EP2652191A1 - Polymer composite materials for building air conditioning or dehumidification and preparation method thereof - Google Patents

Polymer composite materials for building air conditioning or dehumidification and preparation method thereof

Info

Publication number
EP2652191A1
EP2652191A1 EP10860689.8A EP10860689A EP2652191A1 EP 2652191 A1 EP2652191 A1 EP 2652191A1 EP 10860689 A EP10860689 A EP 10860689A EP 2652191 A1 EP2652191 A1 EP 2652191A1
Authority
EP
European Patent Office
Prior art keywords
composite material
polymer composite
solution
air conditioning
hydrophilic polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10860689.8A
Other languages
German (de)
French (fr)
Other versions
EP2652191A4 (en
EP2652191B1 (en
Inventor
Young-Soo Ahn
Jeong-Gu Yeo
Kuck-Tack Chue
Churl-Hee Cho
Chang-Kook Hong
Sang-Youn Oh
Se-Hee Kim
Hyeong-Seon Oh
Jae-Sik Ryu
Seung-Hyun Shin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Institute of Energy Research KIER
Original Assignee
Korea Institute of Energy Research KIER
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Institute of Energy Research KIER filed Critical Korea Institute of Energy Research KIER
Publication of EP2652191A1 publication Critical patent/EP2652191A1/en
Publication of EP2652191A4 publication Critical patent/EP2652191A4/en
Application granted granted Critical
Publication of EP2652191B1 publication Critical patent/EP2652191B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D19/00—Regenerative heat-exchange apparatus in which the intermediate heat-transfer medium or body is moved successively into contact with each heat-exchange medium
    • F28D19/04—Regenerative heat-exchange apparatus in which the intermediate heat-transfer medium or body is moved successively into contact with each heat-exchange medium using rigid bodies, e.g. mounted on a movable carrier
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
    • F24F3/00—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems
    • F24F3/12—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling
    • F24F3/14—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification
    • F24F3/147—Air-conditioning systems in which conditioned primary air is supplied from one or more central stations to distributing units in the rooms or spaces where it may receive secondary treatment; Apparatus specially designed for such systems characterised by the treatment of the air otherwise than by heating and cooling by humidification; by dehumidification with both heat and humidity transfer between supplied and exhausted air

Definitions

  • the present disclosure relates to polymer composite materials for building air conditioning or dehumidi f icat ion and a method for preparing the same. More particularly, the present disclosure relates to the preparation of high-efficiency composite materials for building air conditioning or dehumidi f icat ion having superior antibacterial properties and durability as well as excellent water adsorption/desorption ability due to a large surface area by electrospinning of a polymer composite material solution with a cross linking agent or a cross linking agent and a porous filler added to a hydrophilic polymer solution to prepare a fiber sheet composed of fibers having a nano or a submicron scale diameter followed by crossl inking.
  • Air conditioning of a building includes heating, cooling, ventilation and heat exchage. Quality air conditioning provides a healthy and comfortable environment, improves satisfaction with the indoor environment and enhances productivity.
  • Two heat loads - sensible heat and latent heat - determine the capacity of an air conditioning system.
  • the latent heat load accounts for 30-50% of the total heat load.
  • the sensible heat means the heat exchanged during a change of temperature
  • the latent heat refers to the heat that cannot be observed as a change of temperature, e.g. heat absorbed during the phase change of water. A phase change of water without change of temperature results in an air conditioning load.
  • the air conditioning system includes _a total heat exchanger for a ventilation unit, a dehumidi f icat ion rotor for dehumidif ication/cooling, a rotor-type total heat exchanger, or the like.
  • Fig. 1 shows a rotor-type total heat exchanger, illustrating a process whereby air is supplied from outside and indoor air is exhausted outside.
  • a water- absorbent polymer composite material exchanges heat with water in the air supplied from outside and supplies the air indoors while the rotor-type total heat exchanger rotates, thus providing cool air and ventilation with reduced energy consumption.
  • aspects of the present disclosure are directed to high-efficiency composite materials for building air conditioning or dehumidif ication having antibacterial properties as well as excellent water absorbing ability and being easily applicable to various designs.
  • One aspect of the present disclosure provides a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion, including: (SI) adding a crossl inking agent or a crossl inking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat- treatment. Before or after step S3, the nanofiber sheet may be adhered to a metal sheet, a ceramic fiber sheet or a conductive polymer film.
  • Another aspect of the present disclosure provides a method for preparing a polymer composite material for building air conditioning or dehumidif ication, including: (SI) adding a crosslinking agent or a crosslinking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution directly onto a metal sheet, a ceramic fiber sheet or a conductive polymer film to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat-treatment.
  • SI adding a crosslinking agent or a crosslinking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution
  • S2 electrospinning the polymer composite material solution directly onto a metal sheet, a ceramic fiber sheet or a conductive polymer film to prepare a nanofiber sheet
  • S3 crosslinking the nanofiber sheet by heat-treatment.
  • a further aspect of the present disclosure provides a polymer composite material for building air conditioning or dehumidif ication having superior durability and antibacterial properties prepared from a solution including a hydrophilic polymer and a crosslinking agent, or a crosslinking agent and a porous filler by electrospinning and crosslinking.
  • the polymer composite material for building air conditioning or dehumidi f icat ion has superior antibacterial properties and excellent water-adsorbing ability and durability.
  • the polymer composite material may control humidity when used for air conditioning of a building, thereby reducing air conditioning load and improving energy efficiency.
  • the polymer composite material may prevent various diseases and allows supply of pleasant indoor air.
  • the polymer composite material may remove moisture from hot and humid air in the summer, thus reducing air conditioning load by decreasing latent heat load and saving energy.
  • the high- efficiency polymer composite material may be used in moisture-sensitive production processes or industrial applications requiring moisture control or protection from damage or corrosion by moisture in order to dehumidi fy and provide dry air.
  • the polymer composite material according to the present disclosure may be utilized for water adsorption and dehumidi f icat ion in various fields, for example, in building air conditioning and dehumidif icat ion/coo ling, including a total heat exchanger of a ventilation unit, a dehumidi f icat ion rotor for dehumidif ication/cool ing, a rotor-type total heat exchanger, or the like.
  • Fig. 1 shows a total heat -exchange rotor according to an embodiment of the present disclosure
  • Fig. 2 illustrates a crossl inking mechanism of a PVA polymer in Example l
  • FIG. 3 shows scanning electron micrographs of a PVA nanofiber sheet, a crosslinked sheet and a zeolite-introduced nanofiber sheet in Example 1;
  • Fig. 4 shows water adsorption by a nanofiber sheet in Example 2
  • Fig. 5 shows the amount of polymer remaining after washing as compared to the initial polymer amount in Examples 2-4, as a measure of durability; ⁇ 18> Fig. 6 shows a result of culturing E. coli at 35 ° C for 24 hours in
  • Fig. 7 shows a result of culturing salmonella at 35 ° C for 24 hours in
  • a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion includes: (SI) adding a crossl inking agent or a crossl inking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat- treatment .
  • a crosslinking agent or a crosslinking agent and a porous filler are added to a hydrophilic polymer solution in order to confer durability and antibacterial properties, thereby preparing a polymer composite material solution.
  • the hydrophilic polymer solution may be prepared by dissolving at least one hydrophilic polymer selected from the group consisting of polyvinyl alcohol (PVA), polystyrene sulfonic acid, polystyrene sulfonic acid/maleic acid copolymer, sodium polystyrene sulfonate, polyacrylate, polyethylene glycol, polyethylene oxide, cellulose derivatives, and ion exchange resins in at least one solvent selected from the group consisting of water, alcohol, DMF, NMP and DMAc.
  • PVA polyvinyl alcohol
  • polystyrene sulfonic acid polystyrene sulfonic acid/maleic acid copolymer
  • sodium polystyrene sulfonate polyacrylate
  • the content of the hydrophilic polymer may be 0.5 to 50 wt based on the weight of the hydrophilic polymer solution. If the hydrophilic polymer content exceeds 50 wt%, the resulting high viscosity may prevent effective electrospinning. Conversely, if the hydrophilic polymer content is below 0.5 wt , nanofiber may not be produced because of low viscosity.
  • This step may include: dissolving a hydrophilic polymer in a solvent to prepare a first solution; dissolving another hydrophilic polymer different from the first hydrophilic polymer in a solvent to prepare a second solution; and mixing the first solution and the second solution to prepare the hydrophilic polymer solution.
  • the proportion of the contents of the hydrophilic polymers in the hydrophilic polymer solution is not particularly limited and may be appropriately adjusted considering required physical properties.
  • the crosslinking agent added to improve durability and antibacterial properties may include at least one selected from the group consisting of peroxides such as dibenzoyl peroxide, inorganic precursors such as tetraethyl orthosi 1 icate, si lane coupling agents such as 3,3- diethoxypropyltriethoxysi lane, aldehydes such as glutaraldehyde, polyacrylic acids, di isocyanates, diacids and derivatives thereof, and organic acids containing a sulfonic acid group.
  • peroxides such as dibenzoyl peroxide
  • inorganic precursors such as tetraethyl orthosi 1 icate
  • si lane coupling agents such as 3,3- diethoxypropyltriethoxysi lane
  • aldehydes such as glutaraldehyde
  • polyacrylic acids di isocyanates, diacids and derivatives thereof, and organic acids containing a sulf
  • an organic acid containing a sulfonic acid group selected from the group consisting of sul fosuccinic acid (SSA), polystyrene sulfonic acid and poly(4-styrenesulfonic acid-co-maleic acid) sodium salt may be used.
  • the porous filler added to improve durability and antibacterial properties may be zeolite, SBA-15, MCM-41, silica gel, carbon, carbon nanotube, or the like. Further, a porous filler substituted with metal ions such as Cu or Ag may also be used.
  • the content of the crossl inking agent in the polymer composite material solution may be 20 wt or less based on the weight of the hydrophilic polymer. If the content of the crossl inking agent exceeds 20 wt%, the resulting polymer composite material may be too hard or brittle.
  • the content of the porous filler in the polymer composite material solution may be 50 wt or less based on the weight of the hydrophilic polymer. If the content of the porous filler exceeds 50 wt%, the filler may not be dispersed well but coagulate. Further, the amount or rate of water adsorption may decrease.
  • step S2 electrospinning is carried out.
  • a nanofiber sheet with increased surface area may be prepared.
  • a nanofiber structure may be more effectively formed.
  • the diameter of the nanofiber may be adjusted.
  • the nanofiber may have a diameter ranging from tens of nanometers to tens of micrometers.
  • the surface area of the composite material sheet may be controlled to confer a very large water adsorbing capacity.
  • step S3 the nanofiber sheet prepared in step S2 is crossl inked by heat treatment.
  • the crosslinking is initiated by heating and performed while maintaining the elevated temperature.
  • the solution is left at room temperature for predetermined time and then the crossl inking is performed in the same manner.
  • the nanofiber sheet may be adhered to a metal sheet, a ceramic fiber sheet or a conductive polymer film.
  • a metal sheet such as aluminum sheet or stainless steel sheet, a ceramic fiber sheet, or a conductive polymer film such as polyvinyl chloride may be adhered to the crossl inked polymer composite material sheet or to the nanofiber sheet prior to crossl inking.
  • an adhesive may be applied on the surface of the metal sheet and the nanofiber sheet may be adhered to either or both sides of the metal sheet .
  • a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion comprises: (SI) adding a crossl inking agent or a crossl inking agent and ._a__Dor_oiis fjJULer for conferring— dur-ab-i-l-i-t— and- antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution directly onto a metal sheet, a ceramic fiber sheet or a conductive polymer film to prepare a nanofiber sheet; and (S3) crossl inking the nanofiber sheet by heat-treatment.
  • This embodiment is the same as the above embodiment, except that the nanofiber sheet is prepared by directly electrospinning the polymer composite material solution onto the metal sheet, the ceramic fiber sheet or the conductive polymer film.
  • the polymer composite material for building air conditioning or dehumidif ication may be used for various applications, including a total heat exchanger for a ventilation unit, a dehumidif ication rotor for dehumidi f icat ion/cooling, a rotor-type total heat exchanger, and the like.
  • the total heat exchanger for a ventilation unit is a rectangular-shaped heat exchanger fabricated using an insulating exchange membrane with superior water permeability.
  • An insulating exchange membrane that transmits water but blocks polluted air is prepared in the form of a honeycomb.
  • the total heat exchanger transmits latent heat of water included in the air through the paper insulating membrane to the introduced air during ventilation, thereby lowering indoor temperature and humidity, removes fine dust such as pollen, thereby preventing various diseases, is installed in the ceiling, thereby minimizing noise and providing a quiet environment, provides excellent ventilation through forced ventilation in both directions using separate exhaust and inlet vents, and supplies cleanly filtered fresh outside air, rather than recirculated the indoor air, thereby maintaining a pleasant indoor environment.
  • the dehumidif ication rotor for dehumidif i cat ion/coo ling is a key component of a dehumidi f icat ion/cool ing system, which is used to dehumidify the hot and humid summer air through low-energy cooling by separating the latent heat load and the sensible heat load. Further, it is used to dehumidify the air for the purpose of cooling and drying of products, quality improvement and maintenance, humidity control of a production process, or the 1 ike.
  • the rotor-type total heat exchanger is a high-efficiency, energy-saving device capable of controlling thermal balance associated with introduction and exhaust of indoor and outdoor air, effectively purifying indoor air, and reducing cooling/heating load.
  • the rotor-type total heat exchanger may be utilized as a heat recovery ventilator for forced air supply/discharge by reducing the latent heat of water in the exhausted air during ventilation and exchanging heat with the water- in the air supplied from outside, without requiring an additional heating or cooling source.
  • the absorbent of the rotor-type total heat exchanger which serves as a latent heat exchange medium, is impregnated in, coated on or adhered to a cylindrical honeycomb structure.
  • the polymer composite material for building air conditioning of the present disclosure may be used as the latent heat exchange medium employed in the honeycomb structure.
  • the polymer composite material for building air conditioning or dehumidi f icat ion according to the present disclosure has superior water- adsorbing ability because of the increased surface area and the hydration by ions, and has excellent durability and antibacterial properties.
  • it may reduce the latent heat load of water included in the indoor air, thereby saving energy by reducing air conditioning load and supplying pleasant indoor air.
  • dehumidif icat ion/cool ing it can remove moisture from hot and humid air, thus reducing air conditioning load by decreasing the latent heat load and saving energy.
  • the present disclosure is applicable to various fields for water adsorption and dehumidi f icat ion.
  • PVA polyvinyl alcohol
  • the prepared polymer composite material solution was electrospun using an electrospinning apparatus (NT-PS-35K, NTSEE Co. , Korea) to prepare a polymer nanofiber sheet.
  • the voltage used for the electrospinning was 20 kV, and the distance between the positively charged syringe needle and the negatively charged collector was 18 cm.
  • the syringe used to hold the spinning solution was a 10 mL glass syringe, and the diameter of the syringe needle was 0.5 mm.
  • the feed rate of the solution was 0.7 mL/hr, and the collector rotation speed was 300 rpm.
  • the thickness of the nanofiber sheet was controlled by adjusting spinning time.
  • the nanofiber sheet prepared in this example had a thickness of 30 pm.
  • the prepared nanofiber sheet was subjected to crosslinking by heating at 120 ° C for 1 hour.
  • the associated crosslinking mechanism is illustrated in Fig. 2.
  • the nanofiber sheet was observed using a scanning electron microscope (SEM, Hitachi S-4700). Scanning electron micrographs of the PVA nanofiber sheet, the cross linked sheet and the zeolite-introduced nanofiber sheet are shown in Fig. 3.
  • adsorption rate was 2.48 x 10 cm/s for the PVA nanofiber sheet and 2.96 x
  • the prepared polymer composite material solution was electrospun using an electrospinning apparatus (NT-PS-35K, NTSEE Co., Korea) to prepare a polymer nanofiber sheet.
  • the voltage used for the electrospinning was 20 kV, and the distance between the positively charged syringe needle and the negatively charged collector was 18 cm.
  • the syringe used to hold the spinning solution was a 10 mL glass syringe, and the diameter of the syringe needle was 0.5 mm.
  • the feed rate of the solution was 0.7 mL/hr, and the collector rotation speed was 300 rpm.
  • the thickness of the nanofiber sheet was controlled by adjusting spinning time.
  • the prepared nanofiber sheet was subjected to crosslinking by heating at 120 ° C for 1 hour.
  • the adsorption rate of the sample of Example 2 was 2.59X10 cm/s before the crosslinking and 1.79X10 cm/s after the crosslinking.
  • Example 7 zeolite A was added thereto in an amount of 1 wt% based on the polymer weight to prepare a polymer composite material solution (Example 7).
  • E. coli and salmonella bacteria were cultured in the prepared polymer composite material solutions. After culturing at 35 ° C for 24 hours, photographs were taken to evaluate the antibacterial properties. For measurement of the antibacterial properties against E. coli, E. coli samples were cultured separately. Results are shown in Fig. 6. The sample of Example 5 is denoted as "1" , the sample of Example 6 is denoted as "3" , and the sample of Example 7 is denoted as "4" .
  • Fig. 7 shows the result of culturing salmonella bacteria.
  • the right side shows the result when only the bacteria were cultured, and the left side shows the result when the polymer solution was used.
  • Some salmonella bacteria were observed in Example 5, but none was observed in Example 6 or Example 7.
  • the addition of the crbssl inking agent and the porous filler results in far superior antibacterial properties.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Drying Of Gases (AREA)

Abstract

The present disclosure relates to the preparation of a polymer composite material for building air conditioning or dehumidification having superior water-adsorbing ability, durability and antibacterial properties by electrospinning. Specifically, the disclosed method for preparing a polymer composite material for building air conditioning or dehumidification includes: (Sl) adding a crosslinking agent or a crosslinking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution antibacterial properties to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat-treatment. Since the disclosed polymer composite material for building air conditioning or dehumidification has superior antibacterial properties and excellent water-adsorbing ability and durability, the polymer composite material can perform dehumidification when used for air conditioning of a building, thereby reducing air conditioning load and improving energy efficiency. Further, through dehumidifying cooling, the high-efficiency polymer composite material can remove moisture from the hot and humid air in the summer, thus reducing air conditioning load by decreasing latent heat load and saving energy. In addition, the polymer composite material can be used in moisture-sensitive production processes, industrial applications requiring moisture control or protection from damage or corrosion by moisture to reduce moisture and provide dry air.

Description

[DESCRIPTION]
[Invention Title]
POLYMER COMPOSITE MATERIALS FOR BUILDING AIR CONDITIONING OR DEHUMIDIFICATION AND PREPARATION METHOD THEREOF
[Technical Field]
<i> The present disclosure relates to polymer composite materials for building air conditioning or dehumidi f icat ion and a method for preparing the same. More particularly, the present disclosure relates to the preparation of high-efficiency composite materials for building air conditioning or dehumidi f icat ion having superior antibacterial properties and durability as well as excellent water adsorption/desorption ability due to a large surface area by electrospinning of a polymer composite material solution with a cross linking agent or a cross linking agent and a porous filler added to a hydrophilic polymer solution to prepare a fiber sheet composed of fibers having a nano or a submicron scale diameter followed by crossl inking.
[Background Art]
<2> Recently, government regulations have been instituted which require air conditioning systems to perform decontamination functions in addition to basic air conditioning functions. Air conditioning of a building includes heating, cooling, ventilation and heat exchage. Quality air conditioning provides a healthy and comfortable environment, improves satisfaction with the indoor environment and enhances productivity. Two heat loads - sensible heat and latent heat - determine the capacity of an air conditioning system. The latent heat load accounts for 30-50% of the total heat load. The sensible heat means the heat exchanged during a change of temperature, whereas the latent heat refers to the heat that cannot be observed as a change of temperature, e.g. heat absorbed during the phase change of water. A phase change of water without change of temperature results in an air conditioning load. If water is removed from the air using an air conditioning material, the size and energy consumption of an air conditioner may be reduced since the dehumidif icat ion/cool ing system needs only to address the sensible heat load. <3> The air conditioning system includes _a total heat exchanger for a ventilation unit, a dehumidi f icat ion rotor for dehumidif ication/cooling, a rotor-type total heat exchanger, or the like. Fig. 1 shows a rotor-type total heat exchanger, illustrating a process whereby air is supplied from outside and indoor air is exhausted outside. After water is absorbed from the indoor air to be exhausted in order to reduce the latent heat load, a water- absorbent polymer composite material exchanges heat with water in the air supplied from outside and supplies the air indoors while the rotor-type total heat exchanger rotates, thus providing cool air and ventilation with reduced energy consumption.
<4> Current studies on building air conditioning materials focus only upon general water absorbents using super-dense paper, inorganic materials, metal silicates, silica gel, zeolite, or the like. For example, Japan' s Seibu Giken has developed water-absorbent polymer powder and is marketing a total heat exchanger with the water-absorbent polymer powder impregnated in or coated on a metal sheet. However, since the water-absorbent polymer powder adsorbs water through hydration by ions, not by pores, pollutant molecules are discharged into the air without being adsorbed.
<5> Recently, demand for high-efficiency composite materials for building air conditioning or dehumidif ication having antibacterial properties as well as excellent water absorbing ability and being easily applicable to various designs is increasing.
[Disclosure]
[Technical Problem]
<6> Aspects of the present disclosure are directed to high-efficiency composite materials for building air conditioning or dehumidif ication having antibacterial properties as well as excellent water absorbing ability and being easily applicable to various designs.
[Technical Solution]
<7> One aspect of the present disclosure provides a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion, including: (SI) adding a crossl inking agent or a crossl inking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat- treatment. Before or after step S3, the nanofiber sheet may be adhered to a metal sheet, a ceramic fiber sheet or a conductive polymer film.
<8> Another aspect of the present disclosure provides a method for preparing a polymer composite material for building air conditioning or dehumidif ication, including: (SI) adding a crosslinking agent or a crosslinking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution directly onto a metal sheet, a ceramic fiber sheet or a conductive polymer film to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat-treatment.
<9> A further aspect of the present disclosure provides a polymer composite material for building air conditioning or dehumidif ication having superior durability and antibacterial properties prepared from a solution including a hydrophilic polymer and a crosslinking agent, or a crosslinking agent and a porous filler by electrospinning and crosslinking.
[Advantageous Effects]
<io> According to the present disclosure, the polymer composite material for building air conditioning or dehumidi f icat ion has superior antibacterial properties and excellent water-adsorbing ability and durability. As a result, the polymer composite material may control humidity when used for air conditioning of a building, thereby reducing air conditioning load and improving energy efficiency. In addition, the polymer composite material may prevent various diseases and allows supply of pleasant indoor air. Further, through dehumidi fying/cool ing, the polymer composite material may remove moisture from hot and humid air in the summer, thus reducing air conditioning load by decreasing latent heat load and saving energy. Furthermore, the high- efficiency polymer composite material may be used in moisture-sensitive production processes or industrial applications requiring moisture control or protection from damage or corrosion by moisture in order to dehumidi fy and provide dry air.
<ii> The polymer composite material according to the present disclosure may be utilized for water adsorption and dehumidi f icat ion in various fields, for example, in building air conditioning and dehumidif icat ion/coo ling, including a total heat exchanger of a ventilation unit, a dehumidi f icat ion rotor for dehumidif ication/cool ing, a rotor-type total heat exchanger, or the like. [Description of Drawings]
<i2> The above and other aspects, features and advantages of the present disclosure will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
<13> Fig. 1 shows a total heat -exchange rotor according to an embodiment of the present disclosure;
<14> Fig. 2 illustrates a crossl inking mechanism of a PVA polymer in Example l;
<i5> Fig. 3 shows scanning electron micrographs of a PVA nanofiber sheet, a crosslinked sheet and a zeolite-introduced nanofiber sheet in Example 1;
<16> Fig. 4 shows water adsorption by a nanofiber sheet in Example 2;
<17> Fig. 5 shows the amount of polymer remaining after washing as compared to the initial polymer amount in Examples 2-4, as a measure of durability; <18> Fig. 6 shows a result of culturing E. coli at 35°C for 24 hours in
Examples 5-7, in order to evaluate antibacterial properties; and
<i9> ' Fig. 7 shows a result of culturing salmonella at 35°C for 24 hours in
Examples 5-7, in order to evaluate antibacterial properties.
[Best Mode]
<20> Exemplary embodiments of the present disclosure will now be described.
<2i> In one embodiment, a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion according to the present disclosure includes: (SI) adding a crossl inking agent or a crossl inking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and (S3) crosslinking the nanofiber sheet by heat- treatment .
<22> In step SI, a crosslinking agent or a crosslinking agent and a porous filler are added to a hydrophilic polymer solution in order to confer durability and antibacterial properties, thereby preparing a polymer composite material solution. The hydrophilic polymer solution may be prepared by dissolving at least one hydrophilic polymer selected from the group consisting of polyvinyl alcohol (PVA), polystyrene sulfonic acid, polystyrene sulfonic acid/maleic acid copolymer, sodium polystyrene sulfonate, polyacrylate, polyethylene glycol, polyethylene oxide, cellulose derivatives, and ion exchange resins in at least one solvent selected from the group consisting of water, alcohol, DMF, NMP and DMAc. The content of the hydrophilic polymer may be 0.5 to 50 wt based on the weight of the hydrophilic polymer solution. If the hydrophilic polymer content exceeds 50 wt%, the resulting high viscosity may prevent effective electrospinning. Conversely, if the hydrophilic polymer content is below 0.5 wt , nanofiber may not be produced because of low viscosity.
<23> This step may include: dissolving a hydrophilic polymer in a solvent to prepare a first solution; dissolving another hydrophilic polymer different from the first hydrophilic polymer in a solvent to prepare a second solution; and mixing the first solution and the second solution to prepare the hydrophilic polymer solution.
<24> The proportion of the contents of the hydrophilic polymers in the hydrophilic polymer solution is not particularly limited and may be appropriately adjusted considering required physical properties.
<25> The crosslinking agent added to improve durability and antibacterial properties may include at least one selected from the group consisting of peroxides such as dibenzoyl peroxide, inorganic precursors such as tetraethyl orthosi 1 icate, si lane coupling agents such as 3,3- diethoxypropyltriethoxysi lane, aldehydes such as glutaraldehyde, polyacrylic acids, di isocyanates, diacids and derivatives thereof, and organic acids containing a sulfonic acid group. Particularly, an organic acid containing a sulfonic acid group selected from the group consisting of sul fosuccinic acid (SSA), polystyrene sulfonic acid and poly(4-styrenesulfonic acid-co-maleic acid) sodium salt may be used.
<26> The porous filler added to improve durability and antibacterial properties may be zeolite, SBA-15, MCM-41, silica gel, carbon, carbon nanotube, or the like. Further, a porous filler substituted with metal ions such as Cu or Ag may also be used.
<27> The content of the crossl inking agent in the polymer composite material solution may be 20 wt or less based on the weight of the hydrophilic polymer. If the content of the crossl inking agent exceeds 20 wt%, the resulting polymer composite material may be too hard or brittle.
<28> ΐη addition, the content of the porous filler in the polymer composite material solution may be 50 wt or less based on the weight of the hydrophilic polymer. If the content of the porous filler exceeds 50 wt%, the filler may not be dispersed well but coagulate. Further, the amount or rate of water adsorption may decrease.
<29> In step S2, electrospinning is carried out. By electrospinning the polymer composite material solution using an electric field after injecting the solution into a syringe or capillary tube, a nanofiber sheet with increased surface area may be prepared. By applying a high-voltage electric field during electrospinning, a nanofiber structure may be more effectively formed. In addition, by controlling the viscosity of the polymer composite material solution, the applied voltage, spinning distance, or the like, the diameter of the nanofiber may be adjusted. The nanofiber may have a diameter ranging from tens of nanometers to tens of micrometers. Thus, the surface area of the composite material sheet may be controlled to confer a very large water adsorbing capacity.
<30> In step S3, the nanofiber sheet prepared in step S2 is crossl inked by heat treatment. The crosslinking is initiated by heating and performed while maintaining the elevated temperature. In the case where a metal peroxide is used as the crosslinking agent, the solution is left at room temperature for predetermined time and then the crossl inking is performed in the same manner. <3i> Before or after step S3, the nanofiber sheet may be adhered to a metal sheet, a ceramic fiber sheet or a conductive polymer film. A metal sheet such as aluminum sheet or stainless steel sheet, a ceramic fiber sheet, or a conductive polymer film such as polyvinyl chloride may be adhered to the crossl inked polymer composite material sheet or to the nanofiber sheet prior to crossl inking. Further, an adhesive may be applied on the surface of the metal sheet and the nanofiber sheet may be adhered to either or both sides of the metal sheet .
<32> In another embodiment, a method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion according to the present disclosure comprises: (SI) adding a crossl inking agent or a crossl inking agent and ._a__Dor_oiis fjJULer for conferring— dur-ab-i-l-i-t— and- antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solution; (S2) electrospinning the polymer composite material solution directly onto a metal sheet, a ceramic fiber sheet or a conductive polymer film to prepare a nanofiber sheet; and (S3) crossl inking the nanofiber sheet by heat-treatment. This embodiment is the same as the above embodiment, except that the nanofiber sheet is prepared by directly electrospinning the polymer composite material solution onto the metal sheet, the ceramic fiber sheet or the conductive polymer film.
<33> The polymer composite material for building air conditioning or dehumidif ication according to the present disclosure may be used for various applications, including a total heat exchanger for a ventilation unit, a dehumidif ication rotor for dehumidi f icat ion/cooling, a rotor-type total heat exchanger, and the like. The total heat exchanger for a ventilation unit is a rectangular-shaped heat exchanger fabricated using an insulating exchange membrane with superior water permeability. An insulating exchange membrane that transmits water but blocks polluted air is prepared in the form of a honeycomb. The total heat exchanger transmits latent heat of water included in the air through the paper insulating membrane to the introduced air during ventilation, thereby lowering indoor temperature and humidity, removes fine dust such as pollen, thereby preventing various diseases, is installed in the ceiling, thereby minimizing noise and providing a quiet environment, provides excellent ventilation through forced ventilation in both directions using separate exhaust and inlet vents, and supplies cleanly filtered fresh outside air, rather than recirculated the indoor air, thereby maintaining a pleasant indoor environment.
<34> The dehumidif ication rotor for dehumidif i cat ion/coo ling is a key component of a dehumidi f icat ion/cool ing system, which is used to dehumidify the hot and humid summer air through low-energy cooling by separating the latent heat load and the sensible heat load. Further, it is used to dehumidify the air for the purpose of cooling and drying of products, quality improvement and maintenance, humidity control of a production process, or the 1 ike. Specific applications include moisture-sens.Lti e__p-r-oduc-t-i-Qn— pr-ocesses- such as pharmaceutical, electronic or food production processes or fields requiring prevention of damage or corrosion by moisture, to remove moisture in the air and provide a dry environment.
<35> The rotor-type total heat exchanger is a high-efficiency, energy-saving device capable of controlling thermal balance associated with introduction and exhaust of indoor and outdoor air, effectively purifying indoor air, and reducing cooling/heating load. The rotor-type total heat exchanger may be utilized as a heat recovery ventilator for forced air supply/discharge by reducing the latent heat of water in the exhausted air during ventilation and exchanging heat with the water- in the air supplied from outside, without requiring an additional heating or cooling source. The absorbent of the rotor-type total heat exchanger, which serves as a latent heat exchange medium, is impregnated in, coated on or adhered to a cylindrical honeycomb structure. The polymer composite material for building air conditioning of the present disclosure may be used as the latent heat exchange medium employed in the honeycomb structure.
i36> The polymer composite material for building air conditioning or dehumidi f icat ion according to the present disclosure has superior water- adsorbing ability because of the increased surface area and the hydration by ions, and has excellent durability and antibacterial properties. Thus, when used to air condition a building, it may reduce the latent heat load of water included in the indoor air, thereby saving energy by reducing air conditioning load and supplying pleasant indoor air. Further, when used for dehumidif icat ion/cool ing, it can remove moisture from hot and humid air, thus reducing air conditioning load by decreasing the latent heat load and saving energy. In addition, it may be used in moisture-sensitive production processes or industrial applications requiring moisture control or protection from damage or corrosion by moisture in order to dehumidify and provide dry air. Accordingly, the present disclosure is applicable to various fields for water adsorption and dehumidi f icat ion.
[Mode for Invention]
<37> Hereinafter, Examples of the present disclosure will be described in detail. However, it will be apparent to those skilled in the art that the present disclosure is not limited to these examples disclosed below but can be implemented in various ways.
<38>
<39> Example 1
<40> A polyvinyl alcohol (PVA) solution was prepared by dissolving PVA
(87-89% hydrolyzed, Sigma-Aldr ich) in distilled water to 10 wt at 60°C. After adding sul fosuccinic acid (SSA, Aldrich) to the PVA solution as a crossl inking agent in an amount of 20 wt% based on the weight of PVA, the mixture was stirred for over 1 hour. Then, zeolite A was added in an amount of 1 wt% based on the weight of PVA to prepare a polymer composite material solution.
<4i> The prepared polymer composite material solution was electrospun using an electrospinning apparatus (NT-PS-35K, NTSEE Co. , Korea) to prepare a polymer nanofiber sheet. The voltage used for the electrospinning was 20 kV, and the distance between the positively charged syringe needle and the negatively charged collector was 18 cm. The syringe used to hold the spinning solution was a 10 mL glass syringe, and the diameter of the syringe needle was 0.5 mm. The feed rate of the solution was 0.7 mL/hr, and the collector rotation speed was 300 rpm. The thickness of the nanofiber sheet was controlled by adjusting spinning time. The nanofiber sheet prepared in this example had a thickness of 30 pm.
<42> The prepared nanofiber sheet was subjected to crosslinking by heating at 120 °C for 1 hour. The associated crosslinking mechanism is illustrated in Fig. 2. Also, the nanofiber sheet was observed using a scanning electron microscope (SEM, Hitachi S-4700). Scanning electron micrographs of the PVA nanofiber sheet, the cross linked sheet and the zeolite-introduced nanofiber sheet are shown in Fig. 3.
<43> The water adsorption rate of the nanofiber sheet was measured.
Experiments were performed according to the KS standard for heat exchange efficiency measurement. The diffusion coefficient was calculated from Fick's law. Under the condition of 30 °C and relative humidity 60%, the water
-11 2
adsorption rate was 2.48 x 10 cm/s for the PVA nanofiber sheet and 2.96 x
-11 2
10 cm/s for the 1% zeol it e- introduced nanofiber sheet.
<44>
<45> Examples 2 to 4
<46> A PVA solution was prepared by dissolving PVA (87-89% hydrolyzed,
Sigma-Aldrich) in distilled water to 10 wt% at 60°C. A 10 wt polystyrene sulfonic acid-maleic acid copolymer (PSSA-MA, Sigma-Aldrich) solution was prepared separately using distilled water. Thus prepared 10 wt% PVA solution and 10 wt% PSSA-MA solution were mixed at 9:1 (Example 2), 8:2 (Example 3) or 7:3 (Example 4), based on PVA:PSSA-MA, and then stirred to prepare a PVA/PSSA-MA solution. After adding SSA (Aldrich) to the resultant mixture solution as a crosslinking agent in an amount of 20 wt% based on the weight of PVA, the mixture was stirred for over 1 hour.
<47> The prepared polymer composite material solution was electrospun using an electrospinning apparatus (NT-PS-35K, NTSEE Co., Korea) to prepare a polymer nanofiber sheet. The voltage used for the electrospinning was 20 kV, and the distance between the positively charged syringe needle and the negatively charged collector was 18 cm. The syringe used to hold the spinning solution was a 10 mL glass syringe, and the diameter of the syringe needle was 0.5 mm. The feed rate of the solution was 0.7 mL/hr, and the collector rotation speed was 300 rpm. The thickness of the nanofiber sheet was controlled by adjusting spinning time. The prepared nanofiber sheet was subjected to crosslinking by heating at 120 °C for 1 hour.
<48> The water adsorption rate of the nanofiber sheet was measured and the results are shown in Fig. 4. Experiments were performed according to the KS standard for heat exchange efficiency measurement. The diffusion coefficient was calculated from Fick's law. The results show that the water adsorption rate was increased above the anticipation through the crosslinking reaction by addition of SSA. Under the condition of 30°C and relative humidity 60%,
-9 2
the adsorption rate of the sample of Example 2 was 2.59X10 cm/s before the crosslinking and 1.79X10 cm/s after the crosslinking.
<49> To evaluate durability of the nanofiber sheets prepared in these examples, each of the nanofiber sheets was washed for 1 hour using distilled water at 60°C. After washing, the amount of remaining polymer was calculated as a percentage of the initial polymer amount. Results are shown in Fig. 5. The sample of Example 2 is denoted as "1" , the sample of Example 3 is denoted as "2" , and the sample of Example 4 is denoted as "3" . It can be seen that use of the crosslinking agent resulted in a remarkable improvement in durabi 1 ity.
<50>
<5i> Examples 5 to 7
<52> A PVA solution was prepared by dissolving PVA (87-89% hydrolyzed,
Sigma-Aldrich) in distilled water to 10 wt% at 60°C . A 10 wt% PSSA-MA (Sigma- Aldrich) solution was prepared separately using distilled water. The prepared 10 wt% PVA, solution and 10 wt% PSSA-MA solution were mixed 9:1 (Example 5), based on PVA:PSSA-MA, and then stirred to prepare a PVA/PSSA-MA solution. Further, after adding SSA (Aldrich) to the resultant solution as a crosslinking agent in an amount of 20 wt% based on the weight of PVA, the mixture was stirred for over 1 hour to prepare a polymer solution (Example 6). Then, zeolite A was added thereto in an amount of 1 wt% based on the polymer weight to prepare a polymer composite material solution (Example 7). <53> In order to evaluate antibacterial properties, E. coli and salmonella bacteria were cultured in the prepared polymer composite material solutions. After culturing at 35°C for 24 hours, photographs were taken to evaluate the antibacterial properties. For measurement of the antibacterial properties against E. coli, E. coli samples were cultured separately. Results are shown in Fig. 6. The sample of Example 5 is denoted as "1" , the sample of Example 6 is denoted as "3" , and the sample of Example 7 is denoted as "4" . Some E. coli was observed in the sample of Example 5, but none was observed in Example 6 or Example 7. When the experiment was performed repeatedly, very slight E. coli was found from the sample of Example 6. Fig. 7 shows the result of culturing salmonella bacteria. In the figure, the right side shows the result when only the bacteria were cultured, and the left side shows the result when the polymer solution was used. Some salmonella bacteria were observed in Example 5, but none was observed in Example 6 or Example 7. Even when the experiment was performed repeatedly, no salmonella bacteria was observed in Example 6 or Example 7. Thus, it was confirmed that the addition of the crbssl inking agent and the porous filler results in far superior antibacterial properties.

Claims

[CLAIMS]
[Claim 1]
A method for preparing a polymer composite material for building air conditioning or dehumidi f icat ion, comprising:
(51) adding a crossl inking agent or a crossl inking agent and a porous filler for conferring durability and antibacterial properties into a hydrophilic polymer solution to prepare a polymer composite material solut ion!
(52) electrospinning the polymer composite material solution to prepare a nanofiber sheet; and
(53) crosslinking the nanofiber sheet by heat-treatment.
[Claim 2]
The method according to claim 1, further comprising: adhering the nanofiber · sheet to a metal sheet, a ceramic fiber sheet or a conductive polymer film before or after heat treatment.
[Claim 3]
The method according to claim 1, further comprising: adhering the nanofiber sheet to a metal sheet, a ceramic fiber sheet or a conductive polymer film before or after heat treatment.
[Claim 4]
The method according to any one of claims 1 to 3, wherein, in step SI, the hydrophilic polymer solution is prepared by dissolving a hydrophilic polymer in a solvent.
[Claim 5]
The method according to any one of claims 1 to 3, wherein, in step SI, the hydrophilic polymer solution is prepared by the steps of comprising: dissolving a hydrophilic polymer in a solvent to prepare a first solution; dissolving another hydrophilic polymer different from the hydrophilic polymer in a solvent to prepare a second solution; and
mixing the first solution and the second solution to prepare the hydrophilic polymer solution.
[Claim 6] The method according to claim 4, wherein the solvent is at least one selected from the group consisting of water, alcohol, DMF, NMP and DMAc.
[Claim 7]
The method according to claim 4, wherein the hydrophilic polymer is selected from the group consisting of polyvinyl alcohol (PVA), polystyrene sulfonic acid, polystyrene sulfonic acid/maleic acid copolymer, sodium polystyrene sulfonate, polyacrylate, polyethylene glycol, polyethylene oxide, cellulose derivatives, and ion exchange resins.
[Claim 8]
The method according to claim 4, wherein the hydrophilic polymer is present in an amount of 0.5 to 50 wt based on a weight of the hydrophilic polymer solution.
[Claim 9]
The ,method according to any one of claims 1 to 3, wherein the hydrophilic polymer is polyvinyl alcohol.
[Claim 10]
The method according to any one of claims 1 to 3, wherein the crossl inking agent is at least one selected from the group consisting of: peroxides, inorganic precursors and si lane coupling agents, aldehydes, polyacrylic acids, di isocyanates , diacids and derivatives thereof, and organic acids containing a sulfonic acid group.
[Claim 11]
The method according to claim 10, wherein the organic acid containing the sulfonic acid group is selected from the group consisting of sulfosuccinic acid (SSA) , polystyrene sulfonic acid and poly(4- styrenesulfonic acid-co-maleic acid) sodium salt.
[Claim 12]
The method according to claim 10, wherein the crossl inking agent is present in an amount of 20 wt% or less based on a weight of the hydrophilic polymer.
[Claim 13]
The method according to any one of claims 1 to 3, wherein the porous filler is zeolite, SBA-15, MCM-41, silica gel, carbon, carbon nanotube, or a porous filler substituted with Cu or Ag.
[Claim 14]
The method according to any one of claims 1 to 3, wherein the porous filler is present in an amount of 50 wt% or less based on a weight of the hydrophilic polymer.
[Claim 15]
A polymer composite material for building air conditioning or dehumidiiication having superior durability and antibacterial properties prepared from a solution comprising a hydrophilic polymer and a crossl inking agent, or a crosslinking agent and a porous filler by electrospinning and crossl inking.
[Claim 16]
The polymer composite material according to claim 15, wherein the polymer composite material for building air conditioning or dehumidiiication is used for an air conditioning system selected from the group consisting of a total heat exchanger for a ventilation unit and a rotor-type total heat exchanger .
[Claim 17]
The polymer composite material according to claim 15, wherein the polymer composite material for building air conditioning or dehumidiiication is used for a dehumidi f icat ion/cool ing system selected from the group consisting of a dehumidiiication rotor for dehumidiiication and a dehumidiiication rotor ior dehumidiiication type cooling.
EP10860689.8A 2010-12-15 2010-12-15 Polymer composite materials for building air conditioning or dehumidification and preparation method thereof Active EP2652191B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2010/008982 WO2012081744A1 (en) 2010-12-15 2010-12-15 Polymer composite materials for building air conditioning or dehumidification and preparation method thereof

Publications (3)

Publication Number Publication Date
EP2652191A1 true EP2652191A1 (en) 2013-10-23
EP2652191A4 EP2652191A4 (en) 2014-06-11
EP2652191B1 EP2652191B1 (en) 2021-03-31

Family

ID=46244833

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10860689.8A Active EP2652191B1 (en) 2010-12-15 2010-12-15 Polymer composite materials for building air conditioning or dehumidification and preparation method thereof

Country Status (4)

Country Link
US (1) US20130299121A1 (en)
EP (1) EP2652191B1 (en)
CN (1) CN102741469A (en)
WO (1) WO2012081744A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9370096B2 (en) 2012-04-18 2016-06-14 Cornell University Method of making conducting polymer nanofibers
CN103275568B (en) * 2013-05-06 2016-01-06 华南理工大学 The preparation method of pipe box finned heat exchanger nonionic adsorption resin hygroscopic coatings
EP2829836A1 (en) * 2013-07-22 2015-01-28 Zehnder Verkaufs- und Verwaltungs AG Enthalpy exchanger element and method for the production
EA201691148A1 (en) 2013-12-02 2020-02-07 Зендер Груп Интернэшнл Аг SYSTEM AND METHOD FOR FASTENING A HEATER OR A COOLING RADIATOR
CN105874295A (en) * 2013-12-26 2016-08-17 东丽株式会社 Method for manufacturing total heat exchanger element, and total heat exchanger element
CN106797998A (en) * 2017-01-16 2017-06-06 江南大学 A kind of method that fresh-keeping joint controlled atmosphere of conditioning peeled shrimp antibacterial activity that shells extends the refrigerated shelf phase
IT201800003884A1 (en) * 2018-03-22 2019-09-22 Univ Mediterranea Di Reggio Calabria Method for making the heat exchanger of an adsorption heat engine and respective heat engine
CN110485061B (en) * 2018-05-15 2021-07-27 北京服装学院 Electrospinning nanofiber filler for solution humidity control air conditioner
EP3862470B1 (en) * 2018-11-01 2023-12-27 Kuraray Co., Ltd. Polyvinyl alcohol fiber
CN109576906A (en) * 2018-12-25 2019-04-05 江苏国源环境科技有限公司 Air dewetting and the dual-purpose electrostatic spinning nano fiber film and preparation method thereof of filtering
CN110984298B (en) * 2019-11-14 2021-04-16 中国科学院宁波材料技术与工程研究所 Preparation method of solar-assisted air water making material, product and application thereof
CN112226911A (en) * 2020-09-22 2021-01-15 上海世龙科技有限公司 Hydrophilic composite membrane and preparation method thereof
CN114150442A (en) * 2021-12-09 2022-03-08 吉林大学 Garlicin-loaded antibacterial packaging film and preparation method thereof
CN115418863B (en) * 2022-10-13 2024-05-24 佛山市顺德区阿波罗环保器材有限公司 Composite material for humidity adjustment, preparation method thereof and humidity adjustment equipment

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6354903A (en) * 1986-08-26 1988-03-09 Agency Of Ind Science & Technol Separation membrane for pervaporation
AU8011698A (en) * 1997-06-20 1999-01-04 Coloplast A/S A hydrophilic coating and a method for the preparation thereof
US6673136B2 (en) * 2000-09-05 2004-01-06 Donaldson Company, Inc. Air filtration arrangements having fluted media constructions and methods
JP2002276998A (en) * 2001-03-15 2002-09-25 Osaka Gas Co Ltd Desiccant dehumidifier
US7105124B2 (en) * 2001-06-19 2006-09-12 Aaf-Mcquay, Inc. Method, apparatus and product for manufacturing nanofiber media
JP2003277439A (en) * 2002-03-20 2003-10-02 Osaka Gas Co Ltd Anti-microbial building material
KR20050056892A (en) * 2003-12-10 2005-06-16 학교법인 성균관대학 Electrical cell including porous continuous fiber membrane
JPWO2006033189A1 (en) * 2004-09-21 2008-05-29 ダイナエアー株式会社 Method for removing VOC from VOC impregnation
JP2006225780A (en) * 2005-02-16 2006-08-31 Kuraray Co Ltd Antibacterial fiber
KR101223559B1 (en) * 2005-06-24 2013-01-22 삼성에스디아이 주식회사 Method of preparing polymer membrane for fuel cell
CN102814080A (en) * 2006-02-13 2012-12-12 唐纳森公司 Web comprising fine fiber and reactive, adsorptive or absorptive particulate
US7942948B2 (en) * 2007-03-05 2011-05-17 Bha Group, Inc. Filter element including a composite filter media
US8308834B2 (en) * 2007-03-05 2012-11-13 Bha Group, Inc. Composite filter media
US20100317249A1 (en) * 2007-11-20 2010-12-16 Aneta Clark Article Comprising Fibers And A Method Of Forming The Same
EP2212457B1 (en) * 2007-11-20 2013-07-24 Dow Corning Corporation Article and method of manufacturing same
KR100975431B1 (en) * 2008-06-24 2010-08-11 한국에너지기술연구원 Method for manufacturing honeycomb structured body for total heat exchanger and honeycomb structured body produced thereby
CN101690843A (en) * 2009-03-30 2010-04-07 田在祥 Nano/micron invisible nasal mask and production process and dedicated wearing device thereof

Also Published As

Publication number Publication date
CN102741469A (en) 2012-10-17
US20130299121A1 (en) 2013-11-14
EP2652191A4 (en) 2014-06-11
WO2012081744A1 (en) 2012-06-21
EP2652191B1 (en) 2021-03-31

Similar Documents

Publication Publication Date Title
EP2652191B1 (en) Polymer composite materials for building air conditioning or dehumidification and preparation method thereof
CA2761826C (en) Water transport membrane featuring desiccant-loaded substrate and polymer coating
JP3346680B2 (en) Adsorbent for moisture exchange
CN110030654A (en) Air conditioning/ventilating system
KR20190013556A (en) Ventilating and air conditioning device
KR102699839B1 (en) Honeycomb adsorbent and dehumidification air conditioning device using the same
CN110016814B (en) Antibacterial asymmetric full heat exchange membrane, full heat exchange core and full heat exchange
KR101237285B1 (en) Polymer composite materials for building air conditioning or dehumidification and preparation method thereof
JP2022158649A (en) Adsorption/desorption element and humidity controller
CN107262048B (en) Low-temperature regeneration dehumidifying material of bacterial cellulose composite moisture absorbent
JP2011121004A (en) Dehumidification apparatus
CN103879034B (en) A kind of high-air-tightness Total heat exchange film and total-heat exchanger
WO2010101110A1 (en) Moisture adsorbent, sheet-like material for dehumidification, and filter material for dehumidification
JP2009019788A (en) Desiccant air conditioner
KR101525492B1 (en) Preparation method of porous film type nonwoven heat transport membrane for total heat recovery ventilator element
CN110511426A (en) A kind of composite polymer material film and preparation method thereof
CN110964280A (en) Moisture-permeable and bacteriostatic composite film for total heat exchanger and preparation method thereof
KR100975431B1 (en) Method for manufacturing honeycomb structured body for total heat exchanger and honeycomb structured body produced thereby
CN103599762A (en) Moisture absorption agent
CN114130207B (en) Multifunctional total heat exchange membrane and preparation method thereof
KR20110121102A (en) Silica gel sheet, preparation method thereof, and honeycomb type dehumidifying material comprising the same
JP2022090997A (en) Moisture permeable sheet, total heat exchange element and total heat exchanger using this
JP3345596B2 (en) Adsorbent for moisture exchange
WO2025263627A1 (en) Absorbing sheet, sheet processed by steps, laminate processed by steps, absorbing element, and dehumidifier
WO2026004027A1 (en) Method for manufacturing condensation stopping member from sponge and condensation stopping material using porous material, hyaluronic acid, and polyvinyl alcohol

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130627

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20140513

RIC1 Information provided on ipc code assigned before grant

Ipc: D01F 6/50 20060101ALI20140507BHEP

Ipc: D01F 1/10 20060101ALI20140507BHEP

Ipc: F24F 3/147 20060101ALI20140507BHEP

Ipc: D01D 5/00 20060101ALI20140507BHEP

Ipc: D01F 6/14 20060101ALI20140507BHEP

Ipc: D04H 1/728 20120101ALI20140507BHEP

Ipc: D04H 3/16 20060101AFI20140507BHEP

Ipc: F28D 19/04 20060101ALI20140507BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20170519

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20201110

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1377026

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210415

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010066711

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210630

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210630

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210331

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1377026

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210731

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210802

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010066711

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20220104

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20211215

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211215

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211215

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211215

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20101215

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250930

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20251008

Year of fee payment: 16