WO2001014296A1 - Procede de recuperation de polyoxyalkylene polyol par decomposition - Google Patents

Procede de recuperation de polyoxyalkylene polyol par decomposition Download PDF

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Publication number
WO2001014296A1
WO2001014296A1 PCT/JP2000/005455 JP0005455W WO0114296A1 WO 2001014296 A1 WO2001014296 A1 WO 2001014296A1 JP 0005455 W JP0005455 W JP 0005455W WO 0114296 A1 WO0114296 A1 WO 0114296A1
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WO
WIPO (PCT)
Prior art keywords
polyoxyalkylene polyol
temperature
decomposition
molecular weight
water
Prior art date
Application number
PCT/JP2000/005455
Other languages
English (en)
Japanese (ja)
Inventor
Katsuhisa Kodama
Kouichi Murayama
Takashi Kumaki
Yoshiyuki Nagase
Ryuichi Fukuzato
Fumihiko Kasuya
Original Assignee
Takeda Chemical Industries, Ltd.
Kobe Steel Ltd.
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 Takeda Chemical Industries, Ltd., Kobe Steel Ltd. filed Critical Takeda Chemical Industries, Ltd.
Priority to AU64768/00A priority Critical patent/AU6476800A/en
Publication of WO2001014296A1 publication Critical patent/WO2001014296A1/fr

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to a method for decomposing and recovering a polyoxyalkylene polyol into low molecular weight glycols using high-temperature high-pressure liquid water or supercritical water. More specifically, polyoxyalkylenepolyols obtained by chemical decomposition of polyurethane resin ⁇ Polyoxyalkylenepolyols The present invention relates to a method for decomposing and recovering low-molecular-weight glycol using high-temperature high-pressure liquid water or supercritical water. Background art
  • Polyoxyalkylene polyols are also commonly referred to as polyether polyols, PPG, and the like, and have been widely used as raw materials for polyurethane resins and surfactants.
  • an active hydrogen-containing compound such as a low molecular weight hydroxyl-containing compound such as propylene glycol or glycerin, or an amino-containing compound such as ethylenediamine, is used as an initiator, and an alkali metal hydroxide such as caustic. It has been produced by ring-opening polymerization of an alkylene oxide such as propylene oxide / ethylene oxide using the catalyst as a catalyst.
  • an alkylene oxide such as propylene oxide / ethylene oxide
  • the type of initiator and the type and addition amount of alkylene oxide products with various functional groups and molecular weights can be manufactured.
  • various polyoxyalkylene polyols are industrially available depending on the application. It has been used for
  • polyurethane resins have been widely used together with the polyisocyanate compound as a main raw material for polyurethane resins. That is, polyurethane resins are widely and widely used as soft, semi-rigid, and rigid urethane foams for furniture such as sofas and beds, beddings, cushioning materials for automobile seats, and heat insulating materials for refrigerators and the like. It is also widely used as an elastomer for shoe soles, tires and belts. Recently, importance has been placed on resource protection and environmental preservation, and methods of recycling and reusing various plastic products are being studied individually, but polyurethane resins are no exception.
  • Known polyurethane resin recycling methods can be broadly classified into (1) material recycling technology, (2) chemical recycling technology, and (3) energy recycling technology.
  • the material recycling technology (1) involves cutting polyurethane foam into appropriate size as necessary, reusing it as a cushioning material by means such as rebonding or compression molding, or pulverizing foam or elastomer to form a new material. This is a technology for mixing and using raw materials as fillers.
  • the chemical recycling technology (2) is a technology that decomposes polyurethane resin into raw materials for polyurethane or chemical substances that can be used as raw materials, and reuses them.Glycolysis, amine decomposition, hydrolysis, etc. are known. ing.
  • the energy recycling technology (3) uses polyurethane resin as fuel and recovers it as heat or steam.
  • the technology of the above (1) has a problem in quality as a cushioning material and a heating material, and its use is limited to only a part. It has been pointed out that the technology of (3) may cause new pollution problems such as generation of harmful substances by combustion.
  • the chemical recycling technology (2) can be said to be an ideal recycling technology if it can be implemented economically and industrially.
  • the glycol decomposition method and the amine decomposition method are based on the urethane bond, which is relatively susceptible to decomposition, among various bonds such as urethane bond, urea bond, biuret bond, and arophanate bond existing in the polyurethane resin.
  • Arophanate bonds, biuret bonds, etc. are cleaved with glycosylamine compounds and exchange It liquefies in response.
  • glycolamine used as a decomposing agent newly forms a urethane bond or a urea bond, and is mixed into the liquid decomposed product as a perylene or urea derivative. Therefore, this technique does not mean that the polyurethane resin is decomposed into the polyol / polyamine compound, which is the raw material thereof, and is recovered, so that the use of the recovered material is limited.
  • the perylene bond and the urea bond in the polyurethane resin are hydrolyzed, and as a product, a polyoxyalkylene polyol which is a raw material of the polyurethane and a polyamine compound which is an intermediate raw material of the polyisocyanate compound are produced. Since it is recovered, it seems to be the best method in terms of material reuse.
  • this method there is a problem with this method. That is, when the polyamine compound produced by decomposition is usually a single compound such as toluenediamine, it can be easily separated and purified by distillation or the like, but the polyoxyalkylene polyol which is produced by decomposition at the same time can be obtained. Is a mixture of compounds with different numbers of functional groups and molecular weights, and it is usually impossible to separate them individually.
  • An object of the present invention is to provide a method for decomposing and recovering, for example, a polyoxyalkylene polyol mixture that is recovered in a chemical cycle or discharged as waste in a manufacturing process into a reusable substance. Disclosure of the invention
  • polyether polyol which is a raw material of polyurethane
  • polyether polyol which is a raw material of polyurethane
  • the polyoxyalkylene polyol used as a raw material of the present invention may be any one that is used as a raw material for producing a surfactant / polyurethane resin. Commonly used ones have 1 to 8 functional groups, a hydroxyl value of 20 to 30 Omg KOH / g, and a molecular weight of about 200 to 7,000. Specific examples include polyols such as water, methanol, ethanol, butanol, phenol, ethylene glycol, propylene glycol, glycerin, trimethylol pulp bread, erythritol, sorbitol, and soy rose.
  • polyoxyalkylene polyols obtained by subjecting amines such as ethanolamine, ethylenediamine, and tolylenediamine as initiators to addition polymerization of propylene oxide and ethylene oxide. These poly The oxyalkylene polyol may be used alone or as a mixture of two or more.
  • the method of the present invention can be used as a part of the chemical recycling method of polyurethane resin.
  • polyurethane resin is used, for example, glycolide using glycols such as ethylene glycol and propylene glycol.
  • Decomposition by cis method for example, solvolysis method such as aminolysis method using amine compounds such as tolylenediamine, ethylenediamine, ethanolamine, etc., hydrolysis method using water or alkali decomposition method, and decomposition as necessary It is desirable to use a product obtained by removing an amine compound from the product by distillation or the like as a raw material.
  • the decomposed product When decomposing polyurethane resin by the glycolysis method or aminolysis method, depending on the type of decomposer and reaction conditions, the decomposed product may be recovered as a urethane or urea compound and may not be easily removed like a polyamine compound However, in such a case, if the decomposition mixture is treated with high-temperature and high-pressure liquid water at 250 to 320, urethane and urea compounds are decomposed into polyamine compounds. It can be easily removed by fractionation or the like.
  • the temperature required to hydrolyze the polyoxyalkylene polyol is usually from 320 to 500.
  • Water is 22.1 megapascals (MPa),
  • the produced low molecular weight glycol is oxidized and the yield decreases.
  • More preferred hydrolysis temperatures are from 330 to 450, especially from 350 to
  • the pressure in this step does not directly affect the decomposition rate of the polyoxyalkylene polyol, but is higher than the pressure at which the high-temperature and high-pressure water can maintain the liquid state.
  • a pressure higher than the supercritical water can maintain the supercritical state is required.
  • the ratio (hydrolysis ratio) of the polyoxyalkylene polyol to water depends on the type of the polyol to be decomposed, but the weight ratio of the former is 1 to the latter 0.5 to 10.0, preferably 1.0 to 1.0. The range is 5.0. If the water ratio is less than 0.5, the decomposition of ether bonds may be incomplete.If the water ratio is more than 1.0, a large device is not only required, but also energy loss is increased, which is uneconomical. Become.
  • the time required for the decomposition reaction of the present invention is usually 10 minutes to 2 hours, preferably 20 minutes to 1 hour, depending on the type of the polyoxyalkylene polyol and the reaction temperature.
  • the products decomposed by this reaction are low-molecular-weight glycols having a molecular weight of 150 or less, such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, and these are separated into individual glycols by distillation or other means as necessary. Can be separated.
  • the recovered low-molecular-weight glycols can be effectively reused as a mixture, or after being separated individually, as a raw material for producing polyurethane resin, polyether resin, polyester resin, and the like.
  • a trifunctional polyoxypropylene triol with a molecular weight of 3,000 (ACTCOL 79-56) 50 g of pure water and 350 g of pure water were charged and the inside was replaced with nitrogen gas. The reaction temperature was raised to 35 O: and held at this temperature for 30 minutes. The temperature in the autoclave was lowered to room temperature, and the contents were taken out and water was removed to obtain 54 g of a low-viscosity oily substance. The obtained oil was analyzed by gas chromatography, and it was confirmed that propylene glycol (PG) was produced by 27% by weight and dipropylene glycol (DPG) was produced by 24% by weight.
  • PG propylene glycol
  • DPG dipropylene glycol
  • the temperature was raised to 270 and maintained at this temperature for 30 minutes. During this time, the pressure showed 6.
  • IMP a After cooling to room temperature, the content was transferred to a mold flask, water was removed at normal pressure, and then vacuum distillation of 5 mmHg at 250 was performed to remove low boiling substances.
  • the recovered polyoxyalkylene polyol generated by the chemical decomposition of the polyurethane or the waste polyol discharged in the production process of the polyoxyalkylene polyol is decomposed into a recyclable low molecular weight glycol. It is now possible to recover it, and a true chemical recycling method for polyurethane resins has been completed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

On hydrolyse un polyoxyalkylène polyol avec de l'eau liquide haute pression, présentant une température de 320 à 500 °C ou avec de l'eau supercritique, pour produire des glycols possédant un poids moléculaire de 150 ou moins. On récupère ensuite lesdits glycols. Ainsi, on a mis en oeuvre un procédé de recyclage chimique de résine polyuréthane au sens propre du terme.
PCT/JP2000/005455 1999-08-23 2000-08-14 Procede de recuperation de polyoxyalkylene polyol par decomposition WO2001014296A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU64768/00A AU6476800A (en) 1999-08-23 2000-08-14 Method for recovering polyoxyalkylene polyol through decomposition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/235251 1999-08-23
JP23525199 1999-08-23

Publications (1)

Publication Number Publication Date
WO2001014296A1 true WO2001014296A1 (fr) 2001-03-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2000/005455 WO2001014296A1 (fr) 1999-08-23 2000-08-14 Procede de recuperation de polyoxyalkylene polyol par decomposition

Country Status (2)

Country Link
AU (1) AU6476800A (fr)
WO (1) WO2001014296A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993016976A1 (fr) * 1992-02-20 1993-09-02 Exxon Research And Engineering Company Procede de recyclage de polymeres comprenant des liaisons ether repetitives
JPH10310663A (ja) * 1997-05-09 1998-11-24 Takeda Chem Ind Ltd ポリウレタン樹脂の分解回収方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993016976A1 (fr) * 1992-02-20 1993-09-02 Exxon Research And Engineering Company Procede de recyclage de polymeres comprenant des liaisons ether repetitives
JPH10310663A (ja) * 1997-05-09 1998-11-24 Takeda Chem Ind Ltd ポリウレタン樹脂の分解回収方法

Also Published As

Publication number Publication date
AU6476800A (en) 2001-03-19

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