WO2010125743A1 - Procédé de décomposition d'un composé de polyurée issu d'un polyméthylène-polyphénylène polyisocyanate - Google Patents

Procédé de décomposition d'un composé de polyurée issu d'un polyméthylène-polyphénylène polyisocyanate Download PDF

Info

Publication number
WO2010125743A1
WO2010125743A1 PCT/JP2010/002350 JP2010002350W WO2010125743A1 WO 2010125743 A1 WO2010125743 A1 WO 2010125743A1 JP 2010002350 W JP2010002350 W JP 2010002350W WO 2010125743 A1 WO2010125743 A1 WO 2010125743A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric mdi
polyurea compound
water
decomposing
based polyurea
Prior art date
Application number
PCT/JP2010/002350
Other languages
English (en)
Japanese (ja)
Inventor
古川睦久
小椎尾謙
本九町卓
Original Assignee
日本ポリウレタン工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ポリウレタン工業株式会社 filed Critical 日本ポリウレタン工業株式会社
Publication of WO2010125743A1 publication Critical patent/WO2010125743A1/fr

Links

Images

Classifications

    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/14—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with steam or water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
    • C08G18/832—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides by water acting as hydrolizing agent
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/02—Polyureas
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention hydrolyzes a polymethylene polyphenylene polyisocyanate (hereinafter abbreviated as polymeric MDI) -based polyurea compound in carbon dioxide in a supercritical state or subcritical state, thereby polymethylene polyphenyl polyamine (hereinafter abbreviated as PMDA). ) Is recovered, and the method of decomposing the polymeric MDI-based polyurea compound.
  • polymeric MDI polymethylene polyphenylene polyisocyanate
  • PMDA polymethylene polyphenyl polyamine
  • Polyurethane is a polymer material synthesized by polyaddition reaction of polyisocyanate and polyol. Polyurethane can be imparted with various physical properties by blending, formulation, molding method and the like. For this reason, it is used in a wide variety of forms such as foams, elastomers, paints, and adhesives.
  • Polyisocyanate which is a raw material for polyurethane, is obtained by reacting a corresponding polyamine with phosgene, and a polyurea residue is produced as a by-product at this time.
  • This residue is a tar-like substance that solidifies at room temperature and is difficult to handle, so that it has conventionally been a waste that is exclusively incinerated. In this incineration process, not only CO 2 but also NO x is generated, so that there is a problem from the viewpoint of environmental protection.
  • Patent Document 1 proposes a method of treating polyurea residue using water in a supercritical state or a subcritical state.
  • the object of the present invention is to recover a reusable polyamine without adding a hydrolysis accelerator such as an alkali to the residue containing a polyurea compound by-produced during the production of the polymeric MDI, which until now had only been disposed of.
  • Another object of the present invention is to provide a method for decomposing a polymeric MDI-based polyurea compound that does not cause the corrosive problem of the reactor.
  • the inventors of the present invention added a polymeric MDI-based polyurea compound in supercritical or subcritical carbon dioxide (supercritical point: 31 ° C., 7.4 MPa). By decomposing, the PMDA was efficiently recovered and suitable conditions therefor were found, and the present invention was completed. That is, the present invention is shown in the following (1) to (4).
  • the method of the present invention makes it possible to efficiently convert the residue during the production of polymeric MDI, which has been conventionally disposed of as industrial waste, into PMDA without using an additive such as an alkali.
  • the polymeric MDI-based polyurea compound is represented by the following formula (1): —NH—CO—NH— (urea group) is — (C 6 H 4 ) n — (polymethylene polyphenylene) A group adjacent to the group), and a part of the urea group is a biuret group. Specifically, it is mainly generated as a by-product residue during the production of polymeric MDI. The residue means a residue generated during the production of polymeric MDI.
  • the polymeric MDI-based polyurea compound used for the decomposition of the present invention may be generated in any process as long as it is a by-product residue during the production of the polymeric MDI. Specifically, it is a residue produced as a by-product in any of the PMDA production process, the PMDA and phosgene reaction process, the polymeric MDI purification process, and the like. These residues may be melted and dissolved in each step.
  • the residue applicable to the present invention is not limited to the polymeric MDI produced using phosgene, and when produced by the non-phosgene method, the residue produced as a by-product in any of these steps should be decomposed. Needless to say, you can.
  • Any residue may be used, but it is usually used after the residue generated in each step is separated from the liquid component by a solid-liquid separation step, a distillation step or the like.
  • the residue produced as a by-product during the production of these polymeric MDIs is a mixture mainly composed of thermal polycondensation products such as polyamines and polyisocyanates.
  • the thermal polycondensate has groups or rings such as urea (urethane), biuret, carbodiimide, isocyanurate and the like. In particular, many compounds having a complicated structure having a plurality of these groups or rings are contained.
  • the polymeric MDI-based polyurea compound such as the above residue is hydrolyzed into PMDA using liquid or gaseous water in supercritical or subcritical carbon dioxide.
  • water / polymeric MDI-based polyurea compound 10/1 to 50/1, and particularly preferably 20/1 to 40/1.
  • the temperature during hydrolysis is preferably 180 ° C. or higher and lower than 374 ° C., more preferably 190 ° C. or higher and lower than 374 ° C. When the temperature is lower than 180 ° C., the decomposition rate becomes slow.
  • the pressure is preferably 5 MPa to 11 MPa, and more preferably 7.4 to 9.2 MPa. When the pressure is low, carbon dioxide does not sufficiently permeate the polymeric MDI-based polyurea compound, and when the pressure is high, water does not sufficiently permeate the polymeric MDI-based polyurea compound, so the decomposition rate decreases.
  • the hydrolysis time of the polymeric MDI-based polyurea compound is not particularly limited, but is 1 minute to 300 minutes, preferably 1 minute to 150 minutes after reaching a predetermined temperature.
  • Mixing and heating of water and the polymeric MDI polyurea compound may be performed by any of the following methods, but 3) is preferable.
  • 1) Water and a polymeric MDI-based polyurea compound are mixed at a predetermined temperature.
  • 2) Water is heated to a predetermined temperature when mixed with the polymeric MDI-based polyurea compound, and the decomposition temperature is set by mixing the heated water and the polymeric MDI-based polyurea compound.
  • 3) Water and a polymeric MDI-based polyurea compound are mixed in advance at a predetermined concentration in a slurry preparation drum or the like to prepare a slurry, and then heated to a decomposition temperature.
  • PMDA is contained as a main component in the aqueous solution obtained by decomposing the polymeric MDI-based polyurea compound in this way, and PMDA is easily recovered by a method such as ordinary distillation or extraction. be able to.
  • the recovered PMDA can be used as a raw material in the polymeric MDI production process after further purification if necessary.
  • a light boiling component mainly composed of carbon dioxide is dissolved in the aqueous solution from which PMDA is separated, but it can be used for hydrolysis after removing it by performing steam stripping or the like. It can also be recycled as water. Or it can also drain after carrying out normal wastewater treatment.
  • the distillation residue during the production of the polymeric MDI may be any distillation residue generated by distillation in any step of the production facility of the polymeric MDI. Normal, It is mainly produced by distilling the reaction solution obtained in the amine production step or the step of reacting an amine with a carbonyl source such as phosgene.
  • the amount of by-products of this distillation residue varies depending on the production method, but is about 10% by mass relative to the produced polymeric MDI.
  • This distillation residue is usually liquid.
  • examples of an apparatus for recovering from the above distillation residue to a state that does not substantially contain a volatile component include those used in a normal volatile recovery process such as a thin film evaporator, an apparatus having a stirring and heating means such as a kneader. .
  • a two-phase flow evaporator having piston flow properties it is particularly preferable to use a two-phase flow evaporator having piston flow properties.
  • the evaporation device having piston flow means a facility through which an evaporation target flows in a certain direction from upstream to downstream of the device.
  • the two-phase flow type evaporator is an evaporator having at least a gas-liquid or gas-solid two-phase flow, and gas-liquid-solid three phases may coexist.
  • Typical examples of these include kneaders and double tube heat exchangers.
  • a tubular evaporator that forms at least one of a wavy flow, a slag flow, an annular flow, and a spray flow is particularly preferable.
  • An apparatus in which the flow state is formed by a gas generated inside the evaporation apparatus is most preferable, and for example, a double tube heat exchanger or the like is suitably used.
  • the polymeric MDI based polyurea compound 12.83g of a brown solid was obtained 97.9% yield in dried under reduced pressure.
  • the obtained polymeric MDI-based polyurea compound swelled in DMF, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMA), and did not dissolve in organic solvents such as methanol and chloroform.
  • Decomposition ratio (%) was defined as the weight reduction rate from the charged amount.
  • Table 1 Methanol insoluble matter (filtered material) (brown powder) was subjected to FT-IR measurement (FIG. 1), and no significant difference was found from the chart of the polymeric MDI-based polyurea compound (brown solid) before decomposition.
  • the component soluble in methanol obtained by concentrating using a rotary evaporator was a brown viscous substance.
  • the substance could be identified as polymethylene polyphenyl polyamine (PMDA).
  • the weight loss temperature of the polymeric MDI-based polyurea compound measured using a thermogravimetric loss (TGA) measuring device is 296.6 ° C., 10% weight loss (T d10 ) of 5% weight loss (T d5 ). Was 320.5 ° C. Similar results were obtained for the methanol-insoluble component obtained after the decomposition test.
  • FT-IR measurement conditions Measuring instrument: FTS3000 type FT-IR measuring device (manufactured by Bio-Rad) Measurement method: KBr method detector: MCT Measurement range: 400 to 4000 cm -1 Sensitivity: 2 Resolution: 4cm -1 Integration count: 32
  • Thermogravimetric loss (TGA) measurement conditions Measuring instrument: Thermo Plus station and TG8120 (manufactured by Rigaku Corporation) Standard sample: Alumina (Al 2 O 3 ) Temperature range: 30-450 ° C Temperature increase rate: 10 ° C./min Nitrogen flow rate: 20 ml / min
  • Comparative Example 3 without water addition
  • Examples 3, 6 to 8 water addition amount (ml) 10, 20, 40, 80) in Table 1 were reacted at a temperature of 190 ° C. and a pressure of 7.3 MPa for 2 hours.
  • FIG. 3 shows the influence of the amount of water added on the decomposition rate of the polymeric MDI-based polyurea compound. In Comparative Example 3 (without addition of water), it is hardly decomposed, and when 20 to 40 ml of water is added, it is almost completely decomposed.
  • the degradation rate decreased when the amount of water added was 10 ml or less, or 40 ml or more.
  • the amount of water is too small, the diffusion of water into the polymeric MDI-based polyurea compound becomes insufficient, and when there is too much water, the diffusion of carbon dioxide becomes insufficient.
  • FIG. 4 shows a graph with the vertical axis representing the decomposition rate and the horizontal axis representing the temperature for Comparative Example 1 and Examples 1 and 3 in Table 1.
  • the weight loss rate at 120 ° C. was 6.8.
  • the decomposition rate increased remarkably with heating. From FIG. 4, the decomposition reaction of the polymeric MDI-based polyurea compound is accelerated by heating.
  • FIG. 5 shows a graph in which the vertical axis represents the decomposition rate and the horizontal axis represents the pressure based on Comparative Example 2 and Examples 2 to 5 in Table 1. This shows the weight loss rate under various pressures at 190 ° C., 20 ml of water, and reaction time of 2 hours. As the pressure increased, the decomposition rate also increased. The decomposition rate was close to 100% at 7.4 to 9.2 MPa, but the decomposition rate decreased to 89.2% at 11.8 MPa. This is because when the pressure is low, carbon dioxide does not sufficiently permeate the polymeric MDI-based polyurea compound, and when the pressure is high, water does not sufficiently permeate the polymeric MDI-based polyurea compound. It is done.
  • 2 is an FT-IR spectrum of a polymeric MDI-based polyurea compound before decomposition and a filtrate after decomposition in Example 1.
  • 1 is a 1 H-NMR chart of a deuterated chloroform (CDCl 3 ) soluble material. This is the decomposition result of the polymeric MDI-based polyurea compound when the amount of water added was changed under a constant temperature (190 ° C.), a substantially constant pressure (7.0 to 7.4 MPa), and a reaction time of 2 hours. This is a result of decomposition of a polymeric MDI-based polyurea compound when the temperature was changed under a substantially constant pressure (7.2 to 7.4 MPa), a constant amount of water added (20 ml), and a reaction time of 2 hours. It is the decomposition result of a polymeric MDI type
  • FIG. 2 FT-IR chart of a polymeric MDI-based polyurea compound before decomposition. 2. : FT-IR chart of the filtrate after decomposition.
  • a is a hydrogen peak of a methylene group adjacent to the amino group.
  • b A hydrogen peak of a methylene group adjacent to a methyl group.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de décomposition de composés de polyurée issus de polyméthylène-polyphénylène polyisocyanate (MDI polymère), dans lequel un polyméthylène polyphényl polyamine réutilisable (PMDA) peut être récupéré à partir d'un reste de polyurée qui est généré comme sous-produit lorsque le MDI polymère est obtenu et qui était mis au rebut de façon inévitable jusqu'ici, sans ajouter un accélérateur d'hydrolyse tel qu'un alcali. Le procédé ne fait pas naître de problème concernant une corrosion du réacteur. Le procédé de décomposition des composés de polyurée issus de MDI polymère est caractérisé par le fait que les composés de polyurée issus de MDI polymère sont hydrolysés en dioxyde de carbone supercritique ou sous-critique.
PCT/JP2010/002350 2009-04-28 2010-03-31 Procédé de décomposition d'un composé de polyurée issu d'un polyméthylène-polyphénylène polyisocyanate WO2010125743A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009109835A JP2010254924A (ja) 2009-04-28 2009-04-28 ポリメチレンポリフェニレンポリイソシアネート系ポリウレア化合物の分解処理方法
JP2009-109835 2009-04-28

Publications (1)

Publication Number Publication Date
WO2010125743A1 true WO2010125743A1 (fr) 2010-11-04

Family

ID=43031903

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/002350 WO2010125743A1 (fr) 2009-04-28 2010-03-31 Procédé de décomposition d'un composé de polyurée issu d'un polyméthylène-polyphénylène polyisocyanate

Country Status (2)

Country Link
JP (1) JP2010254924A (fr)
WO (1) WO2010125743A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192495A (ja) * 2000-01-06 2001-07-17 Chubu Electric Power Co Inc 架橋ポリオレフィンの再生方法
WO2003035592A1 (fr) * 2001-10-26 2003-05-01 Teijin Limited Procede de depolymerisation de polycarbonate aromatique
JP2004043744A (ja) * 2002-07-16 2004-02-12 Nippon Polyurethane Ind Co Ltd ポリメチレンポリフェニルポリイソシアネートの製造方法
JP2005082710A (ja) * 2003-09-09 2005-03-31 Keio Gijuku 超臨界流体を用いるポリエステル、ポリカーボネート又はポリ乳酸の連続解重合方法、及び連続解重合装置
JP2006248998A (ja) * 2005-03-10 2006-09-21 Mitsui Chemicals Polyurethanes Inc ポリイソシアネートの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192495A (ja) * 2000-01-06 2001-07-17 Chubu Electric Power Co Inc 架橋ポリオレフィンの再生方法
WO2003035592A1 (fr) * 2001-10-26 2003-05-01 Teijin Limited Procede de depolymerisation de polycarbonate aromatique
JP2004043744A (ja) * 2002-07-16 2004-02-12 Nippon Polyurethane Ind Co Ltd ポリメチレンポリフェニルポリイソシアネートの製造方法
JP2005082710A (ja) * 2003-09-09 2005-03-31 Keio Gijuku 超臨界流体を用いるポリエステル、ポリカーボネート又はポリ乳酸の連続解重合方法、及び連続解重合装置
JP2006248998A (ja) * 2005-03-10 2006-09-21 Mitsui Chemicals Polyurethanes Inc ポリイソシアネートの製造方法

Also Published As

Publication number Publication date
JP2010254924A (ja) 2010-11-11

Similar Documents

Publication Publication Date Title
CN109748822B (zh) 一种制备异氰酸酯单体的方法和系统
JP6144204B2 (ja) トルエンジイソシアネートの合成工程から排出されるタール廃棄物残渣からのトルエンジアミンの回収
KR101205858B1 (ko) 폐폴리우레탄으로부터 글리콜 해중합법을 이용한 폴리올의 제조방법
JP2002518369A (ja) トリレンジイソシアネートの合成で生成する蒸留残渣の後処理
Pan et al. High‐performance segmented polyurea by transesterification of diphenyl carbonates with aliphatic diamines
US20100324336A1 (en) Process for the production of aromatic amines
Liu et al. Degradation process investigation of thermoplastic polyurethane elastomer in supercritical methanol
KR20100082831A (ko) 이소시아네이트의 제조 방법
JP4096080B2 (ja) イソシアナート基とウレタン基とを含むプレポリマーの製造方法
CN103435504A (zh) 一种可降解伯胺固化剂的制备方法
CN108623799A (zh) 一种聚碳酸酯的制备方法
WO2010125743A1 (fr) Procédé de décomposition d'un composé de polyurée issu d'un polyméthylène-polyphénylène polyisocyanate
WO2010103720A1 (fr) Procédé de décomposition de composés polyurées à base de diisocyanate de tolylène
WO2010023922A1 (fr) Procédé pour la décomposition de composés de type polyurées de diisocyanate d’hexaméthylène
JP5240678B2 (ja) ウレア化合物の分解処理方法
JP4112750B2 (ja) 固体残さ分解方法
JP2004262835A (ja) 芳香族イソシアネートの製造方法
EP3572397B1 (fr) Procédé de production de n-(alpha-hydroxyéthyl)formamide et procédé de production de n-vinylformamide
WO2009024407A1 (fr) Procédé de préparation de compositions de polyisocyanate polyaromatique
Wang et al. The preparation of hybrid trimer by cyclo-oligomerization of TDI and HDI and its curing process with polyols to form elastic PU coating
JP2006069941A (ja) イソシアネート系化合物の分解回収方法
JP6669159B2 (ja) ジアミン化合物及びその中間体の製造方法
RU2479599C1 (ru) Способ получения фторсодержащего форполимера с изоцианатными группами
TW202214735A (zh) 源自回收寶特瓶之熱可塑性聚氨酯、其製備配方和製造方法
CN112384496A (zh) 从蒸馏残余物中回收二异氰酸酯的方法

Legal Events

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

Ref document number: 10769445

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10769445

Country of ref document: EP

Kind code of ref document: A1