WO2020045339A1 - Procédé pour la production de latex de polymère - Google Patents

Procédé pour la production de latex de polymère Download PDF

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Publication number
WO2020045339A1
WO2020045339A1 PCT/JP2019/033270 JP2019033270W WO2020045339A1 WO 2020045339 A1 WO2020045339 A1 WO 2020045339A1 JP 2019033270 W JP2019033270 W JP 2019033270W WO 2020045339 A1 WO2020045339 A1 WO 2020045339A1
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organic solvent
emulsion
polymer
pressure
polymer latex
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PCT/JP2019/033270
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English (en)
Japanese (ja)
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吉隆 佐藤
小出村　順司
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日本ゼオン株式会社
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Priority to CN201980050373.0A priority Critical patent/CN112513147A/zh
Priority to BR112021003445-5A priority patent/BR112021003445B1/pt
Priority to KR1020217004897A priority patent/KR20210049800A/ko
Priority to JP2020539439A priority patent/JP7342871B2/ja
Publication of WO2020045339A1 publication Critical patent/WO2020045339A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/075—Concentrating
    • C08C1/12—Concentrating by evaporation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • 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
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/20—Concentration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • the present invention relates to a method for producing a polymer latex, and more particularly, to a method for producing a polymer latex that can be produced in a short time while achieving a high yield.
  • a film molded product such as a dip molded product obtained by dip molding a latex composition containing a latex of natural rubber or synthetic rubber has been suitably used as a nipple, a balloon, a glove, a balloon, a sack and the like.
  • Patent Literature 1 as a method for producing a synthetic rubber latex, an emulsion is obtained by mixing a solution of a synthetic rubber in which a synthetic rubber is dissolved in an organic solvent and an aqueous solution of an emulsifier. A method for removing an organic solvent by heating an obtained emulsion at a temperature higher than the boiling point of the organic solvent under reduced pressure conditions is disclosed.
  • the technique of Patent Document 1 has a problem that it takes a long time to remove the organic solvent, and thus the productivity is poor.
  • An object of the present invention is to provide a method for producing a polymer latex that can be produced in a short time while realizing a high yield.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, a polymer solution or dispersion obtained by dissolving or dispersing a polymer in an organic solvent and an aqueous solution of an emulsifier were obtained.
  • the organic solvent is distilled off from the emulsion, the above-mentioned object can be achieved by performing the distillation of the organic solvent from the emulsion in a vessel adjusted to a pressure condition of 0.02 MPa or more at a gauge pressure. And completed the present invention.
  • the organic solvent is distilled off from the emulsion obtained by mixing the polymer solution or dispersion obtained by dissolving or dispersing the polymer in the organic solvent and the aqueous solution of the emulsifier.
  • a method for producing a polymer latex comprising: There is provided a method for producing a polymer latex, in which the organic solvent is distilled off from the emulsion in a vessel adjusted to a pressure condition of 0.02 MPa or more at a gauge pressure.
  • the content of the organic solvent in the emulsion before the organic solvent is distilled off is preferably 30 to 60% by weight.
  • the organic solvent is preferably distilled off from the emulsion in a vessel adjusted to a gauge pressure of 0.02 to 0.18 MPa.
  • the organic solvent is an organic solvent selected from cyclohexane, normal hexane, cyclopentane, and normal pentane.
  • the distillation of the organic solvent is performed by heating by a method in which steam whose pressure is adjusted is charged into a jacket provided in the container.
  • the polymer is preferably a synthetic polyisoprene and / or a styrene-isoprene-styrene copolymer.
  • the content of the emulsifier in the emulsion before removing the organic solvent is 0.1 to 30 parts by weight based on 100 parts by weight of the polymer. Preferably, there is.
  • FIG. 1 is a diagram illustrating an example of an emulsifying apparatus used in the method for producing a polymer latex of the present invention.
  • the method for producing the polymer latex of the present invention comprises: A polymer solution or dispersion obtained by dissolving or dispersing the polymer in an organic solvent, and an emulsion obtained by mixing an aqueous solution of an emulsifier, comprising a step of distilling off the organic solvent, The organic solvent is distilled off from the emulsion in a container adjusted to a pressure condition of 0.02 MPa or more at a gauge pressure.
  • the emulsion used in the production method of the present invention is obtained by mixing a polymer solution or dispersion obtained by dissolving or dispersing a polymer in an organic solvent with an aqueous solution of an emulsifier.
  • the polymer solution or dispersion is not particularly limited as long as it is a solution or dispersion in which the polymer is dissolved or dispersed in an organic solvent.
  • the polymer is not particularly limited and various polymers can be used without limitation. Examples thereof include natural rubber; homopolymers of conjugated diene monomers such as synthetic polybutadiene, synthetic polyisoprene, and synthetic polychloroprene; Copolymers: styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isoprene-styrene block copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-butadiene-isoprene copolymer And a conjugated diene monomer such as butyl acrylate-butadiene copolymer and another monomer copolymerizable therewith; an acrylate (co) polymer; Among these, natural rubber, synthetic polyisoprene, and styrene-isoprene-
  • the polymer constituting the solution or dispersion of the polymer used in the production method of the present invention is a synthetic polyisoprene and / or a styrene-isoprene-styrene block copolymer
  • the polymer solution or dispersion used in the method is not limited to the solution or dispersion of the synthetic polyisoprene and / or styrene-isoprene-styrene block copolymer.
  • the synthetic polyisoprene may be a homopolymer of isoprene or a copolymer of isoprene and another ethylenically unsaturated monomer copolymerizable with isoprene.
  • the content of the isoprene unit in the synthetic polyisoprene is preferably 70% by weight or more based on all the monomer units, since a film molded body such as a dip molded body having flexibility and excellent tensile strength can be easily obtained.
  • the content is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 100% by weight (a homopolymer of isoprene).
  • ethylenically unsaturated monomers copolymerizable with isoprene include, for example, conjugated diene monomers other than isoprene such as butadiene, chloroprene and 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ - Ethylenically unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate (meaning "methyl acrylate and / or methyl methacrylate” And ethyl (meth) acrylate), ethylenically unsaturated carboxylic acid ester monomers such as ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; Is mentioned.
  • Synthetic polyisoprene can be prepared in a known manner, for example, using a Ziegler-based polymerization catalyst comprising trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium in an organic solvent using isoprene. And, by solution-polymerizing another copolymerizable ethylenically unsaturated monomer used as needed, a synthetic polyisoprene obtained by dissolving a synthetic polyisoprene in an organic solvent can be obtained as a solution of a synthetic polyisoprene. .
  • the solution of the synthetic polyisoprene obtained by the solution polymerization may be used as it is in the emulsification step, but after taking out the solid synthetic polyisoprene from the solution obtained by the solution polymerization, the solution is dissolved in an organic solvent. , May be used.
  • organic solvent used for the polymerization examples include, for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane, and cyclohexene; butane, normal pentane, normal hexane, and the like. Suitable examples include aliphatic hydrocarbon solvents such as heptane; halogenated hydrocarbon solvents such as methylene chloride, chloroform and ethylene dichloride. In addition, even when solid synthetic polyisoprene is taken out of a solution obtained by solution polymerization and then dissolved again in an organic solvent, these organic solvents can be suitably used.
  • aromatic hydrocarbon solvents such as benzene, toluene, and xylene
  • alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane, and cyclohe
  • the isoprene units in the synthetic polyisoprene there are four types of cis-bond units, trans-bond units, 1,2-vinyl-bond units, and 3,4-vinyl-bond units, depending on the bonding state of isoprene.
  • the content ratio of the cis-bond unit in the isoprene unit contained in the synthetic polyisoprene is preferably at least 70% by weight based on all the isoprene units, It is more preferably at least 90% by weight, further preferably at least 95% by weight.
  • the weight average molecular weight of the synthetic polyisoprene is preferably 10,000 to 5,000,000, more preferably 500,000 to 5,000,000, and still more preferably, in terms of standard polystyrene by gel permeation chromatography analysis. Is from 800,000 to 3,000,000.
  • the weight average molecular weight of the synthetic polyisoprene is in the above range, the tensile strength of the obtained film molded body in the case of a film molded body such as a dip molded body is improved, and the synthetic polyisoprene latex is easily manufactured. Tend.
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C) of the synthetic polyisoprene is preferably 50 to 80, more preferably 60 to 80, and further preferably 70 to 80.
  • Styrene-isoprene-styrene block copolymer is a block copolymer of styrene and isoprene.
  • the content ratio of the styrene unit to the isoprene unit in the styrene-isoprene-styrene block copolymer is not particularly limited, but is usually from 1:99 to 90:10, preferably from 3 to 9, based on the weight ratio of “styrene unit: isoprene unit”. : 97 to 70:30, more preferably 5:95 to 50:50, even more preferably 10:90 to 30:70.
  • the styrene-isoprene-styrene block copolymer can be prepared by a conventionally known method, for example, using a Ziegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
  • a Ziegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
  • a styrene-isoprene-styrene block copolymer solution obtained by dissolving a styrene-isoprene-styrene block copolymer in an organic solvent can be obtained. it can.
  • the styrene-isoprene-styrene block copolymer solution obtained by the block copolymerization may be used as it is in the emulsification step, but the solid styrene-isoprene-styrene block is obtained from the solution obtained by the block copolymerization.
  • the copolymer After taking out the copolymer, the copolymer may be dissolved in an organic solvent and used. Examples of the organic solvent used for the polymerization include the same ones as the above-mentioned synthetic isoprene.
  • the content ratio of the cis-bond unit in the isoprene unit contained in the styrene-isoprene-styrene block copolymer is, with respect to all the isoprene units, from the viewpoint of improving the tensile strength of the obtained film-formed body such as the dip-formed body. It is preferably at least 90% by weight, more preferably at least 95% by weight, even more preferably at least 98% by weight.
  • the weight average molecular weight of the styrene-isoprene-styrene block copolymer is preferably from 10,000 to 1,000,000, more preferably from 50,000 to 500, in terms of standard polystyrene by gel permeation chromatography analysis. 000, more preferably 100,000 to 300,000.
  • the weight average molecular weight of the styrene-isoprene-styrene block copolymer within the above range, when a film molded product such as a dip molded product is obtained, the tensile strength of the obtained film molded product is improved, and styrene-isoprene is obtained.
  • -Styrene block copolymer latex tends to be easily produced.
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the styrene-isoprene-styrene block copolymer is preferably 50 to 80, more preferably 60 to 80, and even more preferably 70 to 80.
  • the content of the polymer in the polymer solution or dispersion used in the production method of the present invention is not particularly limited, but is preferably 3 to 30% by weight, more preferably 5 to 20% by weight, and further preferably It is 7 to 15% by weight.
  • the emulsifier constituting the aqueous solution of the emulsifier used in the production method of the present invention is not particularly limited, but an anionic emulsifier can be preferably used.
  • the anionic emulsifier include fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, sodium rosinate, potassium rosinate; sodium dodecylbenzenesulfonate, dodecylbenzenesulfonate Alkylbenzene sulfonates such as potassium, sodium decylbenzenesulfonate, potassium decylbenzenesulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate, di (2-ethylhexyl) sulfosuccinate Alkyl s
  • fatty acid salts, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates are preferred, and the generation of aggregates in the resulting polymer latex is more appropriate.
  • fatty acid salts and alkylbenzene sulfonates are more preferable, fatty acid salts are more preferable, and sodium rosinate and potassium rosinate are preferable. Particularly preferred. It is also preferable to use a combination of a fatty acid salt and an alkylbenzene sulfonate.
  • the content of the emulsifier in the aqueous solution of the emulsifier used in the production method of the present invention is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 0.3 to 3% by weight, and still more preferably 0 to 3% by weight. 0.5 to 2% by weight.
  • a polymer solution or dispersion obtained by dissolving or dispersing such a polymer in an organic solvent, and an aqueous solution of an emulsifier are supplied to a mixing device, and mixed.
  • An emulsion can be obtained.
  • the solution or dispersion of the polymer and the aqueous solution of the emulsifier are continuously supplied to a mixing device to obtain an emulsion continuously.
  • FIG. 1 is a diagram showing an example of an emulsifying apparatus used in the method for producing a polymer latex of the present invention.
  • the emulsifying apparatus shown in FIG. 1 includes a polymer tank 10, an emulsifier tank 20, a mixing apparatus 30, a storage tank 40, a distillation pipe 60, a condenser 70, And a solvent recovery tank 80.
  • the polymer solution or dispersion from the polymer tank 10 and the aqueous solution of the emulsifier from the emulsifier tank 20 are continuously sent to the mixing device 30, respectively.
  • the mixing device 30 By continuously mixing the solution or dispersion of the polymer and the aqueous solution of the emulsifier in 30, an emulsion can be obtained continuously.
  • the emulsified liquid thus continuously obtained is continuously supplied to the storage tank 40.
  • the supply ratio thereof is not particularly limited, but the emulsification of the polymer is allowed to proceed more appropriately.
  • the volume ratio is preferably 1: 2 to 1: 0.3, more preferably 1: 1.5 to 1: 0.5. , More preferably 1: 1 to 1: 0.7.
  • the method for continuously feeding the polymer solution or dispersion and the aqueous solution of the emulsifier from the polymer tank 10 and the emulsifier tank 20 to the mixing device 30 is not particularly limited.
  • the aqueous solution of the emulsifier may be directly sent to the mixing device 30 by a pump, or a premixing device such as a line mixer may be provided upstream of the mixing device 30 to provide a premixing device.
  • the pre-mixing may be performed in such a manner that the pre-mixed state is sent to the mixing device 30 in the pre-mixed state.
  • the mixing device 30 is not particularly limited, but is preferably a mixing device capable of continuously mixing, for example, a product name “TK Pipeline Homomixer” (manufactured by Tokushu Kika Kogyo Co., Ltd.), and a product name “ Colloid mill “(manufactured by Shinko Pantech), trade name” Slasher “(manufactured by Nippon Coke Industry), trade name” trigonal wet pulverizer “(manufactured by Mitsui Miike Kakoki Co., Ltd.), trade name” Cavitron “(eurotech) ), Trade name "Milder” (manufactured by Taiheiyo Kiko), trade name “Fine Flow Mill” (manufactured by Taiheiyo Kiko) and the like.
  • the conditions of the mixing operation by the mixing device 30 are not particularly limited, and a processing temperature, a processing time, and the like may be appropriately selected so that a desired dispersion state is obtained.
  • the temperature of the solution or dispersion of the polymer and the aqueous solution of the emulsifier when the polymer solution or dispersion and the aqueous solution of the emulsifier are continuously fed to the mixing device 30 are not particularly limited.
  • the temperature is preferably from 20 to 100 ° C., more preferably from 40 to 90 ° C., and still more preferably from 60 to 80 ° C., from the viewpoint that satisfactorily can be carried out.
  • the temperature at which these are mixed is the temperature at which the polymer solution or dispersion is stored in the polymer tank 10 and the aqueous solution of the emulsifier is mixed with the emulsifier tank so that the mixing temperature becomes the desired temperature.
  • the temperature at the time of storing in 20 is just to control by adjusting the temperature at the time of storing in 20 respectively.
  • the polymer solution or dispersion at 60 ° C. and the aqueous solution of the emulsifier at 60 ° C. are mixed by the mixing device 30, the polymer solution or dispersion is stored in the polymer tank 10.
  • the temperature when the aqueous solution of the emulsifier is stored in the emulsifier tank 20 may be 60 ° C.
  • the content of the organic solvent in the emulsion used in the production method of the present invention is usually 30 to 60% by weight, preferably 35 to 60% by weight based on 100% by weight of all components constituting the emulsion. %, More preferably 37 to 50% by weight.
  • the content of the emulsifier in the emulsion used in the production method of the present invention is generally 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, more preferably 3 to 20 parts by weight, per 100 parts by weight of the polymer. 1515 parts by weight.
  • Organic solvent distillation step In the production method of the present invention, as described above, a polymer solution or dispersion obtained by dissolving or dispersing the polymer in an organic solvent, and an emulsion obtained by mixing an aqueous solution of an emulsifier, An organic solvent distilling step of distilling (removing) the organic solvent is provided. Then, in the production method of the present invention, the distillation (removal) of the organic solvent from the emulsion in such an organic solvent distilling step is performed in a vessel adjusted to a pressure condition of 0.02 MPa or more by gauge pressure. It is performed in.
  • the organic solvent distilling step the organic solvent is sent from the mixing device 30 and stored in the storage tank 40.
  • the organic solvent contained in the emulsion is distilled off in a state where the pressure in the storage tank 40 is controlled to a pressure of 0.02 MPa or more by gauge pressure for the emulsion.
  • the storage tank 40 includes the stirring blade 50, and further includes a jacket (not shown) for circulating the steam on the outside thereof.
  • a distillation pipe 60 and a condenser 70 connected to the distillation pipe 60 are provided above the storage tank 40.
  • the pressure in the storage tank 40 is adjusted and the organic solvent is distilled off as follows. That is, in the organic solvent distilling step of the manufacturing method of the present invention, the system including the storage tank 40, the distilling pipe 60, and the condenser 70 is kept in a closed system sealed from the outside air, and While the emulsion is being stirred, steam whose pressure has been adjusted is continuously fed into a jacket provided outside the storage tank 40 to heat the emulsion stored in the storage tank 40. Then, the pressure in the storage tank 40 is increased by evaporating (evaporating or boiling) the organic solvent from the heated emulsion, whereby the inside of the storage tank 40 is pressurized. On the other hand, a part of the organic solvent vaporized from the heated emulsion passes through the distillation pipe 60, is cooled by the condenser 70, and is recovered in the organic solvent recovery tank 80.
  • the organic solvent is distilled off while maintaining the pressurized state by utilizing the pressure increase inside the storage tank 40 due to the vaporization of the organic solvent. Is what you do. Specifically, the organic solvent is distilled off in a state where the pressure inside the storage tank 40 is maintained under a pressure condition of 0.02 MPa (gauge pressure) or more.
  • the upper limit of the pressure inside the storage tank 40 in the organic solvent distillation step is not particularly limited, but is preferably 0.18 MPa (gauge pressure) or less from the viewpoint of equipment.
  • the organic solvent is preferably distilled while maintaining the pressure inside the storage tank 40 at a pressure of 0.05 to 0.09 MPa (gauge pressure).
  • the organic solvent is distilled off while maintaining the pressure condition of 0.07 to 0.09 MPa (gauge pressure).
  • the pressure inside the storage tank 40 in the organic solvent distillation step can be adjusted by, for example, a heating temperature when the emulsion stored in the storage tank 40 is heated. For example, as the heating temperature increases, the pressure can be increased.
  • the organic solvent distilling step of the production method of the present invention the organic solvent is distilled off under such a pressurized condition of 0.02 MPa (gauge pressure) or more, and the distillation is performed under the pressurized condition.
  • the organic solvent contained in the emulsion can be distilled off in a short time while achieving a high yield.
  • the inventors of the present invention have studied that, although the distillation of the organic solvent is generally performed under reduced pressure conditions, conversely, when the pressure is increased to 0.02 MPa (gauge pressure) or more. It has been found that the time required for distilling off the organic solvent is reduced, and based on such knowledge, the distilling off of the organic solvent is performed under a pressure condition of 0.02 MPa (gauge pressure) or more.
  • the foaming of the liquid surface can be suppressed by applying a pressure condition of 0.02 MPa (gauge pressure) or more.
  • the amount of the emulsified liquid is relatively large, preferably 50 to 85% by volume, more preferably 55 to 85% by volume, and still more preferably 70 to 85% by volume with respect to the volume of the storage tank 40. Even when the amount is relatively large, it is possible to effectively suppress the problem that a part of the emulsion flows into the condenser 70 due to foaming and lowers the yield. As a result, the productivity can be improved.
  • the pressure is 0.02 MPa (gauge pressure) or more
  • the inside of the storage tank 40 is filled with the vaporized organic solvent, This allows the wall surface of the storage tank 40 to be kept wet during the removal of the organic solvent. Therefore, even when the emulsified liquid adheres to the wall surface of the storage tank 40, it is possible to effectively suppress the solidification of the emulsified liquid and the remaining of the polymer component adhered thereto. It is possible to suppress a decrease in the yield due to the polymer component remaining on the wall surface, and to realize a high yield.
  • the heating temperature for heating the emulsion stored in the storage tank 40 is not particularly limited.
  • the temperature may be set according to the desired pressure, but the boiling point is higher than the boiling point Tb of the organic solvent contained in the emulsion (that is, the organic solvent derived from the polymer solution or dispersion) under atmospheric pressure.
  • the temperature is preferably Tb or higher, more preferably in the range of Tb + 1 to Tb + 35 ° C, more preferably in the range of Tb + 5 to Tb + 35 ° C, and still more preferably in the range of Tb + 10 to Tb + 30 ° C.
  • the heating temperature may be set based on the boiling point of the organic solvent having the higher content.
  • the pressure applied inside the storage tank 40 in the organic solvent distillation step can be appropriately controlled.
  • the heating temperature can be appropriately adjusted by adjusting the flow rate and the flow rate of the steam to be charged into the jacket provided outside the storage tank 40.
  • the pressure applied to the inside of the storage tank 40 in the organic solvent distillation step may be within the above range in terms of gauge pressure, but is preferably 0.1213 to 0.2813 MPa, more preferably 0.1513 to absolute pressure.
  • the pressure is 0.1913 MPa, and more preferably 0.1713 to 0.1913 MPa.
  • the system including the storage tank 40, the distillation pipe 60, and the condenser 70 is maintained in a closed system that is closed from the outside air, and the organic solvent is removed.
  • the heating of the storage tank 40 is started, it is connected to the upper part of the condenser 70 for the purpose of removing air contained in the storage tank 40.
  • the pressure valve may be opened to remove air. At this time, it is desirable to close the pressure valve after the removal of the air contained in the storage tank 40 is completed and the liquefaction of the organic solvent by the condenser 70 is confirmed, thereby forming a closed system.
  • the pressure in the storage tank 40 in the organic solvent distillation step may be adjusted by the heating temperature.
  • the pressure is adjusted by a pressure valve connected to the upper part of the condenser 70. The methods may be used in combination.
  • the distillation of the organic solvent from the emulsion under the pressure condition of 0.02 MPa (gauge pressure) or more in the organic solvent distillation step is based on 100% by weight of the polymer in the emulsion.
  • the process is preferably performed until the content of the organic solvent in the emulsion becomes preferably 500 ppm by weight or less, more preferably 100 ppm by weight or less.
  • the organic solvent is distilled off from the emulsion under a pressure condition of 0.02 MPa (gauge pressure) or more.
  • the organic solvent may be distilled off under reduced pressure conditions in combination.
  • a decompression pump may be connected to the downstream side of the condenser 70 so that the pressure is reduced by the decompression pump.
  • a polymer latex can be obtained.
  • the polymer latex thus obtained is usually blended in the field of latex, such as a pH adjuster, an antifoaming agent, a preservative, a chelating agent, an oxygen scavenger, a dispersant, an antioxidant and the like. Additives may be blended.
  • Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; carbonates of alkali metals such as sodium carbonate and potassium carbonate; hydrogen carbonates of alkali metals such as sodium hydrogen carbonate; ammonia Organic amine compounds such as trimethylamine and triethanolamine; and the like, with preference given to alkali metal hydroxides or ammonia.
  • a concentration operation by centrifugation may be performed to increase the solid content of the polymer latex.
  • the volume average particle diameter of the polymer latex produced by the production method of the present invention is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and still more preferably 1 to 2 ⁇ m.
  • the solid content of the polymer latex produced by the production method of the present invention is preferably 30 to 70% by weight, more preferably 40 to 70% by weight.
  • the polymer latex of the present invention thus obtained can be made into a latex composition by, for example, blending various additives such as a cross-linking agent, and the latex composition can be used as a dip molded article or the like. In addition to being used for obtaining a film molded product, it can also be used for adhesives.
  • Example 1> Preparation of normal hexane solution (a) of synthetic polyisoprene) Synthetic polyisoprene (trade name “Nipol IR2200L (R)”, manufactured by Zeon Corporation) was mixed with normal hexane (boiling point: 69 ° C.), and the temperature was raised to 60 ° C. with stirring to dissolve. A normal hexane solution (a) of synthetic polyisoprene having a concentration of 15% by weight was prepared.
  • emulsifier aqueous solution (b1) An emulsifier aqueous solution (b1) having a potassium rosinate concentration of 1.2% by weight was prepared by mixing potassium rosinate as a fatty acid-based emulsifier with water at a temperature of 60 ° C.
  • the normal hexane solution (a) of the synthetic polyisoprene prepared as described above is stored in the polymer tank 10 while being heated to 60 ° C., and is stored in the emulsifier tank 20 as described above.
  • the prepared emulsifier aqueous solution (b1) is stored while being heated to 60 ° C., and these are stored in a line as a premixing device so that the weight ratio of “synthetic polyisoprene”: “emulsifier” becomes 10: 1.
  • the mixture was continuously supplied to the mixing device 30 to continuously obtain an emulsion (the ratio of normal hexane in the emulsion was 37.7% by weight).
  • the emulsified liquid was continuously discharged to a closed storage tank 40 in which the valves other than the connection pipe to the mixing device 30 were closed.
  • a homogenizer (trade name "Milder”, manufactured by Taiheiyo Kiko Co., Ltd.) was used. Further, before the emulsified liquid was discharged from the mixing device 30, the pressure of the storage tank 40 in a closed state was 0 MPa (gauge pressure).
  • the system composed of the storage tank 40, the distillation pipe 60 and the condenser 70 was a closed system which was closed from the outside air.
  • the temperature of the emulsion is raised to 85 ° C. by heating with steam, and the pressure inside the storage tank 40 when the temperature of the emulsion reaches 85 ° C. is 0.08 MPa (gauge pressure). Met.
  • the distillation of normal hexane from the emulsion was continued under the conditions that the temperature of the emulsion was 85 ° C. and the pressure inside the storage tank 40 was 0.08 MPa (gauge pressure).
  • Example 1 the organic solvent distillation time, which is the time from the start of normal hexane vapor aggregation in the condenser 70 to the end of normal hexane distillation, was 9 hours (described later).
  • Example 1 the organic solvent distillation time was measured in the same manner.
  • the foam surface height due to the foaming of the emulsion in the storage tank 40 was observed, the height was 72% of the storage tank volume (maximum foam surface height: 72%) at the highest time. there were.
  • Example 1 after the distillation of normal hexane was completed, the ratio of the synthetic polyisoprene adhered to the wall surface of the storage tank 40 was reduced to 100% by weight of the total amount of the synthetic polyisoprene contained in the emulsion. In contrast, the content was 1.3% by weight, and the volume average particle diameter of the obtained synthetic polyisoprene latex was 1.09 ⁇ m.
  • Example 2 In the same manner as in Example 1, except that the heating temperature of the emulsion was changed from 85 ° C. to 78 ° C. by heating with steam when normal hexane was distilled off in the storage tank 40. N-hexane was distilled off from the mixture.
  • Example 2 when the temperature of the emulsion was set at 78 ° C., the pressure inside the storage tank 40 was 0.06 MPa (gauge pressure). Table 1 shows the results.
  • Example 3 Instead of normal hexane, normal pentane (boiling point: 36 ° C.) is used, and when the normal pentane is distilled off in the storage tank 40, the emulsion is heated to 85 ° C. by heating with steam. The normal pentane was distilled off from the emulsion in the same manner as in Example 1 except that the temperature was changed to 67 ° C. In Example 3, when the temperature of the emulsion was set at 67 ° C., the pressure inside the storage tank 40 was 0.04 MPa (gauge pressure). Table 1 shows the results.
  • Example 4 A styrene-isoprene-styrene copolymer (trade name “Quintac 3620”, manufactured by Zeon Corporation, described as “SIS” in Table 1) was used instead of synthetic polyisoprein, and cyclohexane was used instead of normal hexane. (Boiling point: 80 ° C.) Except for using, in the same manner as in Example 1, an emulsified liquid was obtained, and when the cyclohexane was distilled off in the storage tank 40, the emulsified liquid was heated by steam. Cyclohexane was distilled off from the emulsion in the same manner as in Example 1 except that the heating temperature was changed from 85 ° C. to 82 ° C. In Example 4, when the temperature of the emulsion was 82 ° C., the pressure inside the storage tank 40 was 0.07 MPa (gauge pressure). Table 1 shows the results.
  • Comparative Example 2 a pressure reducing pump was connected to the downstream side of the condenser 70, and the pressure in the storage tank 40 was adjusted to ⁇ 0.02 MPa (gauge pressure) by reducing the pressure with the pressure reducing pump.
  • ⁇ 0.02 MPa gauge pressure

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne un procédé pour la production d'un latex de polymère, qui comprend une étape dans laquelle un solvant organique est retiré par distillation à partir d'une émulsion qui est obtenue par mélange d'une solution aqueuse d'un agent émulsifiant avec une solution ou dispersion liquide d'un polymère, ladite solution ou dispersion liquide étant obtenue par dissolution ou dispersion du polymère dans le solvant organique. En ce qui concerne ce procédé de production d'un latex de polymère, le retrait par distillation du solvant organique à partir de l'émulsion est effectué à l'intérieur d'un récipient dans lequel la pression est régulée à 0,02 MPa ou plus en termes de pression manométrique.
PCT/JP2019/033270 2018-08-29 2019-08-26 Procédé pour la production de latex de polymère WO2020045339A1 (fr)

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KR1020217004897A KR20210049800A (ko) 2018-08-29 2019-08-26 중합체 라텍스의 제조 방법
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CN116589705A (zh) * 2023-04-19 2023-08-15 北京诺维新材科技有限公司 一种胶乳的制备方法及制备装置
CN116891543A (zh) * 2023-09-11 2023-10-17 新疆天利石化股份有限公司 一种采用并串联连续釜式蒸馏法制备人造胶乳的方法

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WO2017159534A1 (fr) * 2016-03-15 2017-09-21 日本ゼオン株式会社 Procédé de fabrication de latex de polymère

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CN103772772A (zh) * 2014-01-21 2014-05-07 大连理工大学 采用稀土聚异戊二烯胶液直接制备胶乳的方法
CN107474587B (zh) * 2016-06-08 2019-08-20 中国石油化工股份有限公司 一种聚异戊二烯胶乳及其制备方法
CN107602877A (zh) * 2017-09-05 2018-01-19 青岛科技大学 一种合成杜仲胶乳的制备方法

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JPS62257902A (ja) * 1986-05-02 1987-11-10 Sumitomo Naugatuck Co Ltd 重合体ラテツクス中の揮発性物質を除去する方法
WO2017159534A1 (fr) * 2016-03-15 2017-09-21 日本ゼオン株式会社 Procédé de fabrication de latex de polymère

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116589705A (zh) * 2023-04-19 2023-08-15 北京诺维新材科技有限公司 一种胶乳的制备方法及制备装置
CN116589705B (zh) * 2023-04-19 2024-04-30 北京诺维新材科技有限公司 一种胶乳的制备方法及制备装置
CN116891543A (zh) * 2023-09-11 2023-10-17 新疆天利石化股份有限公司 一种采用并串联连续釜式蒸馏法制备人造胶乳的方法
CN116891543B (zh) * 2023-09-11 2023-12-19 新疆天利石化股份有限公司 一种采用并串联连续釜式蒸馏法制备人造胶乳的方法

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