WO2021045103A1 - Procédé de production de mousse de polyuréthane souple - Google Patents

Procédé de production de mousse de polyuréthane souple Download PDF

Info

Publication number
WO2021045103A1
WO2021045103A1 PCT/JP2020/033262 JP2020033262W WO2021045103A1 WO 2021045103 A1 WO2021045103 A1 WO 2021045103A1 JP 2020033262 W JP2020033262 W JP 2020033262W WO 2021045103 A1 WO2021045103 A1 WO 2021045103A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane foam
flexible polyurethane
water
mixed solution
volume
Prior art date
Application number
PCT/JP2020/033262
Other languages
English (en)
Japanese (ja)
Inventor
智幸 近藤
惣一郎 廣川
Original Assignee
日清紡ケミカル株式会社
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 日清紡ケミカル株式会社 filed Critical 日清紡ケミカル株式会社
Priority to CN202080058755.0A priority Critical patent/CN114269804B/zh
Priority to JP2021506340A priority patent/JP6909364B1/ja
Publication of WO2021045103A1 publication Critical patent/WO2021045103A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/10—Packings; Fillings; Grids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a method for producing a flexible polyurethane foam.
  • Patent Document 1 describes a water treatment carrier made of a polyurethane foam having pores communicating from the surface of the carrier to the inside, wherein the polyurethane foam is a cube, a rectangular parallelepiped, or a column, and is after water swelling.
  • the length of all sides of a cube or a rectangular parallelepiped, or the diameter and height of a column after water swelling is 8 to 100 mm, the average number of pores after water swelling is 10 to 50/25 mm, and the volume swelling rate is 150.
  • Water treatment carriers characterized by being up to 1000% are described.
  • Patent Document 2 describes a hydrophilic polyurethane prepolymer (c) and a polyisocyanate compound having at least two terminal isocyanate groups in one molecule obtained by reacting the polyisocyanate compound (a 1) with the polyol compound (b).
  • a polyurethane foam obtained by adding water to a mixture with (a 2 ) and reacting the mixture, and at least a part of the polyisocyanate compound (a 1 ) and / or (a 2) does not substantially contain a polypeptide component.
  • a water-swellable polyurethane foam imparted with drug resistance which is a purified diphenylmethane diisocyanate, a method for producing the same, and a carrier for a bioreactor using the same are described.
  • a flexible polyurethane foam for a microbial immobilization carrier for water treatment is generally produced by mixing a polyisocyanate compound and a polyol compound, or a urethane prepolymer and a polyisocyanate compound together with a foaming agent, a foam stabilizer, or the like and foaming them. Will be done. Above all, when the flexible polyurethane foam is manufactured by the batch method, the production efficiency can be improved by manufacturing the individual slabs with a large bottom area and a high height, but when the slabs are large, the input amount of the mixed solution increases.
  • the density, water swellability, and pore structure are due to the fact that the previously charged mixture hardens while the mixture is being charged into the foam container, while there is an upper limit to increasing the discharge rate.
  • the “cell structure”) varied widely in the flexible polyurethane foam slab, and it was difficult to ensure the homogeneity of the physical properties.
  • the slab becomes smaller the density, water swellability, and cell structure differ between the central portion and the peripheral portion (upper surface, lower surface, side surface) in the slab, so that the portion where the homogeneity of physical properties is ensured decreases, and the yield is reduced. Decreases.
  • the upper part of the foam container is usually in an open state, the upper part of the slab is arched, and the flexible polyurethane foam is sliced horizontally on the bottom surface of the slab (hereinafter, also referred to as "horizontal direction") to form a urethane foam sheet.
  • the arch-shaped portion has a problem that the area is small when sliced and the usable range is small, so that the production efficiency is lowered.
  • the present invention has been made to solve such a problem, and provides a method for efficiently producing a flexible polyurethane foam having excellent density, water swellability, and cell structure homogeneity by a batch method.
  • the purpose is to do.
  • a flexible polyurethane foam having excellent density, water swellability, and cell structure homogeneity is efficiently produced by a batch method in which a mixed solution containing a predetermined component is injected into a foam container having a predetermined wall surface temperature and foamed. It is based on the finding that it can be obtained.
  • a method for producing a flexible polyurethane foam used as a microbial immobilization carrier for water treatment has a step of injecting a mixed solution containing a urethane prepolymer and a polyisocyanate compound (a) into a foam container and foaming the mixture to obtain a flexible polyurethane foam.
  • the flexible polyurethane foam has a swelling density of 25 to 70 kg / m 3 at the time of water swelling, an average number of pores of 9 to 30 at the time of water swelling / 25 mm, and a volume at the time of water swelling with respect to a volume in an absolutely dry state.
  • a method for producing a flexible polyurethane foam which has a volume swelling rate of 110 to 1000%.
  • a flexible polyurethane foam having excellent density, water swellability, and cell structure homogeneity can be efficiently obtained by the batch method.
  • the method for producing a flexible polyurethane foam of the present invention is a method for producing a flexible polyurethane foam for a microbial immobilization carrier for water treatment.
  • the production method includes a step of injecting a mixed solution containing a urethane prepolymer and a polyisocyanate compound (a) into a foam container and foaming the mixture to obtain a flexible polyurethane foam, and the mixed solution of the foam container is in contact with the mixed solution.
  • the wall surface temperature TW is 21 to 60 ° C.
  • the flexible polyurethane foam has a swelling density of 25 to 70 kg / m 3 at the time of water swelling, an average number of pores of 9 to 30 at the time of water swelling / 25 mm, and a volume at the time of water swelling with respect to a volume in an absolutely dry state.
  • the volume swelling rate represented by the ratio of is 110 to 1000%.
  • the term "at the time of water swelling” as used in the present invention refers to a state in which the flexible polyurethane foam is immersed in water at 25 ° C. for 1 hour.
  • the "swelling density" referred to in the present invention refers to a value obtained as a value obtained by dividing the mass in an absolutely dry state by the volume at the time of water swelling.
  • the swelling density can be measured by the method described in Examples described later.
  • the “absolutely dry state” refers to a state in which the flexible polyurethane foam is dried at 100 ° C. and no decrease in mass is observed. It may be called an absolutely dry state.
  • the “volume swelling rate” referred to in the present invention refers to a value represented by the ratio of the volume at the time of water swelling to the volume in the absolutely dry state.
  • the “volume in the absolute dry state” shall include the pores of the flexible polyurethane foam, and shall be the volume obtained based on the outer dimensions of the flexible polyurethane foam in the absolute dry state.
  • the "volume at the time of water swelling" shall include the pores of the flexible polyurethane foam and the water absorbed therein, and shall be the volume obtained based on the external dimensions of the swelled flexible polyurethane foam.
  • the value calculated as the product of the lengths of the three sides of the rectangular parallelepiped, that is, the length, the width, and the height is taken as the volume of the flexible polyurethane foam.
  • the step of obtaining the flexible polyurethane foam is a step of injecting a mixed solution containing the urethane prepolymer and the polyisocyanate compound (a) into a foam container and foaming the mixture to obtain the flexible polyurethane foam, and the mixing of the foam container.
  • temperature T W (hereinafter, also referred to as temperature T W of the walls.) of wall the solution contacts is 21 ⁇ 60 ° C..
  • the temperature T W of the walls, the mixed solution was injected until foaming is complete, in the range of 21 ⁇ 60 ° C..
  • the mixed solution contains a urethane prepolymer and a polyisocyanate compound (a).
  • the urethane prepolymer is a polymer obtained by reacting a polyol compound with a polyisocyanate compound (b) in an amount such that the molar equivalent ratio of isocyanate groups is excessive, preferably 110% or more, with respect to the hydroxyl group of the polyol compound. It has two or more isocyanate groups in one molecule.
  • the urethane prepolymer may be used alone or in combination of two or more. By using such a prepolymer as a raw material compound, it is easy to obtain a flexible polyurethane foam having excellent water swelling property, a small variation in density and cell structure, and excellent homogeneity.
  • the urethane prepolymer is a polyether urethane prepolymer having two or more isocyanate groups in one molecule, which is obtained by reacting a polyether polyol with a polyisocyanate compound (b), and a polyester polyol and a polyisocyanate compound.
  • a polyether polyol with a polyisocyanate compound (b)
  • a polyester polyol and a polyisocyanate compound examples thereof include polyester-based urethane prepolymers having two or more isocyanate groups in one molecule obtained by reacting with (b).
  • Both the polyether polyol and the polyester polyol can impart hydrophilicity, but the polyether polyol is more excellent in hydrolysis resistance than the polyester polyol.
  • the polyether urethane prepolymer is polyester-based from the viewpoint of the durability of the flexible polyurethane foam.
  • the urethane prepolymer preferably has a viscosity that is not too high from the viewpoint of ease of handling, and the viscosity is preferably 300 to 9500 mPa ⁇ s as measured by a spindle viscometer at 25 ° C. , 300 to 9000 mPa ⁇ s, more preferably 300 to 8500 mPa ⁇ s.
  • polyether polyol examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like. These are obtained by ring-opening polymerization of the cyclic ether compounds, ethylene oxide (EO), propylene oxide (PO), and tetrahydrofuran, respectively.
  • the polyether polyol may be used alone or in combination of two or more. Further, it may be a copolymer of a cyclic ether compound and is used in water as a microbial immobilization carrier for water treatment. Therefore, from the viewpoint of hydrophilicity of the flexible polyurethane foam, EO-PO co-weight is particularly important. Coalescence is preferred.
  • the monomer composition ratio of EO and PO in the EO-PO copolymer is preferably 70/30 to 30/70 by mass ratio, more preferably 65/35 to 40/60, and further preferably 60/40. ⁇ 50/50.
  • the polyisocyanate compound (b) is a compound having two or more isocyanate groups in one molecule, and is not particularly limited.
  • examples of the polyisocyanate compound (b) include toluene diisocyanate (TDI), xylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, biphenylenedi isocyanate, diphenyl ether diisocyanate, trizine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and the like. Be done.
  • the polyisocyanate compound (b) may be used alone or in combination of two or more.
  • the polyisocyanate compound (b) When the polyisocyanate compound (b) is a compound having isomers, it may be only one kind of each isomer or a mixture of two or more kinds of isomers.
  • TDI has two isomers of toluene-2,4-diisocyanate (2,4-TDI) and toluene-2,6-diisocyanate (2,6-TDI), and there are 2,4-TDI and 2 , 6-TDI alone or a mixture of the two may be used.
  • the polyisocyanate compound (b) is preferably toluene diisocyanate from the viewpoint of increasing the viscosity of the obtained prepolymer.
  • the content of the urethane prepolymer in the mixed solution is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, and further preferably 30 to 60% by mass.
  • the polyisocyanate compound (a) is not particularly limited, and specific examples thereof include those similar to those exemplified for the polyisocyanate compound (b) used in the synthesis of the urethane prepolymer.
  • the polyisocyanate compound (a) may be used alone or in combination of two or more. Further, the polyisocyanate compound (a) may be the same as or different from the polyisocyanate compound (b) used in the synthesis of the urethane prepolymer.
  • the polyisocyanate compound (a) is preferably toluene diisocyanate from the viewpoint of obtaining a flexible polyurethane foam for a microbial immobilization carrier for water treatment, which is excellent in durability (elasticity and abrasion resistance).
  • the content of the polyisocyanate compound (a) in the mixed solution is preferably 1 to 30% by mass, more preferably 1.5 to 20% by mass, and further preferably 2 to 10% by mass.
  • the mixed solution preferably contains a foaming agent.
  • the foaming agent include hydrocarbons such as water, hydrofluorocarbon (HFC), hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), carbon dioxide gas, and cyclopentane. These foaming agents may be used alone or in combination of two or more. Among the foaming agents, water is preferable from the viewpoint of ease of handling, cost, environmental protection and the like.
  • the type and content of the foaming agent in the mixed solution can be appropriately set in consideration of the pore size of the flexible polyurethane foam that affects the microbial immobilization performance of the microbial immobilization carrier for water treatment.
  • the mixed solution preferably contains a curing agent.
  • the curing agent is added for cross-linking and curing the urethane prepolymer and the polyisocyanate compound (a), and is sometimes called a cross-linking agent.
  • the curing agent include water; polyhydric alcohols such as glycerin, 1,4-butanediol and diethylene glycol; amine compounds such as ethanolamines and polyethylene polyamines. Examples thereof include polyols obtained by ring-opening polymerization of ethylene oxide, propylene oxide and the like to the polyhydric alcohol, and those in which a small amount of propylene oxide is added to the amine compound.
  • These curing agents may be used alone or in combination of two or more.
  • the curing agents water is preferable from the viewpoint of reactivity, ease of handling, cost and the like.
  • the content of the curing agent in the mixed solution is appropriately set in consideration of the flexibility, elasticity, strength, etc. of the flexible polyurethane foam, which affects the microbial immobilization performance and strength of the microbial immobilization carrier for water treatment. be able to.
  • water is preferably used as a foaming agent and a curing agent in the production of flexible polyurethane foam used as a microbial immobilization carrier for water treatment.
  • the content of water in the mixed solution is preferably 20 to 55% by mass, more preferably 25 to 50% by mass.
  • the mixed solution preferably contains an inorganic filler.
  • an inorganic filler By using an inorganic filler, the specific gravity of the produced flexible polyurethane foam can be adjusted, and when the microbial immobilization carrier for water treatment prepared using the flexible polyurethane foam is put into water, it quickly settles in water. Can be made to.
  • the inorganic filler include barium sulfate, calcium carbonate, talc, silica, alumina, activated carbon, and zeolite.
  • the inorganic filler may be used alone or in combination of two or more.
  • the inorganic filler preferably has a small bulk volume, and from this viewpoint, barium sulfate having a large specific gravity is preferable.
  • the inorganic filler preferably has an average particle size of 0.1 to 100 ⁇ m, more preferably 0.5 to 70 ⁇ m, and further preferably 0.5 to 70 ⁇ m, from the viewpoint of uniform dispersibility in the produced flexible polyurethane foam. It is preferably 1 to 50 ⁇ m.
  • the "average particle size" referred to in the present invention refers to the particle size (D 50 ) at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method. Specifically, a measured D 50 value using a laser diffraction-scattering type particle size distribution measuring device "MT3300" (manufactured by Microtrac Bell Co., Ltd.).
  • the content of the inorganic filler is appropriately adjusted according to physical properties such as the specific gravity of the produced flexible polyurethane foam, but is 30 mass by mass with respect to 100 parts by mass of the urethane prepolymer.
  • the amount is preferably 1 part or less, more preferably 1 to 25 parts by mass, and further preferably 2 to 20 parts by mass.
  • the mixed solution contains, if necessary, a foam stabilizer, a catalyst, a solvent, a coloring agent, an antioxidant, and an ultraviolet absorber. And other additives may be included.
  • the foam stabilizer is added to obtain a flexible polyurethane foam having a more uniform pore size, density, and the like.
  • the foam stabilizer include surfactants, silicone oils and the like. These foam stabilizers may be used alone or in combination of two or more.
  • a surfactant having a hydroxyl group at the molecular terminal and capable of chemically bonding with isocyanate is preferable because it is difficult to dissolve when it is put into a treatment tank as a microbial immobilization carrier for water treatment. ..
  • the surfactants nonionic surfactants, which have less foaming than anionic surfactants, are preferable.
  • the catalyst may be added to accelerate the reaction between the urethane prepolymer and the polyisocyanate compound (a).
  • a known catalyst used for the synthesis of flexible polyurethane foam can be used, and for example, an amine catalyst such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholin, tetramethylguanidine; Tin catalysts such as ate and dibutyltin dilaurate; other metal catalysts such as phenylmercury propionate and lead octenoate can be mentioned.
  • amine catalysts are preferable.
  • the content of the additive in the mixed solution is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass.
  • the method for mixing the components contained in the mixed solution is not particularly limited, but the urethane prepolymer and the polyisocyanate compound (a) are mixed in advance, and a foaming agent is added to the mixture to obtain the urethane prepolymer. It is preferable to foam the mixture containing the polyisocyanate compound (a). Ingredients other than the above may be added to a mixture containing the urethane prepolymer and the polyisocyanate compound (a) or a foaming agent in consideration of its characteristics.
  • Foam container used in the present invention is not particularly limited, the temperature T W of the walls mixed solution is in contact, the mixed solution was injected until foaming is completed, is within a range of 21 ⁇ 60 ° C. ..
  • Flexible polyurethane foams such as those used for microbial immobilization carriers for water treatment generally generate heat when foamed.
  • the temperature of the central part of the flexible polyurethane foam slab is high because the heat generated during foaming is trapped inside, but the temperature of the part near the side surface of the slab (the part close to the wall surface of the foam container) is lower than that of the central part.
  • the reaction rate differs between the central portion and the portion close to the side surface, and as a result, the phenomenon that the physical properties such as the density, water swellability, and cell structure of the flexible polyurethane foam differ between the central portion and the portion close to the side surface is likely to occur.
  • the temperature of the foam container is higher than the central part of the slab of the flexible polyurethane foam
  • the reaction rate becomes faster in the part closer to the side surface than the central part, and as a result, the density, water swelling property of the flexible polyurethane foam.
  • different phenomena such as cell structures are likely to occur in the central portion and the portion close to the side surface, and the density is lowered as a whole.
  • the temperature T W of the walls within the above range it is possible to suppress a rapid temperature drop or rise in temperature of the mixed solution present in the wall portion, as a result, the flexible polyurethane foam which is excellent in uniformity of physical properties, It can be manufactured efficiently.
  • Temperature T W of the walls in the step of obtaining a flexible polyurethane foam, density, water-swellable, and the viewpoint of obtaining a flexible polyurethane foam which is excellent in homogeneity of the cell structure, and from the viewpoint of producing a flexible polyurethane foam efficiently preferably It is 22 ° C. or higher, more preferably 23 ° C. or higher, still more preferably 24 ° C. or higher, and from the same viewpoint, preferably 55 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 45 ° C. or lower.
  • the absolute value of the difference between the temperature T W of the temperature T S and the wall surface of the mixed solution is preferably 0 ⁇ 40 ° C.
  • the "temperature T S of the mixed solution” in the present invention refers to the temperature of the mixed solution immediately after the components of the mixed solution was stirred and mixed all.
  • the absolute value of the difference between the temperature T S and the wall temperature T W of the mixed solution With such a range, more density, water-swellable, and a flexible polyurethane foam which is excellent in homogeneity of the cell structure, more efficient Can be manufactured as a target.
  • the shape of the foam container is preferably a cube type or a rectangular parallelepiped type from the viewpoint of efficiently producing the flexible polyurethane foam.
  • the foam container preferably has a container body having an open upper surface and a lid for closing the open upper surface of the container body. In the process of obtaining the flexible polyurethane foam, by using such a foam container and covering the upper surface of the foam container with a lid, it becomes possible to manufacture the flexible polyurethane foam having a desired shape, and the flexible polyurethane foam can be efficiently produced. Can be manufactured.
  • the temperature of the lid is not particularly limited, and the temperature may not be adjusted, and may be appropriately adjusted to a desired temperature such as the same temperature as the wall surface in contact with the mixed solution of the foam container.
  • the shape of the foam container is a cube or a rectangular parallelepiped
  • the shape of the flexible polyurethane foam can also be obtained as a cube or a rectangular parallelepiped.
  • the height of the inner dimension of the foam container is preferably 300 mm to 1200 mm, more preferably, from the viewpoint of efficient production while ensuring the density, water swellability, and homogeneity of the cell structure of the flexible polyurethane foam. It is 400 mm to 1000 mm, more preferably 500 mm to 800 mm.
  • the volume capable of accommodating the mixed solution inside the foam container is preferably 0.03 to 0.8 m 3 from the viewpoint of efficiently producing the flexible polyurethane foam, and more preferably 0.1 to 0. .6m 3, more preferably from 0.2 ⁇ 0.5 m 3.
  • the method of injecting the mixed solution into the foam container is not particularly limited, but can be carried out by, for example, a method of mixing and injecting using a mixing head.
  • a method of mixing and injecting using a mixing head it is preferable to inject the mixed solution along the wall surface of the foam container.
  • the mixed solution being injected can be injected below the already injected mixed solution, and the bubbles formed by foaming contained in the already injected mixed solution are injected later. It is possible to prevent the mixture from being crushed by the mixed solution.
  • a flexible polyurethane foam having higher density, water swellability, and cell structure homogeneity can be efficiently produced.
  • the injection rate when injecting the mixed solution into the foam container is preferably 5 to 200 kg / min, more preferably 50 to 150 kg, from the viewpoint of obtaining a flexible polyurethane foam having excellent density, water swellability, and cell structure homogeneity.
  • / Min more preferably 75-125 kg / min.
  • the mixed solution may be poured into the foam container with a part or all of the lid on the upper surface, or the lid may be placed during the injection of the mixed solution.
  • the lid may be closed before the injection is complete and the foaming of the mixed solution is complete.
  • the flexible polyurethane foam obtained by the present invention is obtained by injecting a mixed solution containing a urethane prepolymer and a polyisocyanate compound (a) into a foaming container and foaming the foam, and has a swelling density of 25 to 25 to 2 when water swells. It is 70 kg / m 3 , the average number of pores at the time of water swelling is 9 to 30/25 mm, and the volume swelling rate expressed by the ratio of the volume at the time of water swelling to the volume in the absolute dry state is 110 to 1000%. is there.
  • Swelling density during the water swelling of the soft polyurethane foam, as applied to microbial immobilization carrier for water treatment preferably 28 ⁇ 60kg / m 3, more preferably 28.5 ⁇ 50kg / m 3.
  • the flexible polyurethane foam having a swelling density of less than 25 kg / m 3 at the time of water swelling has too little resin, has low strength, and is easily deformed. There is a risk of inconveniences such as clogging of the screen, deformation of the screen, passing through the screen, and leakage from the processing tank. Further, when the amount of resin is small, it is vulnerable to physical wear and the volume is reduced (consumed) quickly. On the other hand, if the swelling density at the time of water swelling exceeds 70 kg / m 3 , the raw material cost becomes excessive, which is not preferable.
  • the cell structure of the flexible polyurethane foam includes microorganisms, oxygen required for respiration of microorganisms, nutrients necessary for activity and proliferation of microorganisms, and objects (organic substances (hydrocarbons), nitrogen compounds, phosphorus) to be removed by microorganisms. From the viewpoint of allowing a substrate such as compound) to sufficiently invade the inside and immobilizing the microorganism on the microbial immobilization carrier for water treatment, a continuous ventilation hole structure is desirable.
  • the average number of pores at the time of water swelling is 9 to 30 pores / 25 mm, preferably 10 to 25 pores / 25 mm, and more preferably 11 to 20 pores / 25 mm.
  • the "average number of pores at the time of water swelling” refers to the average value of the number of pores existing on any three 25 mm long straight lines of the flexible polyurethane foam at the time of water swelling. Specifically, it can be measured by the method described in Examples described later.
  • the flexible polyurethane foam obtained by the present invention has a volume swelling rate of 110 to 1000%, preferably 120 to 800%, more preferably 140 to 500, still more preferably 140 to 500, from the viewpoint of good hydrophilicity and the like. Is 150-300%.
  • the flexible polyurethane foam having a volume swelling rate of less than 110% cannot be said to have sufficient compatibility with water, and cannot be said to be excellent in hydrophilicity.
  • the flexible polyurethane foam having a volume swelling rate of more than 1000% is not preferable because it becomes difficult to maintain the durability required as a microbial immobilization carrier for water treatment.
  • absolute dry density representing the density in absolutely dry conditions, preferably 48 ⁇ 130kg / m 3, more preferably 49 ⁇ 110kg / m 3, more preferably 50 ⁇ 90kg / m 3.
  • the average pore diameter at the time of water swelling is preferably 0.20 to 2.00 mm, more preferably 0.50 to 1.90 mm, and further preferably 0.70 to 1.80 mm.
  • the average pore size at the time of water swelling is within this range, microorganisms, oxygen required for respiration of microorganisms, nutrients necessary for activity and proliferation of microorganisms, and objects removed by microorganisms (organic matter (hydrocarbons)) , Nitrogen compound, phosphorus compound) and the like can be sufficiently invaded inside to facilitate the immobilization of microorganisms.
  • the "average pore diameter at the time of water swelling” means that the major axis and the minor axis are measured for one pore in the cross section of the flexible polyurethane foam at the time of water swelling, and the average value of the major axis and the minor axis is the diameter. In the same way, for a total of 50 pores, the average value of the diameters when they are regarded as perfect circles is used.
  • the width of the minimum portion of the skeleton between adjacent pores at the time of water swelling is preferably 0.05 to the skeleton portion of the flexible polyurethane constituting the cell structure. It is 0.50 mm, more preferably 0.07 to 0.40 mm, still more preferably 0.10 to 0.30 mm.
  • the skeleton portion has a partially membranous structure between adjacent pores rather than a so-called rib structure composed of a thin rod-shaped skeleton. It is preferable to have a so-called wall structure having a large surface area by being partitioned by a wall surface.
  • the flexible polyurethane foam is preferably produced in the form of a slab from the viewpoint of efficiently producing the flexible polyurethane foam.
  • the height of the flexible polyurethane foam produced as a slab is preferably 300 mm to 1200 mm, more preferably 400 mm to 1000 mm, and further preferably 500 mm to 800 mm from the viewpoint of efficiently producing the flexible polyurethane foam.
  • the volume of flexible polyurethane foams from the viewpoint of producing a flexible polyurethane foam efficiently, preferably 0.03 ⁇ 0.8 m 3, more preferably 0.1 ⁇ 0.6 m 3, more preferably 0.2 It is ⁇ 0.5 m 3 .
  • the "volume of the flexible polyurethane foam" referred to in the present invention is assumed to include the pores of the flexible polyurethane foam, and is a volume obtained based on the outer dimensions of the flexible polyurethane foam.
  • the flexible polyurethane foam can be used as a microbial immobilization carrier for water treatment by, for example, cutting a slab-like product into a desired size.
  • -Urethane prepolymer (1) TDI-modified EO-PO copolymer; EO / PO mass ratio: 55/45, number average molecular weight of EO-PO copolymer: 2700 (theoretical value), containing NCO (isocyanate group) Amount: 4.5% by mass, viscosity (25 ° C): 8000 mPa ⁇ s -Urethane prepolymer (2): TDI-modified EO-PO copolymer; EO / PO mass ratio: 50/50, number average molecular weight of EO-PO copolymer: 2500 (theoretical value), containing NCO (isocyanate group) Amount: 4.5% by mass, viscosity (25 ° C): 8000 mPa ⁇ s Polyisocyanate compound (a): TDI; "Coron
  • Example 1 400 kg of TDI-modified EO-PO copolymer (urethane prepolymer (1)), 53.4 kg of TDI (polyisocyanate compound (a)), and 50.0 kg of barium sulfate (inorganic filler) were stirred and mixed to prepare A1 solution. .. Separately from the A1 solution, 350 kg of water and 7 kg of the defoaming agent were stirred and mixed to prepare the B1 solution. Next, the A1 solution (28 ° C.) and the B1 solution (14 ° C.) were pumped from the respective tanks to the mixing head at a blending mass ratio of 1.48 (A1 solution / B1 solution).
  • Example 2 and Comparative Examples 1 and 2 The wall surface temperature T W, respectively the temperature shown in Table 1, and otherwise in the same manner as in Example 1 to produce flexible polyurethane foams.
  • a slab-shaped flexible polyurethane foam was produced 5 times in Example 2, 1 time in Comparative Example 1, and 4 times in Comparative Example 2.
  • Example 3 400 kg of TDI-modified EO-PO copolymer (urethane prepolymer (2)), 53.4 kg of TDI (polyisocyanate compound (a)), and 50.0 kg of barium sulfate (inorganic filler) were stirred and mixed to prepare an A2 solution. .. Separately from the A2 solution, 350 kg of water, 29 kg of the defoaming agent, and 6.7 kg of the catalyst were stirred and mixed to prepare the B2 solution. Next, using the A2 solution (28 ° C.) and B2 liquid (14 ° C.), a wall surface temperature T W to a temperature shown in Table 1, and otherwise in the same manner as in Example 1 to produce flexible polyurethane foams. The slab-shaped flexible polyurethane foam was produced twice.
  • the flexible polyurethane foam piece having all the inside of the region X 10 mm or more inside the side peripheral surface of the flexible polyurethane foam sheet was collected, and the flexible polyurethane having all or part outside the region X was collected.
  • the foam pieces were removed and discarded.
  • the yield of the flexible polyurethane foam produced in the above Examples and Comparative Examples was evaluated by the following method. Specifically, the yield was defined as a value obtained by dividing the total weight of the recovered flexible polyurethane foam pieces by the weight of the mixed solution injected into the foam container and multiplying the value by 100. Table 1 summarizes the yield evaluation results.
  • volume swelling rate The ratio of the volume V w at the time of water swelling to the volume V d in the absolutely dry state was determined as the volume swelling rate (%).
  • Examples 1 and 2 good yields were obtained by setting the wall surface temperature TW to 25 ° C. and 30 ° C. That is, it was confirmed that the flexible polyurethane foam can be efficiently produced by setting the wall surface temperature TW to 21 to 60 ° C. Further, the obtained polyurethane foam has a predetermined swelling density at the time of water swelling, an average number of pores at the time of water swelling, and a volume swelling rate, and the difference in physical property values between the central portion and the vicinity of the side surface is small, and the homogeneity of the physical properties is small. It was confirmed that it was excellent.
  • Comparative Examples 1 and 2 has a low wall surface temperature T W of the foam container, the mixed solution near the walls affected by this, a flexible polyurethane foam after production has a high height of the central portion, the foaming solution It had a mountain-like shape with a low height around the wall surface. As a result, the yield was low, and there were many cases where the difference in physical property values was large between the central portion of the flexible polyurethane foam and the vicinity of the wall surface.
  • the batch method has a predetermined swelling density at the time of water swelling, an average number of pores at the time of water swelling, and a volume swelling rate, and has density, water swellability, and A flexible polyurethane foam having excellent cell structure homogeneity can be efficiently produced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Microbiology (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Biological Treatment Of Waste Water (AREA)

Abstract

L'invention concerne un procédé de production d'une mousse de polyuréthane souple utilisée dans un support d'immobilisation de microorganismes pour le traitement des eaux, le procédé de production de la mousse de polyuréthane souple comprenant une étape dans laquelle une solution mixte contenant un prépolymère d'uréthane et un composé polyisocyanate (a) est injectée dans un récipient de moussage et moussée pour obtenir la mousse de polyuréthane souple, la température TW d'une surface de paroi du récipient de moussage qui entre en contact avec la solution mélangée étant de 21 à 60 °C, et la mousse de polyuréthane souple ayant une densité de gonflement de 25 à 70 kg/m3 dans un état gorgé d'eau, une porosité moyenne de 9 à 30 pores/25 mm dans un état gorgé d'eau, et un taux de gonflement en volume de 110 à 1000 %, représenté par le rapport entre son volume dans un état gorgé d'eau et son volume dans un état sec.
PCT/JP2020/033262 2019-09-02 2020-09-02 Procédé de production de mousse de polyuréthane souple WO2021045103A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202080058755.0A CN114269804B (zh) 2019-09-02 2020-09-02 软质聚氨酯泡沫的制备方法
JP2021506340A JP6909364B1 (ja) 2019-09-02 2020-09-02 軟質ポリウレタンフォームの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019159945 2019-09-02
JP2019-159945 2019-09-02

Publications (1)

Publication Number Publication Date
WO2021045103A1 true WO2021045103A1 (fr) 2021-03-11

Family

ID=74852040

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/033262 WO2021045103A1 (fr) 2019-09-02 2020-09-02 Procédé de production de mousse de polyuréthane souple

Country Status (3)

Country Link
JP (1) JP6909364B1 (fr)
CN (1) CN114269804B (fr)
WO (1) WO2021045103A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023053985A1 (fr) * 2021-09-28 2023-04-06 日清紡ケミカル株式会社 Véhicule de microorganismes immobilisés pour le traitement des eaux

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0951794A (ja) * 1995-06-09 1997-02-25 Nisshinbo Ind Inc バイオリアクター用多孔質担体
JPH10174990A (ja) * 1996-12-17 1998-06-30 Nisshinbo Ind Inc バイオリアクタ−用担体及び方法
JP2005206743A (ja) * 2004-01-26 2005-08-04 Kansai Paint Co Ltd 粒状含水ゲルの製造方法
JP2006274146A (ja) * 2005-03-30 2006-10-12 Nippon Polyurethane Ind Co Ltd 熱硬化ポリウレタンエラストマー形成性組成物及び該組成物を用いた熱硬化ポリウレタンエラストマー成型物の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3834682A (en) * 1972-06-19 1974-09-10 American Hospital Supply Corp Mixing column for medical humidifier and method of humidifying inhalable gases
DE3402696A1 (de) * 1984-01-26 1985-08-01 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von schaumstoffhaltigen polyurethan(harnstoff)-massen, schaumstoffhaltige polyurethan(harnstoff)-massen und ihre verwendung
DE19509499A1 (de) * 1995-03-16 1996-09-19 Elastogran Gmbh Verfahren zur Herstellung von Polyurethan-Weichschaumstoffen mit einer unregelmäßigen Zellstruktur
US20140141233A1 (en) * 2012-07-03 2014-05-22 Peterson Chemical Technology, Inc. Surface Infusion of Flexible Cellular Foams With Novel Liquid Gel Mixture
EP2938666A4 (fr) * 2012-12-27 2016-06-29 Peterson Chemical Technology Inc Infusion de surface de mousses cellulaires flexibles par un nouveau mélange liquide gel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0951794A (ja) * 1995-06-09 1997-02-25 Nisshinbo Ind Inc バイオリアクター用多孔質担体
JPH10174990A (ja) * 1996-12-17 1998-06-30 Nisshinbo Ind Inc バイオリアクタ−用担体及び方法
JP2005206743A (ja) * 2004-01-26 2005-08-04 Kansai Paint Co Ltd 粒状含水ゲルの製造方法
JP2006274146A (ja) * 2005-03-30 2006-10-12 Nippon Polyurethane Ind Co Ltd 熱硬化ポリウレタンエラストマー形成性組成物及び該組成物を用いた熱硬化ポリウレタンエラストマー成型物の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023053985A1 (fr) * 2021-09-28 2023-04-06 日清紡ケミカル株式会社 Véhicule de microorganismes immobilisés pour le traitement des eaux

Also Published As

Publication number Publication date
CN114269804A (zh) 2022-04-01
JPWO2021045103A1 (ja) 2021-09-27
CN114269804B (zh) 2023-05-05
JP6909364B1 (ja) 2021-07-28

Similar Documents

Publication Publication Date Title
JP5390497B2 (ja) ポリウレタンフォームの製造方法及びポリウレタンフォーム
US9951174B2 (en) Polyol compositions, a process for the production of these polyol compositions, and their use in the production of open celled polyurethane foams having high airflow
US6734220B2 (en) Fine cell, high density viscoelastic polyurethane foams
CN1772786B (zh) 具有低堆积密度和压缩强度的软泡沫塑料
CN1404503A (zh) 硬质聚氨酯泡沫塑料
CN1294141A (zh) 用于生产开孔聚氨酯柔性泡沫体的硅氧烷表面活性剂
WO2013043645A1 (fr) Procédé de fabrication de mousses de polyéther à écoulement d'air élevé et mousses obtenues par ce procédé
CN111465630B (zh) 柔性聚氨酯泡沫
CN1578797A (zh) 刚性复合聚氨酯泡沫体
JP2006519918A (ja) 低アミン放出性ポリウレタンフォーム
CN112912412A (zh) 改进的包含羟基封端的预聚物的粘弹性柔性泡沫
JP6917535B1 (ja) 軟質ポリウレタンフォームの製造方法
JP6909364B1 (ja) 軟質ポリウレタンフォームの製造方法
JP2005060643A (ja) ポリウレタンフォーム及びその製造方法
WO2009098966A1 (fr) Mousse de polyuréthane souple à faible élasticité
JP4020972B2 (ja) 軟質弾性連続気泡ポリウレタンフォームの不連続製造法
CN114555683A (zh) 水处理用微生物固定化载体、树脂发泡体及其原料组合物
JP3419683B2 (ja) ポリウレタンフォームの製造法
JP4828370B2 (ja) 水処理用微生物担体の製造方法
WO2021045104A1 (fr) Procédé de production d'un support immobilisant des microorganismes pour le traitement des eaux
JP2021181538A (ja) 低膨潤親水性ウレタンフォーム
WO2023053984A1 (fr) Véhicule fixé de microorganismes pour le traitement des eaux et son procédé de fabrication
JP2006282719A (ja) ポリウレタンフォームの製造方法
JP2006206793A (ja) ポリウレタンフォームの製造方法およびポリウレタンフォーム
JP2004359950A (ja) 薬剤耐性を付与した水膨潤性ポリウレタンフォームとその製造方法及びそれを用いたバイオリアクター用担体

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2021506340

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20861171

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20861171

Country of ref document: EP

Kind code of ref document: A1