WO2022075275A1 - 低臭気エマルションの製造方法 - Google Patents

低臭気エマルションの製造方法 Download PDF

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Publication number
WO2022075275A1
WO2022075275A1 PCT/JP2021/036678 JP2021036678W WO2022075275A1 WO 2022075275 A1 WO2022075275 A1 WO 2022075275A1 JP 2021036678 W JP2021036678 W JP 2021036678W WO 2022075275 A1 WO2022075275 A1 WO 2022075275A1
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Prior art keywords
emulsion
processing container
diameter
container
supply port
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PCT/JP2021/036678
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English (en)
French (fr)
Japanese (ja)
Inventor
廣之 柴田
勝 寺田
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Toagosei Co Ltd
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Toagosei Co Ltd
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Priority to EP21877574.0A priority Critical patent/EP4227326A4/en
Priority to CN202180067612.0A priority patent/CN116323714A/zh
Priority to JP2022555475A priority patent/JP7736009B2/ja
Publication of WO2022075275A1 publication Critical patent/WO2022075275A1/ja
Priority to US18/131,668 priority patent/US20230241570A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/14—Evaporating with heated gases or vapours or liquids in contact with the liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/0095—Control aspects
    • B01J2219/00952—Sensing operations
    • B01J2219/00954—Measured properties
    • B01J2219/00961—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/0095—Control aspects
    • B01J2219/00952—Sensing operations
    • B01J2219/00954—Measured properties
    • B01J2219/00963—Pressure
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present disclosure relates to a method for producing a low odor emulsion, and more particularly to a technique for efficiently removing volatile organic compounds in an aqueous polymer emulsion obtained by an emulsion polymerization method or the like.
  • Aqueous polymer emulsions obtained by emulsion polymerization of monomers such as styrene, vinyl acetate, acrylonitrile, butadiene and alkyl (meth) acrylate in an aqueous medium are rubber-like elastic materials, paints, coating agents, adhesives, etc. It is widely used as a raw material for pressure-sensitive adhesives, binders, thickeners, cosmetic compositions, pharmaceutical compositions and the like.
  • Aqueous polymer emulsions usually contain a small amount of unreacted monomers and volatile organic compounds mainly composed of decomposition products generated during polymerization. There is a concern that such volatile organic compounds may generate a foul odor or affect the workability of the handling operator.
  • Patent Document 1 As a method for removing volatile organic compounds in an emulsion, there is a method in which pressurized steam is blown into the emulsion to expel the volatile organic compounds together with the steam (see, for example, Patent Document 1). Further, a method of adding a redox initiator after polymerization to perform additional polymerization (see, for example, Patent Document 2), and a method of supplying an emulsion from above of a stepped stripper and supplying pressurized steam from below (for example, Patent Document 3). (See), a method of blowing air or an inert gas into a heated emulsion (see, for example, Patent Document 4) and the like have been proposed.
  • the present disclosure has been made in view of the above problems, the amount of agglomerates generated during the deodorizing treatment can be suppressed to a low level, the stability over time is good, and the volatile organic compounds in the emulsion are sufficiently contained.
  • the main purpose is to provide a method for producing a reduced low odor emulsion.
  • the present inventors have set the ratio of the diameter of the supply port for supplying pressurized steam into the processing container to the inner diameter of the processing container within a specific range. It has been found that the thermal history of an aqueous polymer emulsion can be reduced and that volatile organic compounds can be easily removed in a short time.
  • the first configuration of the present disclosure relates to a method for producing a low odor emulsion, wherein the aqueous polymer emulsion is charged in a processing container capable of reducing the pressure, and the temperature of the aqueous polymer emulsion is set in the range of 50 ° C to 90 ° C.
  • the ratio of the diameter of the mouth to the inner diameter of the processing container is such that the inner diameter of the processing container is 30 to 3000 with respect to the diameter 1 of the supply port.
  • the present disclosure it is possible to produce an aqueous polymer emulsion in which volatile organic compounds are sufficiently reduced in a short treatment time (for example, within 10 hours) by using a general-purpose device capable of reducing the pressure. Therefore, the aqueous polymer emulsion obtained by the method of the present disclosure has a low odor and a small amount of agglomerates, and is therefore excellent in terms of environment and safety and health. Further, since the amount of agglomerates generated can be kept low during the deodorizing treatment, it is excellent not only in quality but also in productivity and manufacturing cost. Further, since the aqueous polymer emulsion produced by the method of the present disclosure is excellent in stability over time, it is less likely to cause problems even after long-term storage and can be used safely.
  • FIG. 1 is a vertical sectional view showing a schematic configuration of a batch type deodorizing treatment device.
  • FIG. 2 is a vertical sectional view showing a schematic configuration of a continuous deodorizing treatment device.
  • FIG. 3 is a cross-sectional view of an end portion of the supply pipe on the supply port side.
  • FIG. 4 is a cross-sectional view of an end portion of the supply pipe on the supply port side.
  • (meth) acrylic means acrylic or methacrylic.
  • aqueous polymer emulsion means an emulsion obtained by dispersing a polymer in a solvent mainly composed of water.
  • solvent mainly containing water means a liquid containing 70% by mass or more, preferably 80% by mass or more of water with respect to the entire solvent.
  • the method for producing a low odor emulsion of the present disclosure is a treatment for removing volatile organic compounds contained in an aqueous polymer emulsion (deodorization treatment) to obtain a low odor aqueous solution. It produces a polymer emulsion (hereinafter, also referred to as "low odor emulsion").
  • This manufacturing method includes the following steps A and B. Step A: A step of charging an emulsion in a deodorizing container capable of reducing the pressure and supplying the emulsion with pressurized steam under reduced pressure.
  • Step B A step of discharging the water vapor of the gas phase portion in the deodorizing treatment container and the volatile organic compound volatilized from the emulsion to the outside of the system.
  • the timing at which the step B is carried out is not particularly limited as long as the volatile organic compounds volatilized from the steam and the emulsion in the vapor phase portion in the deodorizing treatment container can be discharged to the outside of the system. That is, the present manufacturing method may be a mode in which the process B is carried out after the step A is carried out, or a mode in which the step A and the step B are carried out at the same time.
  • This manufacturing method may be applied to a batch type or a continuous type.
  • a low odor emulsion can be produced by a method including the above steps A and B.
  • this production method is continuously applied, it is preferable to produce a low odor emulsion by a method including the following step C in addition to the above steps A and B.
  • Step C A step of extracting the emulsion from which the volatile organic compounds have been removed by the above step B from the deodorizing treatment container and supplying the undeodorized emulsion to the deodorizing treatment container at a constant speed at the speed of extracting the emulsion from the deodorizing treatment container.
  • the emulsion of interest for removing volatile organic compounds is preferably an emulsion containing polymer particles produced by emulsion polymerization in an aqueous medium.
  • a vinyl monomer can be preferably used as the monomer constituting the polymer particles.
  • the vinyl monomer include (meth) acrylic acid ester compounds, aromatic vinyl compounds, unsaturated carboxylic acids, unsaturated acid anhydrides, hydroxy group-containing vinyl compounds, amino group-containing vinyl compounds, and amide group-containing vinyls. Examples thereof include compounds, alkoxy group-containing vinyl compounds, nitrile group-containing vinyl compounds, vinyl ether compounds, sulfonic acid group-containing vinyl compounds, and polyoxyalkylene group-containing vinyl compounds.
  • the vinyl monomer one of these may be used alone, or two or more thereof may be used in combination.
  • Emulsion polymerization for obtaining an emulsion can be carried out according to a conventionally known method.
  • the emulsion polymerization is preferably carried out in the presence of at least one of a surfactant and a protective colloid.
  • the surfactant include anions, cations and nonions as ionic species, and anions and / or nonions are more preferable.
  • a radical polymerization initiator for the emulsion polymerization.
  • the radical polymerization initiator a known oil-soluble polymerization initiator or water-soluble polymerization initiator can be used.
  • a water-soluble polymerization initiator is preferable.
  • the aqueous medium after polymerization usually contains about 1000 to 3000 ppm of a volatile organic compound.
  • Volatile organic compounds include unreacted monomers, alcohols produced by hydrolysis from unreacted monomers, alcohols produced by hydrolysis from ester bonds in copolymers, and in monomers and emulsifiers. Examples include impurities contained in.
  • steps A and B are carried out in this production method, whereby the volatile organic compounds are removed from the emulsion.
  • Step A Supply of pressurized steam>
  • the emulsion to be deodorized is charged in a deodorizing treatment container capable of reducing the pressure, and pressurized steam is supplied to the emulsion in the deodorizing treatment container under reduced pressure.
  • the deodorizing treatment container (hereinafter, also simply referred to as “treatment container”) is a treatment tank for accommodating the emulsion to be deodorized, and the inside thereof has an accommodating portion for accommodating the emulsion.
  • the size and shape of the accommodating portion are not particularly limited. Examples of the shape of the accommodating portion include a cylindrical shape and a rectangular cross section.
  • the processing container is provided with a supply pipe (hereinafter, also referred to as “steam supply pipe” or simply “supply pipe”) for supplying pressurized steam into the processing container.
  • the processing container has a heating unit for heating the emulsion in the container, a stirrer for stirring the emulsion in the container, a thermometer (for example, a thermocouple) for measuring the temperature in the container (that is, the emulsion temperature), and air in the container.
  • a pressure gauge for measuring the pressure of the phase portion, an exhaust pump for exhausting the gas phase in the container, and the like may be attached. From the viewpoint of efficiently releasing the volatile organic compound from the emulsion (more specifically, in an aqueous medium), it is preferable to uniformly stir the emulsion in the tank during the deodorizing treatment.
  • a stirrer having a stirring blade suitable for stirring such as a three swept wing, a paddle blade, a propeller blade, an anchor blade, and a large blade.
  • a stirring blade suitable for stirring such as a three swept wing, a paddle blade, a propeller blade, an anchor blade, and a large blade.
  • the large wing include a full zone (manufactured by Kobelco Eco-Solutions Co., Ltd.), a max blend (manufactured by Sumitomo Heavy Industries Process Equipment Co., Ltd.), a bend leaf wing (manufactured by Hakkou Sangyo Co., Ltd.), and the like.
  • the size of the stirring blade is not particularly limited, but from the viewpoint of sufficient stirring, it is preferable that the size of the blade diameter of the stirring blade is 0.3 or more with respect to the inner diameter 1 of the processing container. It is more preferably 0.4 or more.
  • FIGS. 1 and 2 The schematic configuration diagram of the processing container is shown in FIGS. 1 and 2.
  • FIG. 1 is a batch type and FIG. 2 is a continuous type.
  • the processing container 10 is a bottomed container provided with an accommodating portion 11 inside.
  • the undeodorized emulsion Em is stored in the lower part of the accommodating portion 11, and the emulsion Em is deodorized in a state where the gas phase portion Gs is formed in the upper part of the accommodating portion 11.
  • the accommodating portion 11 is provided with a stirrer 12.
  • the stirrer 12 is arranged in the accommodating portion 11 so that the stirring blade 13 provided at the lower end of the stirring shaft is arranged at the bottom of the accommodating portion 11.
  • the processing container 10 shown in FIGS. 1 and 2 is provided with a stirrer 12 having three swept wings as the stirrer blade 13.
  • the processing container 10 is provided with a supply pipe 15 for supplying pressurized steam from the supply port 14 in the accommodating portion 11.
  • the supply pipe 15 is inserted into the accommodating portion 11 from the bottom of the processing container 10.
  • the supply pipe 15 is inserted into the accommodating portion 11 from the upper part of the processing container 10.
  • An exhaust pipe 16 for discharging the gas in the gas phase portion Gs above the accommodating portion 11 to the outside of the system is provided in the upper part of the processing container 10.
  • the continuous processing container 10 is further provided with an extraction hole 17 at the bottom of the processing container 10 for extracting the deodorized emulsion from the accommodating portion 11.
  • the use of a stirrer can increase the contact efficiency between the emulsion and the pressurized steam in the processing container and enhance the effect of removing volatile organic compounds, but it is considered that excessive stirring tends to cause foaming. .. Therefore, in order to suppress foaming, an appropriate amount of antifoaming agent may be used.
  • the emulsion is further extracted from the liquid phase portion (that is, the lower part of the processing container) to the outside of the system, and the extracted emulsion is circulated by a circulation pump to circulate the extracted emulsion to the gas phase portion (that is, the lower part of the processing container). That is, the flash may be ejected from the upper part of the processing container).
  • the volatile organic compounds contained in the emulsion are separated from the liquid phase portion and are contained in the gas phase portion.
  • the pressurized steam supplied into the processing container it is preferable to use steam having a gauge pressure of about 0.05 to 0.50 MPa (temperature 110 to 160 ° C.), and steam having a gauge pressure of 0.05 to 0.30 MPa is used. It is more preferable to use steam of 0.10 to 0.30 MPa.
  • the pressurized steam may be directly supplied into the emulsion in the processing container.
  • the pressurized steam may be indirectly supplied to the emulsion in the processing container by supplying the pressurized steam to the gas phase portion in the processing container.
  • it is preferable to directly supply the pressurized steam into the emulsion stored in the processing container and it is more preferable to directly supply the pressurized steam into the emulsion in the processing container from the bottom of the processing container.
  • step A the temperature of the emulsion in the processing container is maintained within a predetermined temperature range so that the volatile organic compounds can be sufficiently removed from the emulsion.
  • the method for maintaining the temperature of the emulsion in the treatment container within a predetermined range is not particularly limited, but the treatment for heating the emulsion to be deodorized is that the temperature can be controlled easily and with high accuracy. Is preferable.
  • This heat treatment can be performed using a heating jacket, a heat exchanger provided on the outside of the treatment container, or the like.
  • the emulsion may be supplied to the treatment container after preheating the emulsion by batch treatment using a heat treatment container or continuous treatment by line heating using a heat exchanger.
  • the temperature of the emulsion in the processing container is adjusted so that the temperature of the emulsion in the processing container (that is, the temperature in the container) is in the range of 50 to 90 ° C.
  • the emulsion temperature exceeds 90 ° C., a relatively large amount of polymer film is likely to be generated on the inner wall surface of the container, especially at the interface of the gas-liquid phase, the temperature inside the container becomes non-uniform, and the accuracy of temperature control deteriorates. It ends up.
  • the ester bonds of the polymer and the unreacted monomer are likely to be hydrolyzed to generate new alcohol, and it tends to take a long time to remove the volatile organic compounds in the emulsion. If the temperature inside the container is less than 50 ° C., the removal rate of the volatile organic compounds becomes slow, and the productivity decreases.
  • the temperature inside the container is preferably 50 to 85 ° C, more preferably 50 to 80 ° C.
  • the emulsion temperature is such that the inside of the processing container (more specifically, the gas phase portion in the processing container) has a saturated water vapor pressure, that is, the water content in the processing container is boiling. And control the pressure in the processing vessel. Specifically, during the deodorizing treatment, the pressure of the gas phase portion in the treatment container is in the range of 12 KPa (90 mmHg) to 57 KPa (430 mmHg).
  • the pressure inside the container is preferably 12 KPa (90 mmHg) to 40 KPa (300 mmHg) in that the emulsion temperature during the deodorizing treatment can be set to a lower temperature and the generation of agglomerates of polymer particles can be suppressed low. More preferably, it is 12 KPa (90 mmHg) to 30 KPa (225 mmHg).
  • Step B Emission of volatile organic compounds and water vapor from the system>
  • step B after the pressurized steam is supplied into the processing container in the above step A, and / or the pressurized steam is supplied into the processing container, the gas in the processing container is exhausted to the outside of the system. As a result, the pressure inside the system is reduced, and the inside of the system is maintained within a predetermined pressure range.
  • the volatile organic compounds decomposed by the supply of the pressurized steam and the amount of steam equal to the amount of the steam supplied into the processing vessel. Is discharged to the outside of the system.
  • the method of exhaust treatment at this time is not particularly limited, but it is preferable to provide an exhaust pump in the treatment container and use the exhaust pump, and the exhaust gas is exhausted from the upper part of the treatment container through the exhaust pipe 16 to reduce the pressure. More preferred. Further, a condenser may be provided at a position between the processing container and the exhaust pump, and the condenser may be used to condense and remove the condenser.
  • step A pressurized steam is supplied to the emulsion in the processing vessel, and in step B, the volatile organic compound and the amount of steam supplied in the processing vessel are discharged to the outside of the system. ..
  • the amount of pressurized steam supplied into the processing container is preferably 5 to 100 parts by mass, more preferably 5 to 90 parts by mass, per 100 parts by mass of the emulsion. It is more preferable that the amount is 15 to 70 parts by mass.
  • the time for deodorizing the emulsion by steps A and B varies depending on the amount of pressurized steam supplied and other conditions, but from the viewpoint of productivity, it is preferably 10 hours or less, and the productivity and low odor are low. From the viewpoint of the above, 1 to 8 hours is more preferable, and 2 to 6 hours is even more preferable.
  • step C Emulsion extraction and supply>
  • the emulsion from which the volatile organic compounds have been removed by steps A and B is continuously withdrawn from the processing container into another tank (for example, a tank), and at the same time, or before or after being withdrawn, deodorization is not performed.
  • the processed emulsion is supplied at a constant speed and a speed at which the deodorized emulsion is continuously withdrawn from the processing container. As a result, a certain amount of emulsion is present in the processing container in a steady state.
  • the average residence time of the emulsion in the processing container can be appropriately selected by selecting the supply amount with respect to the internal volume of the processing container.
  • the residence time of the emulsion is preferably 10 hours or less, more preferably 1 to 8 hours, still more preferably 2 to 6 hours from the viewpoint of productivity and low odor.
  • a sufficiently long residence time (for example, 1 hour or more) is suitable because the removal of volatile organic compounds can be sufficiently removed.
  • the temperature of the emulsion in the processing container In order to sufficiently remove volatile organic compounds from the emulsion, it is preferable to maintain the temperature of the emulsion in the processing container within a predetermined temperature range. Therefore, when the temperature of the emulsion in the processing container is lowered by supplying the undeodorized emulsion to the processing container, it is preferable to preheat the undeodorized emulsion. Examples of this heat treatment method include batch treatment using a heat treatment container and continuous treatment by line heating using a heat exchanger.
  • the emulsion may be neutralized to an appropriate pH range before and / or during the deodorizing treatment.
  • a suitable pH range is 5 to 10, more preferably 6 to 10, still more preferably 6.5 to 9.5, and even more preferably 7 to 9.
  • the pH is 10 or less, it is possible to suppress the formation of new alcohol due to the hydrolysis of the ester bonds of the polymer and the unreacted monomer, and the volatile organic compounds in the emulsion can be suppressed. The time required for removal can be shortened.
  • the pH is 5 or more, the generation of agglomerates of polymer particles can be suppressed and the productivity can be improved.
  • the stability of the emulsion over time can be ensured, and the quality of the emulsion can be maintained satisfactorily.
  • Examples of the basic compound used for neutralization include alkylamines such as ammonia, trimethylamine, triethylamine and butylamine, 2-dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, triisopropanolamine and 2-amino-2-methyl-.
  • alkylamines such as ammonia, trimethylamine, triethylamine and butylamine, 2-dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, triisopropanolamine and 2-amino-2-methyl-.
  • Examples thereof include ether amines such as 1-propanol, 2-amino-2-methyl-1,3-propanediol and morpholin; and metal hydroxides such as potassium hydroxide and sodium hydroxide.
  • Examples of the method for adjusting the pH of the emulsion include a method of adding the emulsion before the deodorizing treatment, a method of dividing the emulsion during the deodorizing treatment, a method of continuously adding the emulsion during the deodorizing treatment, and the like.
  • the supply pipe 15 has a supply passage as a passage through which pressurized steam flows, and is connected to the processing container 10 so that the supply passage and the inside of the processing container 10 (that is, the accommodating portion 11) are communicated with each other (FIG. FIG. See 1 and 2).
  • the supply pipe 15 may be any as long as it can supply pressurized steam into the processing container 10, and its shape, material, and the like are not particularly limited.
  • the supply pipe 15 is, for example, a pipe made of resin or metal.
  • a supply port 14 for supplying pressurized steam into the processing container 10 from the supply passage in the supply pipe 15 is provided.
  • the shape and number of supply ports 14 are not particularly limited. Examples of the shape of the supply port 14 include a rectangular shape, a circular shape, an elliptical shape, a star shape, and the like.
  • one aspect of the supply port 14 is a mode in which the opening portion of the pipe as the supply pipe 15 constitutes the supply port 14. In this case, the supply port 14 has a diameter corresponding to the pipe diameter of the pipe.
  • a porous member having a large number of holes (for example, a wire mesh or a flat plate provided with a large number of through holes in the thickness direction) is provided as a supply passage.
  • a large number of supply ports 14 are provided in the supply passage.
  • each hole of the wire mesh and the flat plate corresponds to one supply port 14.
  • FIG. 4 shows a case where the wire mesh 18 is arranged as a large number of members in the opening of the supply pipe 15.
  • the end portion on the side where the supply port 14 is provided may be expanded in diameter toward the supply port 14 or may be reduced in diameter.
  • the position where the supply port 14 is arranged is not particularly limited, and the supply port 14 may be arranged at at least one of the side wall portion, the ceiling portion, the bottom portion, and the like of the processing container 10.
  • the supply port 14 is arranged at least at the bottom of the processing container 10 from the viewpoint of directly supplying the pressurized steam to the emulsion in the processing container 10 and thereby efficiently contacting the volatile organic compounds in the emulsion with the pressurized steam. It is preferable that it is.
  • the supply port 14 is arranged in the vicinity of the stirrer blade 13.
  • the stirrer 12 is provided so that the stirring blade 13 is arranged at the bottom of the processing container 10, and the supply port 14 is provided at the bottom of the processing container and in the vicinity of the stirring blade 13 from the bottom of the processing container 10.
  • An embodiment in which the pressurized steam is directly supplied into the emulsion is preferable in that the volatile organic compounds in the emulsion can be efficiently brought into contact with the pressurized steam.
  • the position of the supply port 14 with respect to the stirring blade 13 is 0.5 ⁇ d1 [from the surface (outer edge) of the stirring blade 13 when the blade diameter of the stirring blade 13 is d1 [m]. It is preferably less than or equal to [m], more preferably 0.4 ⁇ d1 [m] or less, and even more preferably 0.3 ⁇ d1 [m] or less. Further, the supply port 14 is preferably arranged at the same height as the upper end of the stirring blade 13 or below the upper end of the stirring blade 13, and is arranged below the upper end of the stirring blade 13. Is more preferable.
  • the material of the supply pipe 15 is made of metal, the surface temperature of the supply pipe 15 tends to be high, and the emulsion may be dried instantly to form a film. Therefore, if necessary, the metal portion of the supply pipe 15 may be coated with a resin or the like so that the heat of the supply pipe 15 does not come into direct contact with the emulsion.
  • the resin include fluororesins such as polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, and ethylene / tetrafluoroethylene copolymer.
  • the size of the foam of pressurized steam with respect to the scale of the processing container 10 can be adjusted by the ratio of the diameter of the supply port 14 to the inner diameter (tank diameter) of the processing container 10.
  • the inner diameter of the processing container 10 means the maximum inner diameter of the accommodating portion 11 in which the undeodorized emulsion is contained.
  • the ratio between the diameter of the supply port 14 and the inner diameter of the processing container 10 is determined as follows.
  • the diameter of the supply port 14 is D1 [m]
  • the inner diameter of the processing container 10 is D2 [m] (see FIGS. 1 to 4)
  • the ratio of the diameter D1 of the supply port 14 to the inner diameter D2 of the processing container 10 is "D2".
  • / D1 is defined.
  • the diameter of the supply port 14 is the diameter D1
  • the diameter inside the container of the processing container 10 that is, the tank diameter
  • a corresponding diameter is used as the diameter and / or the inner diameter.
  • the ratio (D2 / D1) of the diameter D1 of the supply port 14 to the inner diameter D2 of the processing container 10 is set to 30 to 3000. This makes it possible to improve the stability of the emulsion over time by deodorizing treatment using pressurized steam.
  • the ratio of the diameter D1 of the supply port 14 to the inner diameter D2 of the processing container 10 is less than 30, a large amount of agglomerates of polymer particles are generated, which tends to cause a decrease in productivity and a decrease in quality.
  • the stability of the emulsion after the deodorizing treatment with time is lowered, and the quality of the emulsion tends to be lowered.
  • the ratio of the diameter D1 of the supply port 14 to the inner diameter D2 of the processing container 10 exceeds 3000, the foam of the pressurized steam becomes too fine and the liquid surface foams, which tends to make deodorization difficult. be.
  • the ratio of the diameter D1 of the supply port 14 to the inner diameter D2 of the processing container 10 is preferably 200 to 3000, more preferably 350 to 3000.
  • the configuration for setting the ratio D2 / D1 to the above range is not particularly limited.
  • a pipe having a pipe diameter of D1 having a ratio D2 / D1 satisfying the above range is used as the supply pipe 15, and the pipe is connected to the processing container 10 as it is without attaching anything to the opening of the pipe. (See Fig. 3).
  • the diameter of the opening at the tip of the pipe is set to D1
  • the diameter of the supply port 14 is set to D1.
  • a wire mesh 18 having a mesh opening dimension of D1 having a ratio D2 / D1 satisfying the above range is arranged at the tip of the supply pipe 15, and the supply pipe 15 with the wire mesh 18 attached is connected to the processing container 10. (See FIG. 4).
  • a large number of supply ports 14 are provided in the supply passage because it is easy to design the ratio D2 / D1 to satisfy the above range and a sufficient amount of pressurized steam can be efficiently supplied to the emulsion in a short time. It is preferable that the pressurized steam is supplied into the processing container 10 from the supply passage through the large number of supply ports 14.
  • a low odorous aqueous polymer emulsion having a concentration of volatile organic compounds of preferably 300 ppm or less by deodorization treatment for a short time of about 1 to 10 hours by selecting various conditions. Can be manufactured.
  • the concentration of the volatile organic compound is more preferably 100 ppm or less, further preferably 50 ppm or less, further preferably 35 ppm or less, and more preferably close to 0 ppm.
  • the concentration of the volatile organic compound in the emulsion is a value measured by gas chromatography according to the method described in Examples.
  • the ester bond possessed by the polymer or the unreacted monomer is more important than the odor of the unreacted monomer itself. It may be preferable to reduce the odor of the alcohol produced by the hydrolysis of.
  • the concentration of alcohol in the emulsion is preferably 100 ppm or less, more preferably 30 ppm or less, and more preferably closer to 0 ppm.
  • a low-odor aqueous polymer emulsion having a small amount of volatile organic compounds and aggregates and excellent stability over time can be obtained by a simple operation using a general-purpose device capable of reducing the pressure.
  • Such emulsions have strict requirements for environment, safety, quality, etc., such as rubber-like elastic materials, paints, coating agents, adhesives, pressure-sensitive adhesives, binders, thickeners, cosmetic compositions, pharmaceutical compositions, etc. It can be used in a wide range of applications.
  • a monomer preemulsion was prepared by mixing 3 parts of methacrylic acid (hereinafter referred to as MAA), 10 parts of G-15, and 45 parts of water.
  • MAA methacrylic acid
  • the obtained monomer preemulsion and 20 parts of a 5% ammonium persulfate aqueous solution as a polymerization initiator were continuously added dropwise into the flask over 4 hours from different dropping funnels, while maintaining the liquid temperature at about 80 ° C.
  • Emulsion polymerization was performed. After the completion of the dropping, the liquid temperature was kept at 80 ° C. for another 2 hours, and the mixture was aged. During aging, 5 parts of a 5% ammonium persulfate aqueous solution was added. Then, it cooled to 50 degreeC and the polymerization was terminated. 0.1 part of an antifoaming agent (manufactured by San Nopco Ltd., trade name: SN Deformer PC) was added to the obtained emulsion to obtain an aqueous polymer emulsion (A) having a solid content of 45.0% and a pH of 2.1.
  • an antifoaming agent manufactured by San Nopco Ltd., trade name: SN Deformer PC
  • the amount of the main volatile organic compounds contained in the obtained aqueous polymer emulsion (A) was measured by gas chromatography and found to be as follows.
  • MMA 211 ppm, BA; 277 ppm, HA; 104 ppm, St; 82 ppm, methanol; 5 ppm, n-butanol; 264 ppm, 2-ethylhexanol; 70 ppm
  • Example 1 A water vapor supply pipe and an exhaust pipe were attached to a cylindrical flask (inner diameter: 120 mm) containing the aqueous polymer emulsion (A) obtained in Production Example 1.
  • the supply pipe shall be a pipe with a pipe diameter of 1 mm, and with a wire mesh of 100 mesh (opening size: 0.154 mm) attached to the tip of the pipe, the end of the pipe on the side to which the wire mesh is attached is inserted from the bottom of the flask and stirred.
  • a steam supply port was arranged at a position where the steam supply port (hereinafter, also referred to as “steam supply port”) overlaps (see FIG. 1). Three swept wings were used as the stirring blades.
  • the supply port 14 in FIG. 1 corresponds to the steam supply port.
  • the diameter of the steam supply port corresponds to the opening size of the wire mesh and is 0.154 mm. After raising the liquid temperature to 55 ° C.
  • pressurized steam at a pressure of 0.2 MPa was applied to 100 parts of the aqueous polymer emulsion (A) at 0.
  • the pressure in the flask is reduced to 15 KPa by exhausting the steam in the system through the exhaust pipe while blowing into the liquid through the steam supply pipe at 1 part / min, and the water in the system boils. I kept it in the state of being.
  • 25% aqueous ammonia was added as appropriate to maintain the pH in the range of 7-9.
  • Example 2> The deodorizing treatment was carried out in the same manner as in Example 1 except that the steam supply pipe was changed to a pipe having a diameter of 1 mm and a wire mesh of 300 mesh attached to the tip of the pipe (diameter of the steam supply port: 0.05 mm). bottom.
  • Example 3> The deodorizing treatment was carried out in the same manner as in Example 1 except that the steam supply pipe was changed to a pipe having a diameter of 1 mm and a wire mesh of 50 mesh attached to the tip of the pipe (diameter of the steam supply port: 0.3 mm). bottom.
  • Example 4 The deodorizing treatment was carried out in the same manner as in Example 1 except that the steam supply pipe was changed to a pipe having a diameter of 1 mm and a wire mesh of 30 mesh attached to the tip of the pipe (diameter of the steam supply port: 0.5 mm). bottom.
  • Example 6> The deodorizing treatment was carried out in the same manner as in Example 1 except that the treatment time was changed from 5 hours to 3 hours.
  • Examples 7 to 10> The deodorizing treatment was carried out in the same manner as in Example 1 except that the supply amount of the pressurized steam was changed as shown in Tables 1 and 2.
  • Examples 11, 12, 14 and 15> The deodorizing treatment was carried out in the same manner as in Example 1 except that the pH at the time of the deodorizing treatment was changed as shown in Table 2.
  • Example 13> The deodorization treatment was carried out in the same manner as in Example 1 except that the pH was not adjusted before the deodorization treatment and 25% aqueous ammonia was not added during the deodorization treatment.
  • Example 16 In a heat treatment container (internal volume 5 L) equipped with a stirrer, a thermometer, and a cooler, 3000 g of the aqueous polymer emulsion (A) obtained in Production Example 1 was charged, and the liquid temperature was 55 under stirring with three swept wings. After raising the temperature to ° C., the pH was adjusted to 8 with 25% aqueous ammonia. On the other hand, an aqueous polymer emulsion (inner diameter: 200 mm) provided with a stirrer, a thermometer, a cooler, a steam supply pipe and an exhaust pipe at a supply amount of 3.3 g / min from the heat treatment container (inner diameter: 200 mm). A) was continuously supplied.
  • the steam supply pipe is a pipe with a pipe diameter of 1 mm, and with a wire mesh of 100 mesh (opening size: 0.154 mm) attached to the tip of the pipe, the end of the pipe on the side where the wire mesh is attached is from the top of the deodorizing container. Inserted into the deodorizing container, the vicinity of the stirring blade (the side of the stirring blade with a blade diameter of 90 mm, the distance D4 from the outer edge of the stirring blade is 10 mm, and the steam supply port is from the upper surface of the stirring blade. A steam supply port was placed at the lower position) (see FIG. 2). The supply port 14 in FIG. 2 corresponds to the steam supply port. The diameter of the steam supply port corresponds to the opening size of the wire mesh and is 0.154 mm.
  • Deodorization treatment When the amount of liquid in the container reaches 1000 g (5 hours from the start of supply), the same amount of liquid (emulsion) as the supply amount of the aqueous polymer emulsion (A) is withdrawn from the system and continuously deodorized. Was carried out. During the deodorizing treatment, 25% aqueous ammonia was appropriately added to maintain the pH in the range of 7 to 9.
  • Examples 17 to 24 The deodorizing treatment was carried out in the same manner as in Example 1 except that the pressure inside the container, the temperature inside the container and the position of the steam supply port at the time of the deodorizing treatment were changed as shown in Table 3.
  • Example 25 A steam supply pipe and an exhaust pipe were attached to a reaction kettle (inner diameter: 1200 mm) containing the aqueous polymer emulsion (A) of Production Example 1, and the liquid temperature was raised to 55 ° C.
  • the steam supply pipe is a pipe with a pipe diameter of 50 mm, a flat plate having 30 holes of ⁇ 1 mm is attached to the tip of the pipe, and the end of the pipe on the side where the flat plate is attached is inserted into the deodorizing treatment container from the bottom of the deodorizing treatment container.
  • pressurized steam at a pressure of 0.2 MPa is blown into the liquid at 0.1 part / min with respect to 100 parts of the aqueous polymer emulsion (A) and exhausted.
  • the pressure in the processing container was reduced to 15 KPa, and the inside of the system was maintained in a boiling state.
  • 25% aqueous ammonia was added as appropriate to maintain the pH in the range of 7-9.
  • ⁇ Comparative Example 1> The deodorizing treatment was carried out in the same manner as in Example 1 except that the pressure inside the container during the deodorizing treatment was changed to 20 KPa (a state in which water does not boil).
  • ⁇ Comparative Example 2> The deodorizing treatment was carried out in the same manner as in Example 1 except that pressurized steam was not supplied during the deodorizing treatment.
  • ⁇ Comparative Example 3> The deodorizing treatment was carried out in the same manner as in Example 1 except that the pressure inside the container and the temperature inside the container during the deodorizing treatment were changed as shown in Table 4. However, there was a lot of foaming and it was difficult to control the vacuum, so it stopped in 1 hour.
  • Example 4 The deodorizing treatment was carried out in the same manner as in Example 1 except that the pressure inside the container and the temperature inside the container during the deodorizing treatment were changed as shown in Table 4.
  • Examples 1 to 25 in which the deodorizing treatment was performed by this production method, a general-purpose device capable of depressurizing was used, and the temperature was relatively low and the time was short. It has been found that a low odor aqueous polymer emulsion in which the volatile organic compounds in the aqueous polymer emulsion are reduced to a minute amount can be easily obtained. In addition, it has been clarified that the aqueous polymer emulsion obtained by this production method has excellent stability over time and is less likely to deteriorate in quality even when stored for a long period of time. Further, it can be said that Examples 1 to 25 are excellent in temperature controllability and productivity in the processing container because the wall surface inside the container is less contaminated during the deodorization treatment and after the deodorization treatment.
  • Comparative Example 1 and Comparative Example 2 the degree of reduction of volatile organic compounds in the emulsion was insufficient.
  • Comparative Example 3 since the pressure inside the container was as low as 10 KPa, there was a lot of foaming when the pressurized steam was blown, and it was difficult to control the vacuum.
  • Comparative Example 4 since the temperature inside the container was as high as 95 ° C., there were many agglomerates due to the skinning of the emulsion. In addition, the emulsion has an excessive heat history, so that the stability over time is also lowered.
  • Comparative Example 5 a large amount of agglomerates of polymer particles were generated.
  • Comparative Example 6 the ratio D2 / D1 was large, and the bubbles of the pressurized steam became too fine and foamed from the liquid surface, and the wall surface of the processing container was contaminated.

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PCT/JP2021/036678 2020-10-09 2021-10-04 低臭気エマルションの製造方法 Ceased WO2022075275A1 (ja)

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EP21877574.0A EP4227326A4 (en) 2020-10-09 2021-10-04 METHOD FOR PRODUCING LOW ODOR EMULSION
CN202180067612.0A CN116323714A (zh) 2020-10-09 2021-10-04 低臭气乳液的制造方法
JP2022555475A JP7736009B2 (ja) 2020-10-09 2021-10-04 低臭気エマルションの製造方法
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JPS58213003A (ja) 1982-06-04 1983-12-10 Japan Synthetic Rubber Co Ltd 重合体ラテツクス中の揮発性物質の除去方法
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JPS5341387A (en) 1976-09-28 1978-04-14 Mitsui Toatsu Chem Inc Removing volatile matter from styrene polymer
JPS58213003A (ja) 1982-06-04 1983-12-10 Japan Synthetic Rubber Co Ltd 重合体ラテツクス中の揮発性物質の除去方法
JP2002060415A (ja) 2000-08-21 2002-02-26 Yayoi Chemical Industry Co Ltd エマルジョン樹脂の製造法
JP2002212207A (ja) 2001-01-16 2002-07-31 Nippon Paint Co Ltd アクリルエマルションの製造方法
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JP2025172684A (ja) * 2024-05-13 2025-11-26 住友化学株式会社 組成物、重合体、硬化物、成形体及びポリメタクリル酸メチルの製造方法

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