WO2025204875A1 - Procédé de récupération de polymère - Google Patents

Procédé de récupération de polymère

Info

Publication number
WO2025204875A1
WO2025204875A1 PCT/JP2025/009169 JP2025009169W WO2025204875A1 WO 2025204875 A1 WO2025204875 A1 WO 2025204875A1 JP 2025009169 W JP2025009169 W JP 2025009169W WO 2025204875 A1 WO2025204875 A1 WO 2025204875A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
liquid
coarse
solvent
emulsion polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/009169
Other languages
English (en)
Japanese (ja)
Inventor
葉子 岩▲崎▼
直佑 堀田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Publication of WO2025204875A1 publication Critical patent/WO2025204875A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08F6/18—Increasing the size of the dispersed particles

Definitions

  • the present invention relates to a method for recovering polymers.
  • a conventional method for recovering a polymer from an emulsion polymerization liquid obtained by emulsion polymerization of a monomer composition containing a monomer, an emulsifier, and a solvent involves dropping the emulsion polymerization liquid into a poor solvent in which the polymer has low solubility, and then filtering and drying the precipitated polymer.
  • the inventors conducted extensive research to solve the above problems. They discovered that adding a solvent to the emulsion polymerization liquid so as to coarsely dissolve the polymer makes it possible to efficiently separate the solid and liquid and efficiently recover the polymer from the emulsion polymerization liquid, leading to the completion of the present invention.
  • the polymer recovery method described in any of [1] to [5] above may further include, before the step of obtaining the coarse polymer particle-containing liquid, a step of emulsion-polymerizing a monomer composition containing a monomer, an emulsifier, and a liquid medium to prepare the emulsion polymerization liquid.
  • polymers can be efficiently recovered from emulsion polymerization liquids.
  • the present invention will be described in detail below.
  • the method for recovering a polymer of the present invention can be used when recovering a polymer from an emulsion polymerization liquid.
  • the method for recovering a polymer of the present invention includes a step of coarsening the polymer contained in the emulsion polymerization liquid to obtain a liquid containing coarse polymer particles (hereinafter, this step may be referred to as the "coarse particle formation step"), and a step of recovering the coarse polymer particles from the liquid containing coarse polymer particles (hereinafter, this step may be referred to as the "recovery step”).
  • the polymer recovery method of the present invention may include a step of preparing an emulsion polymerization liquid (hereinafter, sometimes referred to as a "preparation step") before the coarse particle formation step.
  • the polymer recovery method of the present invention may include a step of subjecting the coarse polymer particles to post-treatment such as drying after the recovery step.
  • the other polymers include repeating units represented by the above formula (I) in which R 1 is a chlorine atom and R 3 and R 4 are hydrogen atoms, such as at least one monomer unit selected from the group consisting of methyl ⁇ -chloroacrylate unit, ethyl ⁇ -chloroacrylate unit, benzyl ⁇ -chloroacrylate unit, 1-adamantyl ⁇ -chloroacrylate unit, 2,2,3,3,3-pentafluoropropyl ⁇ -chloroacrylate unit, 2,2,3,3,4,4,4-heptafluorobutyl ⁇ -chloroacrylate unit, 1-phenyl- 1 -trifluoromethyl-2,2,2-trifluoroethyl ⁇ -chloroacrylate unit, and 2,2,3,3,4,4,5,5,5-nonafluoropentyl ⁇ -chloroacrylate unit, and repeating units represented by the above formula (I) in which R 5 is a methyl group and R 6
  • nonionic emulsifiers include polyethylene glycol ester emulsifiers and Pluronic (registered trademark) emulsifiers such as block copolymers of ethylene oxide and propylene oxide.
  • fatty acid salts are preferred as emulsifiers, with fatty acid salts having 10 or more carbon atoms being more preferred, and saturated fatty acid salts having 10 or more carbon atoms such as sodium decanoate, sodium laurate, potassium palmitate, potassium stearate, and potassium myristate, and unsaturated fatty acid salts having 10 or more carbon atoms such as potassium oleate and sodium oleate being even more preferred.
  • the above-mentioned emulsifiers can be used alone or in combination of two or more.
  • the amount of emulsifier in the emulsion polymerization liquid is not particularly limited, and can be, for example, 0.5 to 30 parts by weight per 100 parts by weight of polymer.
  • Liquid medium Water is usually used as the liquid medium. As long as emulsification with an emulsifier is possible, water alone or a mixture of water and an organic solvent may be used as the liquid medium. When a mixture of water and an organic solvent is used, the proportion of the organic solvent in the liquid medium can be, for example, 10% by volume or less, and preferably 5% by volume or less.
  • Other components include known additives used in emulsion polymerization, such as polymerization initiators, chelating agents, oxygen scavengers, molecular weight adjusters, and pH adjusters.
  • a solvent is added to the emulsion polymerization liquid to coarsely form the polymer contained in the emulsion polymerization liquid, thereby obtaining a liquid containing coarse polymer particles.
  • the addition of a solvent causes the polymer contained in the emulsion polymerization liquid to aggregate or agglomerate and form coarse particles, thereby obtaining a liquid containing coarse polymer particles that have improved sedimentation properties compared to before the addition of the solvent.
  • the particle size of the coarse polymer particles is usually larger than the particle size of the polymer contained in the emulsion polymerization liquid.
  • the solvent is not particularly limited, and any solvent capable of coarsening the polymer into coarse particles can be used depending on the type of polymer and liquid medium contained in the emulsion polymerization liquid.
  • the solvent include ketones such as acetone, methyl ethyl ketone, cyclohexanone, and diisobutyl ketone; ethers such as diethyl ether, dioxane, and tetrahydrofuran; esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, and ⁇ -caprolactone; hydrocarbons such as linear aliphatic hydrocarbons (e.g., hexane), cyclic aliphatic hydrocarbons (e.g., cyclopentane, cyclohexane), and aromatic hydrocarbons (e.g., toluene and xylene); alcohols such as methanol, ethanol, n-propano
  • the solvents mentioned above it is preferable to use a solvent in which the solubility of the polymer contained in the emulsion polymerization liquid at a temperature of 25°C is 5 g/100 g or more, and it is even more preferable to use a solvent in which the solubility is 10 g/100 g or more. If a solvent with a solubility above the above lower limit is used, the polymer can be effectively coarsened into large particles.
  • the SP value of the solvent may be 17.0 MPa 1/2 or more and 23.0 MPa 1/2 or less, preferably 19.0 MPa 1/2 or more and 20.0 MPa 1/2 or less.
  • the London dispersion force term (dD S ) of the Hansen solubility parameter of the solvent may be 12.0 MPa 1/2 or more and 18.0 MPa 1/2 or less, preferably 15.0 MPa 1/2 or more and 17.0 MPa 1/2 or less.
  • the dipole-dipole force term (dP S ) of the Hansen solubility parameter of the polymer may be 3.0 MPa 1/2 or more and 12.0 MPa 1/2 or less.
  • the hydrogen bonding strength term (dH S ) of the Hansen solubility parameter of the polymer may be 5.0 MPa 1/2 or more and 10.0 MPa 1/2 or less, preferably 7.0 MPa 1/2 or more and 8.0 MPa 1/2 or less.
  • the solvent is preferably one in which the absolute value of the difference between the SP value of the polymer contained in the emulsion polymerization liquid and the SP value of the solvent is 7.5 MPa 1/2 or less, more preferably one in which the absolute value of the difference between the SP value of the polymer and the SP value of the solvent is 5.0 MPa 1/2 or less, and even more preferably one in which the absolute value of the difference between the SP value of the polymer and the SP value of the solvent is 2.5 MPa 1/2 or less.
  • the lower limit of the absolute value of the difference between the SP value of the polymer and the SP value of the solvent is not particularly limited, and can be 0 MPa 1/2 or more.
  • the amount of solvent added to the emulsion polymerization liquid can be, for example, 15% by mass or more and 85% by mass or less, and preferably 20% by mass or more and 80% by mass or less, where the total of the amount of liquid medium and the amount of solvent contained in the emulsion polymerization liquid is 100% by mass.
  • the type and amount of the solvent added to the emulsion polymerization liquid preferably satisfy the following condition (1) from the viewpoint of successfully coarsening the polymer particles.
  • Condition (1) The absolute value of the difference (dP P - dP M ) between the dipole-dipole force term (dP P ) of the Hansen solubility parameter of the polymer and the dipole-dipole force term (dP M ) of the Hansen solubility parameter of the mixture of the liquid medium and the solvent is 3.0 MPa 1/2 or more and 5.5 MPa 1/2 or less.
  • the coarse polymer particle-containing liquid obtained by adding a solvent to the emulsion polymerization liquid contains a coarse polymer (coarse polymer particles), an emulsifier, and a mixture of a liquid medium and a solvent, and optionally further contains other components.
  • the method for solid-liquid separation of the liquid containing coarse polymer particles is not particularly limited, and examples thereof include centrifugation, filtration, decantation, etc. These solid-liquid separation methods may be used alone or in appropriate combination of two or more. Among these, decantation is preferred as a method for solid-liquid separation of a liquid containing coarse polymer particles from the viewpoint of easy recovery of the polymer.
  • the coarse polymer particles usually form a mass at the bottom of a container, and solid-liquid separation can be easily performed by simply tilting the container without using tools such as filter paper or a dropper.
  • ⁇ Post-processing step> The coarse particles of the polymer obtained in the recovery step are in the form of coarse agglomerates, whereas polymers are generally stored in powder form. Therefore, in an optional post-treatment step, the recovered polymer can be dissolved in a good solvent and reprecipitated by dropping the solution into a poor solvent, followed by filtration and drying to obtain a powder form of the polymer.
  • Example 1 ⁇ Preparation process> 10.00 g of ⁇ -chloroacrylate-1-phenyl-1-trifluoromethyl-2,2,2-trifluoroethyl ester and 3.55 g of ⁇ -methylstyrene were placed in a bottle as monomers, and 0.10 g of azobisisobutyronitrile (AIBN) as an initiator was added to the bottle.
  • AIBN azobisisobutyronitrile
  • a previously prepared aqueous sodium laurate solution (a mixture of 3.39 g of sodium laurate as an emulsifier and 22.10 g of pure water as a liquid medium) was then added and emulsified with vigorous stirring. The atmosphere in the bottle was replaced with nitrogen, and the mixture was stirred at 75°C for 3 hours.
  • emulsion polymerization liquid containing 13.55 g of polymer A (a polymer composed of ⁇ -chloroacrylate-1-phenyl-1-trifluoromethyl-2,2,2-trifluoroethyl ester units and ⁇ -methylstyrene units).
  • polymer A a polymer composed of ⁇ -chloroacrylate-1-phenyl-1-trifluoromethyl-2,2,2-trifluoroethyl ester units and ⁇ -methylstyrene units.
  • Example 2 The preparation step, coarse-particle formation step, and recovery step were carried out in the same manner as in Example 1, except that in the preparation step, 1.82 g of KORR-18 (trade name; manufactured by Kao Corporation, an aqueous solution of semi-hardened beef tallow fatty acid potassium soap with a solids content of 17.5 to 18.5%) was used instead of sodium laurate as the emulsifier, and the amount of tetrahydrofuran added in the coarse-particle formation step was changed to 33.0 g (an amount such that the proportion of tetrahydrofuran was 60 mass%, assuming that the total of the amount of water contained in the emulsion polymerization liquid and the amount of tetrahydrofuran added was 100 mass%).As a result, the mixed liquid could be decanted well, and the polymer could be recovered.
  • KORR-18 trade name; manufactured by Kao Corporation, an aqueous solution of semi-hardened beef tallow fatty acid potassium soap with a solid
  • Example 3 The preparation step, coarse particle formation step, and recovery step were carried out in the same manner as in Example 1, except that 2.40 g of sodium decanoate was used instead of sodium laurate as the emulsifier in the preparation step. As a result, the mixed liquid could be decanted well, and the polymer could be recovered.
  • Example 4 The preparation step, the coarse-particle formation step, and the recovery step were carried out in the same manner as in Example 1, except that 83.0 g of acetone (an amount such that the proportion of acetone was 79 mass%, assuming that the total of the amount of water contained in the emulsion polymerization liquid and the amount of acetone added was 100 mass%) was used instead of tetrahydrofuran as the solvent to be added to the emulsion polymerization liquid in the coarse-particle formation step. As a result, the mixed liquid could be decanted well, and the polymer could be recovered.
  • 83.0 g of acetone an amount such that the proportion of acetone was 79 mass%, assuming that the total of the amount of water contained in the emulsion polymerization liquid and the amount of acetone added was 100 mass%
  • tetrahydrofuran as the solvent to be added to the emulsion polymerization liquid in the coarse-particle formation step.
  • Example 5 ⁇ Preparation process> 61.1 g of purified water as a liquid medium, 3.0 g of sodium carbonate, and 5.0 g of KORR-18 (trade name; manufactured by Kao Corporation, an aqueous solution of semi-hardened beef tallow fatty acid potassium soap with a solids content of 17.5-18.5%) as an emulsifier were placed in a separable flask and dissolved. 10.0 g of methyl ⁇ -chloroacrylate and 24.1 g of ⁇ -methylstyrene were added as monomers, and the mixture was emulsified with vigorous stirring.
  • KORR-18 trade name; manufactured by Kao Corporation, an aqueous solution of semi-hardened beef tallow fatty acid potassium soap with a solids content of 17.5-18.5%
  • the amount of tetrahydrofuran added was such that the proportion of tetrahydrofuran was 20% by mass, where the total amount of water contained in the emulsion polymerization liquid and the amount of tetrahydrofuran added was taken as 100% by mass. ⁇ Recovery process> Finally, the mixture was left to stand and then decanted to recover the polymer.
  • Example 1 The preparation step and the coarse-particle formation step were carried out in the same manner as in Example 1, except that 2.40 g of sodium decanoate was used instead of sodium laurate as the emulsifier in the preparation step, and the amount of tetrahydrofuran added in the coarse-particle formation step was changed to 9.93 g (an amount such that the proportion of tetrahydrofuran was 31 mass % when the total of the amount of water contained in the emulsion polymerization liquid and the amount of tetrahydrofuran added was 100 mass %), and an attempt was made to carry out the recovery step, but the polymer did not become coarse particles, and decantation was not possible.
  • Example 2 The preparation step and the coarse-particle formation step were carried out in the same manner as in Example 1, except that 9.93 g of acetone (an amount such that the proportion of acetone was 31 mass %, assuming that the total of the amount of water contained in the emulsion polymerization liquid and the amount of acetone added was 100 mass %) was used instead of tetrahydrofuran as the solvent to be added to the emulsion polymerization liquid in the coarse-particle formation step, and an attempt was made to carry out the recovery step, but the polymer did not become coarse particles, and decantation was not possible.
  • 9.93 g of acetone an amount such that the proportion of acetone was 31 mass %, assuming that the total of the amount of water contained in the emulsion polymerization liquid and the amount of acetone added was 100 mass % was used instead of tetrahydrofuran as the solvent to be added to the emulsion polymerization liquid in the coarse-particle formation step, and an attempt was made
  • the polymer can be efficiently recovered from the emulsion polymerization liquid.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention permet de récupérer efficacement un polymère à partir d'un liquide de polymérisation en émulsion. Un procédé de récupération d'un polymère selon la présente invention comprend les étapes consistant à : ajouter un solvant à un liquide de polymérisation en émulsion qui contient un polymère, un émulsifiant et un milieu liquide et former des particules grossières du polymère afin d'obtenir un liquide contenant des particules polymères grossières ; et récupérer les particules polymères grossières à partir du liquide contenant des particules polymères grossières. La valeur absolue de la différence entre le terme de force dipôle-dipôle du paramètre de solubilité de Hansen du polymère et le terme de force dipôle-dipôle du paramètre de solubilité de Hansen d'un liquide mélangé comprenant le solvant et le milieu liquide dans le liquide contenant des particules polymères grossières est de préférence de 3,0 MPa1/2 ou plus et de 5,5 MPa1/2 ou moins.
PCT/JP2025/009169 2024-03-28 2025-03-11 Procédé de récupération de polymère Pending WO2025204875A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024054829 2024-03-28
JP2024-054829 2024-03-28

Publications (1)

Publication Number Publication Date
WO2025204875A1 true WO2025204875A1 (fr) 2025-10-02

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Country Link
WO (1) WO2025204875A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54126288A (en) * 1978-02-21 1979-10-01 Sintef Production of aqueous emusion or dispersion of partially water soluble material
JPS6390513A (ja) * 1986-10-01 1988-04-21 エア・プロダクツ・アンド・ケミカルズ・インコーポレイテツド 逆型重合体エマルジヨンおよびその製造法
JPH01279902A (ja) * 1987-08-12 1989-11-10 Nippon Oil & Fats Co Ltd 重合体非水分散液の製造方法、重合体非水分散液および塗料組成物
JP2010513598A (ja) * 2006-12-14 2010-04-30 ザ・ボーイング・カンパニー ゲル状接着剤剥離組成物および使用方法
JP2016014853A (ja) * 2014-06-13 2016-01-28 キヤノン株式会社 電子写真感光体、その製造方法、電子写真装置及びプロセスカートリッジ、ならびにクロロガリウムフタロシアニン結晶
JP2021160281A (ja) * 2020-03-31 2021-10-11 コスモ石油株式会社 樹脂の溶解方法及び樹脂溶解液の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54126288A (en) * 1978-02-21 1979-10-01 Sintef Production of aqueous emusion or dispersion of partially water soluble material
JPS6390513A (ja) * 1986-10-01 1988-04-21 エア・プロダクツ・アンド・ケミカルズ・インコーポレイテツド 逆型重合体エマルジヨンおよびその製造法
JPH01279902A (ja) * 1987-08-12 1989-11-10 Nippon Oil & Fats Co Ltd 重合体非水分散液の製造方法、重合体非水分散液および塗料組成物
JP2010513598A (ja) * 2006-12-14 2010-04-30 ザ・ボーイング・カンパニー ゲル状接着剤剥離組成物および使用方法
JP2016014853A (ja) * 2014-06-13 2016-01-28 キヤノン株式会社 電子写真感光体、その製造方法、電子写真装置及びプロセスカートリッジ、ならびにクロロガリウムフタロシアニン結晶
JP2021160281A (ja) * 2020-03-31 2021-10-11 コスモ石油株式会社 樹脂の溶解方法及び樹脂溶解液の製造方法

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