consisting of carboxylic acid, sulfonic acid group and phosphoric acid group, Preparing a polymer filter including at least one functional group selected from the group consisting of carboxyl groups, sulfonic groups and phosphoric groups on the surface of the filter; And a step of preparing a metal complex type polymer membrane by supporting a metal in a complex form on a surface of the polymer filter including a functional group on the surface thereof. Thus, the removal efficiency of the volatile organic compound is excellent by a simple process, The present invention relates to a metal complex type polymer membrane for an air purification filter having excellent effects on the property and a method for manufacturing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a metal complex type polymer membrane for air purifying filter,

The present invention relates to a metal complex type polymer membrane for an air purification filter having excellent antibacterial and adsorptive properties and a method for producing the same.

BACKGROUND ART [0002] In general, a semiconductor manufacturing process, a building, and the like are equipped with a purifier such as an air purifier. In recent years, in a purification apparatus, a harmful gas component such as an acidic gas, an alkaline gas, or a volatile organic compound (VOCs) is chemically Chemisorption filters are widely used to remove these gases.

Such a chemisorption filter is manufactured considering the following conditions, which are important factors for determining performance and quality.

1) Whether to remove harmful substances and to secure removability; 2) Whether the filters are worn or dust particles are generated by physical impact such as vibration or wind speed; 3) whether the pressure loss of the fluid passing through the chemisorption filter during filtration can be minimized; 4) Secondary contamination by adsorbent used for filtration. As a typical chemisorption filter, active carbon impregnated adsorption filters are mainly used for the purpose of removing acidic and alkaline substances contained in the air. The impregnated adsorption filter is manufactured by attaching an acidic or alkaline substance such as phosphoric acid, potassium hydroxide, or potassium permanganate to a particulate material having a large surface area and a large pore volume or reacting with harmful substances to be removed.

However, in such a chemisorption filter, since the impregnated materials generate salts by acid-alkali neutralization reaction during the purification operation, and the longer the purification time becomes, the more salt is generated and the pores of the chemisorption filter are blocked, There has been a problem that the function of the filter becomes deteriorated as the cleaning time becomes longer as the fluid causes pressure loss of the fluid passing through the filter for purification, that is, lowering of the flow pressure. In addition, since the impregnated acidic and alkaline materials have high volatility, secondary contamination may occur due to the volatilization of these impregnated materials, which can be used in a clean room of semiconductor manufacturing equipment requiring a high degree of cleanliness There was no problem.

A chemisorption filter for ozone decomposition using activated carbon is disclosed in Korean Patent No. 10-0358262.

The chemical adsorption filter for ozone decomposition has proposed an air filter which is inexpensive and efficient by attaching activated carbon particles to a polyethylene or aluminum net. However, the chemical adsorption filter for ozone decomposition still has a problem of dust generation due to impact and abrasion or secondary contamination due to impregnated material, which makes it difficult to apply it to a clean room of semiconductor equipment requiring cleanliness. In order to compensate for the risk of secondary pollution due to dust generation and volatilization of impregnated material, which is a disadvantage of conventional chemical adsorption filters using activated carbon, recently, a new chemisorption filter having a low risk of dust generation and adsorbed matter It is in progress.

Accordingly, the present applicant has proposed a filter for air purification of a metal complex type carbon-based membrane in Korean Patent No. 1,402,604. Specifically, the air purification filter was produced by modifying the surface of the porous carbon separation membrane and supporting the reformed carbon separation membrane in the form of a complex in the form of a metal.

The metal complex type carbon-dioxide air cleaning filter is excellent in the removal efficiency of volatile organic compounds, deodorizing effect against odor, and antibacterial property, but the manufacturing process of the porous carbon separation membrane is complicated and the manufacturing time is long.

The applicant of the present invention has proposed a method for producing a metal complex type polymer membrane for an air purification filter which can reduce the time and cost by simplifying the manufacturing process while maintaining the removal efficiency of volatile organic compounds equal to or more than the conventional ones, And a metal complex type polymer membrane for an air purification filter obtained therefrom.

In order to achieve the above object, the present invention provides a method for producing a polymer electrolyte membrane, comprising graft polymerizing a polymer filter and a diazonium salt having at least one functional group selected from the group consisting of carboxyl, sulfonic acid and phosphoric acid groups, Preparing a polymer filter including at least one functional group selected from the group consisting of a phosphate group and a phosphoric acid group; And forming a metal complex type polymer membrane by supporting a metal in a complex form on a polymer filter including a functional group on the surface thereof.

The graft polymerization may be carried out using 0.01 to 0.1 mole of potassium sulfate per mole of the diazonium salt.

The graft polymerization may be carried out at 50 to 80 DEG C for 1 minute to 24 hours.

The metal may be at least one selected from the group consisting of silver, copper, gold, zinc and platinum.

The size of the metal may be 1 to 100 nm.

The polymer filter may be at least one material selected from the group consisting of polyethylene, polypropylene, polyurethane, polyethylene terephthalate, styrene-butadiene rubber and nitrile-butadiene rubber.

The polymer filter may have a porosity of 1 to 50%.

The polymer filter may be a nonwoven fabric.

The polymer filter may have a thickness of 1 to 5 mm.

Further, the present invention is a metal complex type polymer membrane obtained by the above production method, which has a specific surface area of 25 to 250 m ² / g, an antibacterial efficiency of 90 to 99%, an adsorption efficiency of a volatile organic compound of 90 to 99% And a deodorization efficiency of the organic compound is 95 to 99%. The present invention also provides a metal complex type polymer membrane for an air purifying filter.

The metal complex type polymer membrane for an air purifying filter according to the present invention is advantageous in that the manufacturing process is simpler than that of the conventional porous carbon separation membrane and thus the time and cost are reduced and the economical efficiency is excellent.

In addition, the metal complex type polymer membrane for an air purifying filter according to the present invention has an excellent removal efficiency of volatile organic compounds and a deodorizing effect against odor and an effect on antibacterial property compared to the conventional filter.

In addition, since the metal complex type polymer membrane for air purifying filter according to the present invention is an adsorption elimination method, secondary byproducts are not produced, thereby being environmentally friendly.

1 is an SEM photograph (b) of a polymeric filter (a) including the functional group prepared in Example 1 and a metal complex type polymer membrane for an air purifying filter manufactured using the polymeric filter (a) according to the present invention,
2 is an SEM photograph (b) of a polymeric filter (a) including the functional group prepared in Example 2-1 according to the present invention and a metal complex type polymer membrane for an air purifying filter manufactured using the polymeric filter (a)
3 is a configuration diagram of an adsorption system for measuring the adsorption performance of a volatile organic compound.

TECHNICAL FIELD The present invention relates to a metal complex type polymer membrane for an air purification filter, which is excellent in the removal efficiency of a volatile organic compound, a deodorizing effect on odors, and an antibacterial effect, and a method for producing the same. In the present invention, the volatile organic compound means a liquid or gaseous organic compound that has a high vapor pressure and is easily evaporated into the atmosphere. It is not only air pollution but also a carcinogenic substance, which is pointed out as a cause of global warming. For example, benzene, toluene, ethylbenzene, xylene, acetylene, and the like.

The method for producing a metal complex type polymer membrane for an air purification filter according to the present invention comprises graft polymerizing a polymer filter and a diazonium salt having at least one functional group selected from the group consisting of carboxyl, sulfonic acid and phosphoric acid groups, Preparing a polymer filter including at least one functional group selected from the group consisting of a sulfonic acid group and a phosphoric acid group; And a step of preparing a metal complex type polymer membrane by supporting a metal in a complex form on a polymer filter including a functional group on the surface.

Hereinafter, a method for producing a metal complex type polymer membrane for an air filter according to the present invention will be described in detail.

First, a polymer filter including at least one functional group selected from the group consisting of carboxyl groups, sulfonic groups, and phosphoric groups is prepared on the filter surface.

The polymer filter including the functional group graft-polymerizes a polymer filter and a diazonium salt having at least one functional group selected from the group consisting of carboxyl, sulfonic acid and phosphoric acid groups. The surface of the polymer filter is modified by the graft polymerization to bind the metal and the polymer filter in the process described below.

The polymer filter is generally used in the art and is not particularly limited as long as it is made of a polymer and filterable. Specifically, the polymer material may be at least one selected from the group consisting of polyethylene, polypropylene, polyurethane, polyethylene terephthalate, styrene-butadiene rubber, and nitrile-butadiene rubber. Considering cost competitiveness, ease of handling, and surface condition and materials, polyethylene and polypropylene are preferred.

In addition, the polymer filter preferably has a porosity of 1 to 50%. When the porosity is less than 1%, the air permeability decreases. When the porosity exceeds 50%, the graft ratio decreases.

The thickness of the polymer filter is preferably 1 to 5 mm. If the thickness is less than 1 mm, uniform grafting may be difficult. If the thickness is more than 5 mm, the workability may be deteriorated.

As described above, it is preferable that the polymer filter is a nonwoven fabric in consideration of porosity, thickness, material, use and cost.

The diazonium salt having at least one functional group selected from the group consisting of a carboxyl group, a sulfonic acid group and a phosphoric acid group may be prepared by a method generally used in the field or a commercially available product may be used. For example, the aromatic primary amine having at least one functional group selected from the group consisting of carboxyl, sulfonic acid group and phosphoric acid group can be obtained by diazotization with nitrous acid, but is not limited thereto.

In order to more efficiently perform the graft polymerization of the present invention, a catalyst such as potassium sulfate, iron, or sodium nitrate may be added, and potassium sulphate is preferable considering the purity of the final product.

The potassium sulfate may be used in an amount of 0.01 to 0.1 mol based on 1 mol of the diazonium salt. If it is less than 0.01 mol, it may be difficult to achieve the desired effect.

The graft polymerization is preferably carried out at 50 to 80 DEG C for 1 minute to 24 hours. If the polymerization temperature is less than 50 캜, the reaction may occur insufficiently. If the polymerization temperature exceeds 80 캜, the fiber itself may be deformed. If the polymerization time is less than 1 minute, the graft polymerization may be unreacted, and if the polymerization time exceeds 24 hours, homopolymer polymer may be produced in a large amount.

Next, a metal complex type polymer membrane is prepared by supporting a metal in complex form on a polymer filter including a functional group on the surface.

The metal is not particularly limited as long as it can exhibit antimicrobial activity. For example, at least one selected from the group consisting of silver, copper, gold, zinc and platinum can be used. Copper is preferable in view of antibacterial efficiency.

At this time, the metal is a precursor. For example, the silver precursor may be at least one selected from the group consisting of silver nitrate, silver sulfate, silver acetylacetonate, silver acetate, silver carbonate and silver chloride. , Copper sulfate, copper acetylacetonate, copper acetate, copper carbonate and silver chloride may be used.

The size of the metal is preferably in the range of 1 to 100 nm, and it is preferable that the metal includes the metal in the above range because it is easy to bind to the surface of the polymer filter in a complex form and increases the antibacterial effect.

The metal complex type polymer membrane for an air purifying filter manufactured by the method described above has a specific surface area of 25 to 250 m ² / g, an antibacterial efficiency of 90 to 99%, an adsorption efficiency of a volatile organic compound of 90 to 99% The deodorization efficiency of the organic compound may be 95 to 99%.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Example One

One) Carboxy group Diazonium salt preparation

Under an ice bath, 1 L of 0.2 M HCl was added to a 2 L reaction vessel and stirred at 300 rpm. After adding 27.428 g of 4-aminobenzoic acid, 250 mL of 0.02 M NaNO ₂ was added slowly by using a 20 mL / min peristaltic pump. Thereafter, the mixture was stirred at 300 rpm for 2 hours to prepare a diazonium salt having a carboxyl group.

2) Function giga Manufacture of Polymer Filters

A polyethylene nonwoven fabric (Taesan, polyethylene) having a size of 5 cm x 5 cm x 0.3 cm and a porosity of 20% was washed with MeOH for 10 minutes and then dried at 70 ° C for 3 hours using a vacuum oven. The weight of the dried polyethylene nonwoven fabric was measured five times repeatedly.

Separately, a constant temperature water bath at 70 ° C was prepared on a hot plate, and a 500 ml flask was immersed in the water bath. Then 100 ml of the diazonium salt having the carboxyl group prepared above was added.

The dried polyethylene nonwoven fabric was further added thereto, sufficiently wetted, and then stirred. Thereafter, 0.03 mol of potassium sulfate was added to 1 mol of the diazonium salt having a carboxyl group, followed by stirring at 500 rpm for 1 hour. (Graft Polymerization)

After the agitation, the nonwoven fabric was taken out, washed with distilled water, and dried in a vacuum oven at 70 ° C for 3 hours. The weight of the dried polyethylene nonwoven fabric was measured five times repeatedly.

3) For air purifying filter Metal complex type Polymer Film Manufacturing

250 mL of 0.2 mM silver nitrate solution was added to a flat bottom flask, and a polyethylene nonwoven fabric containing the above-prepared functional group was added thereto, followed by stirring for 1 hour. Thereafter, the polyethylene nonwoven fabric containing the functional group was taken out, washed with distilled water, and dried at 70 ° C for 3 hours using a vacuum oven.

Example 2

A metal complex type polymer membrane for an air filter was prepared in the same manner as in Example 1, except that a polymer nonwoven fabric (a polymer nonwoven fabric of the following Table 1 was used in place of a nonwoven fabric of Daisan Co., polyethylene.

division Type of polymer filter Manufacturer, Product Name Example 2-1 Polyethylene Daesan Chemical, Polyethylene Example 2-2 polyester Korea 3M, Polyester Example 2-3 Polypropylene Hanawon K.T.C, polypropylene Examples 2-4 Polyethylene Hanawon K.T.C, polypropylene Example 2-5 Polyethylene terephthalate Korea 3M, Polyethylene Terephthalate Examples 2-6 Polyurethane Kumho-iti, polyurethane

Example 3

A metal complex type polymer membrane for an air purification filter was prepared in the same manner as in Example 1 except that a solution of the metal shown in Table 2 was used instead of 250 mL of 0.2 mM silver nitrate solution.

division metal Concentration, usage Example 3-1 Copper 0.2 mM, 250 mL Example 3-2 gold 0.2 mM, 250 mL Example 3-3 zinc 0.2 mM, 250 mL Example 3-4 platinum 0.2 mM, 250 mL

Example 4

Except that the diazonium salt of the following Table 3 was used instead of the diazonium salt having a carboxyl group to prepare a metal complex type polymer membrane for an air filter.

division Type of function machine Example 4-1 Sulfonic acid group Example 4-2 Phosphate

Example 5

The procedure of Example 1 was followed except that the following graft polymerization conditions were carried out as shown in Table 4 to prepare a metal complex type polymer membrane for an air filter.

division Reaction temperature (캜) Reaction time (min) Example 5-1 70 10 Example 5-2 70 20 Example 5-3 70 30 Examples 5-4 50 60 Example 5-5 60 60

Example 6

A metal complex type polymer membrane for an air filter was prepared in the same manner as in Example 1 except that the thickness and the porosity of the polyethylene nonwoven fabric were changed as shown in Table 5 below.

division Thickness (mm) Porosity (%) Example 6-1 5 20 Example 6-2 2 10 Example 6-3 3 30 Example 6-4 4 50 Examples 6-5 One 3

Comparative Example One

250 mL of 0.2 mM silver nitrate solution was added to a flat bottom flask, and a polyethylene nonwoven fabric (Taesan product, polyethylene) having a size of 5 cm x 5 cm x 0.3 cm and a porosity of 20% was added thereto and stirred for 1 hour. Thereafter, the polyethylene nonwoven fabric was taken out, washed with distilled water, and then dried in a vacuum oven at 70 ° C for 3 hours.

Comparative Example 2

Example 1 of Korean Patent No. 1,402,604

Comparative Example 3

Commercial air purification filter (Yuhan-Kimberly)

Experimental Example One

The BET of the metal complex type polymer membranes prepared in the above Examples and Comparative Examples was measured, and the specific surface area thereof is shown in Table 6.

division Specific surface area (m < 2 > / g) Example 1 60 Example 2-3 57 Example 3-1 56 Comparative Example 1 31 Comparative Example 3 32

As shown in Table 6, it can be seen that the embodiment of the present invention is much superior to Comparative Example 1 in which graft polymerization is not performed and the commercially available air purifying filter.

Experimental Example 2: Antimicrobial activity

Antimicrobial activity tests were conducted using the metal complex type polymer membranes prepared in the above Examples and Comparative Examples as dust collecting filters. In the experimental procedure, the microorganisms in the air were collected on the surface of the dust filter, the dust filter was put into the liquid medium, and the liquid medium was shaken out. Then, the liquid medium was cultured for 64 hours and the cell count for the liquid medium was measured. Was confirmed.

division Visible cell count (× 10 ⁷ ) at 720 min Example 1 0 Example 2-3 0 Example 3-1 0 Comparative Example 1 520 Comparative Example 2 0 Comparative Example 3 1100

As shown in Table 7, it can be confirmed that the examples of the present invention are superior in antibacterial activity to those of Comparative Examples 1 and 3. However, Comparative Example 2 has an antibacterial activity equivalent to that of the Example, but has a disadvantage in that the manufacturing process of the filter is very complicated and the manufacturing time is long, so that the manufacturing efficiency is significantly lower than in the Examples.

Experimental Example 3: Measurement of adsorption performance of volatile organic compounds

The test gas having concentrations of toluene, benzene, ethylbenzene and m-, p- and o-xylene of 800 ppb was passed through the metal complex type polymer membrane prepared in the above Examples and Comparative Examples at a cross-sectional flow rate of 0.8 m / The time of continuous adsorption and the amount of final adsorption were measured. The measurement results are shown in Table 8.

At this time, the adsorption performance using the adsorption system as shown in FIG. 4 was used.

division Adsorption time, adsorption amount (min, 10 ^-3 mg / g) toluene benzene Ethylbenzene m, p-xylene o-xylene Example 1 46, 5.02 47, 4.86 51, 5.13 48, 5.35 50, 4.92 Example 2-3 53, 5.69 57, 5.90 55, 5.36 57, 5.72 56, 5.85 Example 3-1 51, 5.02 54, 4.92 56, 5.16 52, 5.20 55, 5.13 Comparative Example 1 14, 1.62 15, 1.55 15, 1.68 13, 1.45 14, 1.66 Comparative Example 2 47, 5.67 48, 5.50 50, 5.61 52, 5.73 51, 5.59 Comparative Example 3 11, 1.03 10, 1.12 12, 1.16 9, 1.21 12, 1.32

As shown in Table 8, it can be seen that the examples according to the present invention have a longer adsorption time and a higher adsorption amount to toluene, benzene, ethylbenzene and m-, p- and o-xylene than the comparative examples.

Experimental Example 4: Measurement of deodorization performance of volatile organic compounds

The metal complex type polymer membrane air purification filter prepared in the above Examples and Comparative Examples was left in a sealed tank by using an ammonia coefficient measuring instrument, and NH ₄ OH solution was added in this state, and the concentration of ammonia (NH ₃ ) Were measured using a gas detection tube. The concentration of ammonia in the tank was measured at 1 hour, 4 hours, and 7 hours, respectively, during the adsorption and decomposition of the ammonia solution in the sample left in the tank. The measurement results are shown in Table 9.

division 1 hours 4 hours 7 hours Deodorization rate (%) Example 1 0.072 0.045 0.008 99.2 Example 2-3 0.073 0.034 0.013 98.7 Example 3-1 0.072 0.013 0.009 99.1 Comparative Example 1 0.481 0.101 0.051 94.9 Comparative Example 2 0.073 0.023 0.012 98.8 Comparative Example 3 0.514 0.120 0.056 94.4

As shown in Table 9, it can be seen that the examples according to the present invention are superior to those of Comparative Examples 1 and 3 by more than 90%, and that the final deodorization rate is 98% or more, as compared with about 50%

Claims

A polypropylene filter containing a carboxyl group on the surface of the filter by graft polymerization at 50 to 80 ° C for 1 minute to 24 hours containing 1 mole of a diazonium salt having a carboxyl group and 0.01 to 0.1 mole of potassium sulfate, Producing; And
And a step of preparing a metal complex type polymer membrane by supporting a metal in a complex form on a polypropylene filter containing a carboxyl group on the surface,
Characterized in that the metal is silver,
The metal complex type polymer membranes prepared above each passed 800 ppb test gas at a cross-sectional flow rate of 0.8 m / s. When measuring the time of continuous adsorption and the final adsorption amount,
Toluene 53min and 5.69x10 ^-3 mg / g and benzene 57min and 5.90x10 ^-3 mg / g and ethylbenzene 55min and 5.36x10 ^-3 mg / g and m, p- xylene was 57min and 5.72x10 ^-3 mg / g and o- xylene production method of 56min and 5.85x10 ^-3 mg / g of the metal complex for the air filter, characterized in the polymer membrane type.

delete

[2] The method according to claim 1, wherein the polypropylene filter has a porosity of 1 to 50%.

The method according to claim 1, wherein the polypropylene filter is a non-woven fabric.

The method according to claim 1, wherein the polypropylene filter has a thickness of 1 to 5 mm.

A metal complex type polymer membrane obtained by the production method of any one of claims 1, 7, 8 and 9, which comprises a polypropylene filter having a carboxyl group on its surface,
When the test gas at the level of 800 ppb was passed at a cross-sectional flow rate of 0.8 m / s, the time of continuous adsorption and the amount of final adsorption were measured at 53 min and 5.69 × 10 ^-3 mg / g of toluene, 57 min and 5.90 × 10 ^-3 mg / g, the ethylbenzene was 55 min and 5.36 x 10 ^-3 mg / g, the p-xylene was 57 min and the 5.72 x 10 ^-3 mg / g, the o-xylene was 56 min and the 5.85 x 10 ^-3 mg / g Characterized in that the metal complex type polymer membrane for air purifying filter.