CN111849001A - Preparation method of waterproof total heat exchange paper - Google Patents

Preparation method of waterproof total heat exchange paper Download PDF

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CN111849001A
CN111849001A CN202010657696.0A CN202010657696A CN111849001A CN 111849001 A CN111849001 A CN 111849001A CN 202010657696 A CN202010657696 A CN 202010657696A CN 111849001 A CN111849001 A CN 111849001A
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heat exchange
total heat
water
antibacterial
solvent
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金伟伟
徐意
王鹏飞
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Shaoxing Bailisheng New Material Technology Co ltd
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Shaoxing Bailisheng New Material Technology Co ltd
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
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Abstract

The invention discloses a preparation method of waterproof total heat exchange paper, which comprises the following steps: adding the high-molecular film-forming substance and the antibacterial and mildewproof material into a solvent, uniformly mixing, filtering by a filter screen to obtain a coating solution, coating the coating solution on low-permeability paper by using an anilox roller, and drying to obtain the total heat exchange membrane. In the invention, the low-air-permeability paper has reasonable porosity and pore size, and provides a high moisture-permeable foundation for forming a waterproof total heat exchange membrane. The high molecular film forming matter and the antibacterial mildew-proof material can be uniformly dissolved in the solvent, and can form a compact protective film after being coated on the low-air-permeability paper, and the paper has the effects of water resistance, antibacterial mildew prevention and the like. The total heat exchange membrane prepared by the invention has higher moisture permeability, can obtain the total heat exchange core block with high enthalpy exchange efficiency, high air tightness, antibiosis and mildew resistance, and has good application prospect.

Description

Preparation method of waterproof total heat exchange paper
Technical Field
The invention relates to the field of environment-friendly and energy-saving materials of air conditioners and fresh air systems, in particular to a preparation method of waterproof total heat exchange paper.
Background
The air conditioner and the fresh air system have the functions of adjusting the air temperature and air circulation, and meanwhile, a large amount of heat (or cold) loss is inevitably caused due to gas exchange. Thus, a significant amount of energy can be saved by using the air heat exchanger. There are two main categories of air heat exchangers, sensible heat recovery and total heat recovery. Sensible heat recovery mainly utilizes the cold-hot balance of dry air to reduce energy consumption, but can not recover moisture energy in the air. In fact, the latent heat brought by the moisture is not low, so the energy-saving effect of sensible heat recovery is not ideal. The total heat recovery mode can greatly improve the energy-saving effect, and at present, the total heat recovery mode mainly comprises a rotating wheel exchanger and a total heat exchange core block. The rotary wheel exchanger has high efficiency and long service life, but is suitable for industrial occasions due to large volume. The total heat exchange core block is suitable for household equipment, mainly takes total heat exchange paper as main material at present, and has the advantages of degradability and low cost. However, the total heat exchange paper is made of cellulose materials, is easy to grow bacteria and mold, is easy to discard once encountering liquid water, and has the service life of only 1-2 years. Therefore, the development of the water-resistant total heat exchange paper has extremely high application value and social value.
Chinese patent CN02802078.2 discloses a total heat exchange paper with high heat transfer, high moisture permeability and air barrier property, which is obtained by applying a moisture absorbent on a non-porous cellulose material with the thickness of less than 100 mu m, wherein the moisture permeability at 20 ℃ and 65% relative humidity is more than 1000g/m2And/24 h. However, the cellulose material is easily corroded by microorganisms, and is usually mildewed due to the narrow space of a fresh air system, so that the living health is not facilitated; meanwhile, the moisture absorbent is easy to absorb moisture in the air to further aggravate mildew, and the moisture absorbent is scrapped once meeting water, so that the maintenance cost is increased.
Chinese patent CN201310041806.0 discloses an antibacterial and mildewproof total heat exchange membrane, which is obtained by coating a functional layer containing a high polymer, a porous material antibacterial agent and a moisture absorbent on a substrate such as cellulose paper, non-woven fabric and the like. However, the high polymer used in the patent is a water-soluble material, and can swell and even dissolve after the moisture absorbent is added, so that the antibacterial effect is difficult to last, and even the result of gas leakage and invalidation of the total heat exchange membrane can occur.
The total heat exchange membrane developed by the invention has higher moisture permeability and air tightness, good water resistance and continuous antibacterial and mildewproof effects, and is innovative.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the preparation method of the waterproof total heat exchange membrane, which has higher moisture permeability and air tightness, good water resistance and continuous antibacterial and mildewproof effects, and has the advantages of high efficiency, energy conservation, health, low maintenance cost and the like when being applied to a fresh air system.
The invention adopts the following technical scheme:
a preparation method of a water-resistant total heat exchange membrane comprises the following steps:
adding the high-molecular film-forming substance and the antibacterial and mildewproof material into a solvent, uniformly mixing, filtering by a filter screen to obtain a coating solution, coating the coating solution on low-permeability paper by using an anilox roller, and drying to obtain the total heat exchange membrane.
In the invention, the low-air-permeability paper has reasonable porosity and pore size, and provides a high moisture-permeable foundation for forming a waterproof total heat exchange membrane. The high molecular film forming matter and the antibacterial mildew-proof material can be uniformly dissolved in the solvent, and can form a compact protective film after being coated on the low-air-permeability paper, and the paper has the effects of water resistance, antibacterial mildew prevention and the like.
The high molecular film-forming substance is one or more than two (including two) of ethylene-vinyl acetate copolymer, polyurethane, polyacrylate, polyvinyl butyral, cellulose diacetate, ethyl cellulose, sulfonated polyphenyl ether and terephthalic acid-ethylene glycol-polyether glycol polyester elastomer. The high molecular film-forming substance contains a certain proportion of polar functional groups and nonpolar functional groups, wherein the polar functional groups can promote the permeation of water molecules, and the nonpolar functional groups ensure that the high molecular film-forming substance and the antibacterial agent are not dissolved by moisture. One or more (including two) of polyurethane, sulfonated polyphenylene ether, and terephthalic acid-ethylene glycol-polyether polyol polyester elastomer are preferable.
The antibacterial and mildewproof material is one or more than two (including two) of benzalkonium chloride, zinc acetate, silver acetate, nano-silver antibacterial agent and methyl quinazolinone. The antibacterial and mildewproof material has good dissolubility and high-efficiency antibacterial property, so that the antibacterial and mildewproof material can be uniformly and stably distributed in a total heat exchange membrane to achieve high-efficiency and lasting antibacterial and mildewproof effects. One or more of zinc acetate and silver acetate are preferable.
The solvent is one or more (including two) of ethanol, isopropanol, n-propanol, n-butanol, isobutanol, butanone, pentanone, chloroform, dichloroethane, cyclohexane, methylcyclohexane, petroleum ether, dimethylformamide, ethyl acetate, butyl acetate, tetrahydrofuran, methyltetrahydrofuran and ethylene glycol monobutyl ether. The solvent can quickly dissolve the high-molecular film-forming substance and the antibacterial agent, and has the advantages of low boiling point and low toxicity.
The solid content of the high-molecular film-forming substance is 3-20%, and preferably 5-10%.
The mass ratio of the antibacterial and mildewproof material to the high molecular film forming substance is 0.001-0.02, and preferably 0.005-0.01.
The high-molecular film-forming substance is an ethylene-vinyl acetate copolymer, the antibacterial and mildewproof material is benzalkonium chloride, and the solvent is a mixed solvent consisting of cyclohexane accounting for 70% of the mass percentage and isopropanol accounting for 30% of the mass percentage. The weight ratio of the ethylene-vinyl acetate copolymer, the benzalkonium chloride and the solvent is 5-15: 0.001-0.1: 80-100, most preferably 10: 0.01: 90.
The polymer film-forming substance is polyurethane emulsion and a water-based curing agent, the antibacterial and mildewproof material is a nano-silver antibacterial agent, and the solvent is deionized water. The weight ratio of the polyurethane emulsion, the water-based curing agent, the nano-silver antibacterial agent and the deionized water is 5-15: 0.5-5: 0.001-0.1: 15-45, most preferably 10: 2: 0.04: 28.
the polymer film-forming substance is sulfonated polyether sulfone, the antibacterial and mildewproof material is methyl-quinazolinone, and the solvent is N, N-dimethylformamide. The weight ratio of the sulfonated polyether sulfone to the methyl-quinazolinone to the N, N-dimethylformamide is (5-15): 0.001-0.1: 80-100, most preferably 10: 0.08: 90.
the viscosity of the coating solution is 100-3000 cP, and preferably 600-1500 cP.
The coating thickness of the anilox roller is 10-50 mu m, and preferably 10-30 mu m.
The low-air-permeability paper is a polyethylene microporous membrane, a polypropylene microporous membrane or a polyvinylidene fluoride microporous membrane.
The porosity of the low-air-permeability paper is 80-90%.
The low-air-permeability paper has the air permeability of 400-600 s/100ml, the pore diameter of 0.05-2 mu m and the tightness of 0.6-1.2g/cm 3The thickness is 15 to 40 μm, the preferred air permeability is 400 to 600s/100ml, the pore diameter is 0.1 to 0.5 μm, and the tightness is 0.8 to 1.2g/cm3The thickness is 25 to 40 μm.
Most preferably, the preparation method of the water-resistant total heat exchange membrane comprises the following steps:
adding 10 parts by weight of sulfonated polyether sulfone produced by Changzhou city Kort chemical Co., Ltd and 0.08 part by weight of methyl-oxazoline ketone with the model of BIT-20 produced by Hangzhou Luochuan chemical Co., Ltd into 90 parts by weight of N, N-dimethylformamide, stirring for 24 hours until the materials are fully dissolved, filtering by a filter screen with 800 meshes to obtain a coating solution, coating the coating solution on a polyvinylidene fluoride microporous membrane by a coating thickness of 10 mu m by using an anilox roller, wherein the polyvinylidene fluoride microporous membrane is a product with the porosity of 90% produced by Jiangsu blue Peel membrane Co., Ltd, and drying at 150 ℃ to obtain the waterproof total heat exchange membrane.
The water-resistant total heat exchange membrane prepared by the method has the moisture permeability of kg/(m)224h) Can reach 2.8, the enthalpy efficiency can reach 70 percent, and the performance is very excellent.
Compared with the prior art, the invention has the following advantages:
1. the low-air-permeability paper and the optimized high-molecular film-forming substance jointly form the high-moisture-permeability and high-compactness total heat exchange membrane, a moisture absorbent is not needed, and the paper is prevented from being wetted.
2. The preferred polymeric film-forming materials are insoluble in water, significantly improving the water resistance of the paper and antimicrobial.
3. The optimized high-efficiency antibacterial agent can be uniformly dissolved in a high-molecular film-forming substance, the conditions of uneven distribution, moisture removal and the like are avoided, and the long-acting antibacterial and mildewproof effects are achieved.
4. The total heat exchange membrane of the invention has a mass of 1800-3000 g/m2Moisture permeability of 24h, wet strength, 99.9 percent of antibiosis and 0 grade of mildew prevention, and has the experimental life of more than 5 years.
5. The total heat exchange membrane prepared by the invention has higher moisture permeability, can obtain the total heat exchange core block with high enthalpy exchange efficiency, high air tightness, antibiosis and mildew resistance, and has good application prospect.
Detailed Description
In the examples, the parts are by weight unless otherwise specified.
Example 1
10 parts of ethylene-vinyl acetate copolymer (DuPont Dow., U.S.A., 40L-03) and 0.01 part of benzalkonium chloride (Kary chemical Co., Ltd., Zaozhuang) were added to 90 parts of a mixed solvent composed of 70 mass% cyclohexane and 30 mass% isopropyl alcohol at room temperature and 25 ℃ and stirred for 24 hours until completely dissolved. The coating solution was obtained by filtration through a 800-mesh screen, and the coating solution having a thickness of 10 μm was applied to a polyethylene microporous membrane (Dupont Dow, Tyvek 1056, porosity 80%) by means of an anilox roll and dried at 50 ℃ to obtain a water-resistant total heat exchange membrane.
Example 2
10 parts of a polyurethane emulsion (Wanhua chemical group,
Figure BDA0002577339250000041
1651) 2 parts of an aqueous curing agent
Figure BDA0002577339250000042
161 and 0.04 part of nano silver antibacterial agent (jin nano technology (mansion) ltd, JDTKS-001) were added to 28 parts of deionized water and stirred until uniformly dispersed. Filtering with 200 mesh filter screen to obtain coating solution, coating 10 μm thick coating solution onto polypropylene microporous membrane (porosity 85% in WUWA Huamei microporous membrane factory) with anilox roller, and drying at 80 deg.C to obtain water-resistant total heat exchange membrane.
Example 3
10 parts of sulfonated polyethersulfone (Kyowa Kort chemical Co., Ltd.) and 0.08 part of methyl-quinazolinone (BIT-20, Hangzhou Luo Chun chemical Co., Ltd.) were added to 90 parts of N, N-dimethylformamide at room temperature of 25 ℃ and stirred for 24 hours until they were sufficiently dissolved. Filtering with 800 mesh filter screen to obtain coating solution, coating 10 μm thick coating solution onto polyvinylidene fluoride microporous membrane (Jiangsu blue sky Peyer membrane Co., Ltd., porosity of 90%), and drying at 150 deg.C to obtain water-resistant total heat exchange membrane.
Comparative example 1
6 parts of polyvinyl alcohol (PVA-1799, Anhui Wei group, Inc.), 0.3 part of glutaraldehyde, 0.2 part of concentrated hydrochloric acid and 0.05 part of nano-silver antibacterial agent (Jinda nano technology (Xiamen, Inc., JDTKS-001) were added to 94 parts of deionized water at 95 ℃ and stirred until they were uniformly dispersed. Filtering with 200 mesh filter screen to obtain coating solution, coating 10 μm thick coating solution onto polypropylene microporous membrane (porosity of 85% in WUWA Huamei microporous membrane factory) with anilox roller, and drying at 80 deg.C to obtain composite membrane.
Comparative example 2
10 parts of styrene-butadiene copolymer (ba ling petrochemical YH-503) and 0.06 part of nanosilver antibacterial agent (Jinda nanotechnology (Xiamen) Co., Ltd., JDTKS-001) were added to 90 parts of toluene at room temperature and 25 ℃ and stirred for 24 hours to be sufficiently dissolved. Filtering with 800 mesh filter screen, coating 10 μm thick solution onto polypropylene microporous membrane (porosity 85% in WUWA Huamei microporous membrane factory) with anilox roller, and drying at 80 deg.C to obtain composite membrane.
Moisture permeability test method: reference to GBT12704.2-2009 textile fabric moisture permeability test method part 2, at 23 ± 2 ℃, 50 ± 2% relative humidity: specific results of method A, evaporation method "are shown in Table 1:
table 1.
Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2
Moisture permeability kg/(m)224h) 2.7 2.5 2.8 1.6 1.3
Enthalpy efficiency 68％ 63％ 70％ 53％ 46％
Also, the invention of examples 1 to 3The total heat exchange membrane has a thickness of 2500-2800 g/m2Moisture permeability of 24h, wet strength, 99.9 percent of antibiosis and 0 grade of mildew prevention, and has the experimental life of more than 5 years.
Therefore, the total heat exchange membrane prepared by the invention has higher moisture permeability, can obtain the total heat exchange core block with high enthalpy exchange efficiency, high air tightness, antibiosis and mildew resistance, and has good application prospect.

Claims (10)

1. The preparation method of the waterproof total heat exchange paper is characterized by comprising the following steps of:
adding the high-molecular film-forming substance and the antibacterial and mildewproof material into a solvent, uniformly mixing, filtering by a filter screen to obtain a coating solution, coating the coating solution on low-permeability paper by using an anilox roller, and drying to obtain the total heat exchange membrane.
2. The method for preparing water-resistant total heat exchange paper according to claim 1, wherein the polymer film-forming substance is at least one of ethylene-vinyl acetate copolymer, polyurethane, polyacrylate, polyvinyl butyral, cellulose diacetate, ethyl cellulose, sulfonated polyphenylene oxide, and terephthalic acid-ethylene glycol-polyether polyol polyester elastomer.
3. The preparation method of water-resistant total heat exchange paper according to claim 1, wherein the antibacterial and mildewproof material is at least one of benzalkonium chloride, zinc acetate, silver acetate, nano-silver antibacterial agent and methyl-quinazolinone.
4. A method for preparing water-resistant total heat exchange paper according to claim 1, wherein the solvent is at least one of ethanol, isopropanol, n-propanol, n-butanol, isobutanol, butanone, pentanone, chloroform, dichloroethane, cyclohexane, methylcyclohexane, petroleum ether, dimethylformamide, ethyl acetate, butyl acetate, tetrahydrofuran, methyltetrahydrofuran, and ethylene glycol monobutyl ether.
5. The preparation method of the water-resistant total heat exchange paper according to claim 1, wherein the coating thickness of the anilox roller is 10-50 μm.
6. The method for preparing the water-resistant total heat exchange paper according to claim 1, wherein the polymer film-forming substance is an ethylene-vinyl acetate copolymer, the antibacterial and mildewproof material is benzalkonium chloride, and the solvent is a mixed solvent consisting of 70% by mass of cyclohexane and 30% by mass of isopropanol;
the weight ratio of the ethylene-vinyl acetate copolymer, the benzalkonium chloride and the solvent is 5-15: 0.001-0.1: 80-100, most preferably 10: 0.01: 90.
7. the preparation method of the water-resistant total heat exchange paper according to claim 1, wherein the polymer film-forming substance is a polyurethane emulsion and a water-based curing agent, the antibacterial and mildewproof material is a nano-silver antibacterial agent, and the solvent is deionized water;
the weight ratio of the polyurethane emulsion, the water-based curing agent, the nano-silver antibacterial agent and the deionized water is 5-15: 0.5-5: 0.001-0.1: 15-45.
8. The preparation method of water-resistant total heat exchange paper according to claim 1, wherein the polymer film-forming substance is sulfonated polyethersulfone, the antibacterial and mildewproof material is methyl-quinazolinone, and the solvent is N, N-dimethylformamide;
The weight ratio of the sulfonated polyether sulfone to the methyl-quinazolinone to the N, N-dimethylformamide is (5-15): 0.001-0.1: 80-100 parts.
9. The method for preparing water-resistant total heat exchange paper according to claim 1, wherein the porosity of the low-air-permeability paper is 80-90%.
10. The method for preparing water-resistant total heat exchange paper according to claim 1, wherein the low-air-permeability paper is a polyethylene microporous membrane, a polypropylene microporous membrane or a polyvinylidene fluoride microporous membrane.
CN202010657696.0A 2020-07-09 2020-07-09 Preparation method of waterproof total heat exchange paper Pending CN111849001A (en)

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CN109107399A (en) * 2018-07-30 2019-01-01 绍兴百立盛新材料科技有限公司 A kind of hydrone permeable membrane and its preparation method and application
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