CN112280095A - Method for recycling waste polyurethane - Google Patents
Method for recycling waste polyurethane Download PDFInfo
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- CN112280095A CN112280095A CN202011158031.1A CN202011158031A CN112280095A CN 112280095 A CN112280095 A CN 112280095A CN 202011158031 A CN202011158031 A CN 202011158031A CN 112280095 A CN112280095 A CN 112280095A
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- polyurethane
- swelling
- solvent
- dissolving
- waste polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 107
- 239000004814 polyurethane Substances 0.000 title claims abstract description 107
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004064 recycling Methods 0.000 title claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 78
- 230000008961 swelling Effects 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 14
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 11
- 239000011496 polyurethane foam Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- 238000004381 surface treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002657 fibrous material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000002861 polymer material Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000002895 organic esters Chemical class 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000008204 material by function Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 45
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 36
- 239000002245 particle Substances 0.000 description 16
- 238000010008 shearing Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000002203 pretreatment Methods 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007777 multifunctional material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
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- 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
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
- C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- 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
- C08J2375/04—Polyurethanes
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- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Sustainable Development (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a method for recycling waste polyurethane, which comprises the steps of crushing the waste polyurethane, putting the pretreated polyurethane into a swelling and dissolving solvent for swelling and dissolving, removing the swelling and dissolving solvent and preparing the polyurethane after removing the swelling and dissolving solvent into functional materials with different utilization values. The method provided by the invention realizes the recovery of the waste polyurethane at normal pressure and low temperature, and the waste polyurethane is prepared into a new product with higher utilization value, the whole process flow is simple, the condition is mild, the energy consumption is low, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for recycling waste polyurethane.
Background
The polyurethane is a polymer with low price, simple synthesis process, and excellent and adjustable mechanical property and processing property. The polymers have wide hardness and density, and are widely applied to various fields of rail transit, chemical equipment, light-weight engineering, wind power energy, green buildings, biological medicine and the like. In recent years, the industrial production technology of polyurethane in China has been rapidly developed, and the production scale is remarkably enlarged, however, with the mass production and application of these materials, a large amount of polyurethane solid waste is inevitably generated, and is often discarded on land or in the sea. Polyurethane polymers are difficult to biodegrade due to their good chemical stability, posing a serious threat to the ecological environment. Direct incineration of these substances releases many harmful chemicals such as isocyanates, hydrocyanic acid and dioxins. In addition, the raw materials for synthesizing the polymer materials are all from limited petroleum resources, so that the polymer materials are potential high-value secondary resources, and if the polymer materials are not recycled, not only can heavy burden be brought to the environment, but also huge waste of resources can be caused. Therefore, how to recycle the high-value organic solid wastes efficiently, simply and greenly has become a problem to be solved in the present society.
At present, the recovery and treatment technologies for waste polyurethane at home and abroad mainly comprise a mechanical recovery method, a biological method, an energy recovery method, a chemical method and the like. Biodegradation methods are often time-consuming, costly and susceptible to environmental influences, making industrial processing difficult to achieve. Mechanical recycling is to pulverize waste polyurethane and use the pulverized waste polyurethane as a filler of a composite material, but the mechanical recycling often causes the quality of the material to be reduced. Compared with heat recovery, the chemical method is a very promising method for recovering waste high polymer resin materials, but a catalyst with stronger corrosivity and high reaction temperature are often adopted in the chemical reaction, or high pressure and long reaction time are needed, and particularly, the separation of products and reaction solution is difficult and complicated due to mutual solubility, the technical cost is high, and the industrial production is not facilitated. Therefore, the method for realizing low energy consumption, quick recovery and high-value utilization of polyurethane is provided, and has great significance for popularizing the industrial production of degrading and recovering the waste polyurethane.
Disclosure of Invention
The invention aims to provide a method for recycling waste polyurethane, which adopts a green low-boiling point solvent to carry out swelling dissolution on the waste polyurethane so as to realize high value-added recycling of the waste polyurethane. The polyurethane can be easily prepared into various functional materials without damaging the structure, and the used swelling and dissolving solvent can be recycled, so that the polyurethane can be recycled and utilized at low cost and low energy consumption, and the method is suitable for industrial production.
The invention is realized by the following technical scheme:
a method for recycling waste polyurethane is characterized by comprising the following steps:
step 1: carrying out crushing pretreatment on waste polyurethane to prepare a polyurethane sample with a certain size;
step 2: putting the pretreated polyurethane sample into a swelling and dissolving solvent, and swelling and dissolving for 0.1-100 h at the temperature of 20-200 ℃;
and step 3: separating the swelling and dissolving solvent from the polyurethane sample treated in the step 2 at the temperature of between 20 and 200 ℃, condensing or purifying the swelling and dissolving solvent obtained by separation, and returning the condensed swelling and dissolving solvent to the step 2 for recycling;
and 4, step 4: preparing a functional material by using the polyurethane obtained in the step 3 after the swelling solvent is removed; the functional material is prepared into a solid surface hydrophobic material, or a polyurethane foam material, or is mixed with a characteristic powder material and/or a fiber material to prepare a composite material.
Further, the method for pretreating the waste polyurethane comprises the step of preparing a polyurethane sample with the size of 0.5-10 cm from the waste thermoplastic polyurethane through mechanical crushing treatment.
Further, the swelling and dissolving solvent is at least one of organic acid, organic ester, organic amine, organic ketone and halogenated hydrocarbon solvent.
Further, in the step 2, the mass ratio of the waste polyurethane to the swelling solvent is 1 (0.5-100).
Further, in the step 3, the swelling solvent is separated by extracting the swelling solvent with an extraction solvent, wherein the extraction solvent comprises at least one of water and alcohol; the alcohol is an alcohol solvent with a boiling point lower than 200 ℃.
Further, the preparation method of the solid surface hydrophobic material comprises the step of carrying out surface treatment on the solid material by using polyurethane after removing the swelling and dissolving solvent to prepare the solid surface hydrophobic material containing the solid surface hydrophobic film.
Further, the solid material may be any one of a glass material, a polymer material, and a steel material.
Further, the preparation method of the polyurethane foam material comprises the steps of putting the polyurethane after swelling and dissolving into a mould, and heating to remove the swelling and dissolving solvent to prepare the polyurethane foam.
Further, the preparation method of the composite material containing the characteristic powder material and/or the fiber material comprises the steps of mixing the polyurethane after swelling and dissolving with the characteristic powder material and the fiber material, and removing the swelling and dissolving solvent to prepare the composite material.
Further, the waste polyurethane comprises at least one of thermoplastic polyurethane foam, polyurethane elastomer and polyurethane-containing composite or mixed material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the method can easily realize the recycling of the waste polyurethane at normal temperature or lower temperature, and the adopted solvent can be recycled and reused, so that the method is suitable for industrial production; the recycled polyurethane is prepared into a multifunctional material, so that the high-value utilization of the multifunctional material is realized.
The solvent adopted by the invention is a series of solvents with lower boiling points, is green and environment-friendly, is low in price and easy to obtain, and has the advantages of excellent swelling and dissolving properties, narrow boiling point range, low viscosity, high flash point, higher evaporation speed and the like; further provides a solvent separation method with simple separation operation, which can realize high-efficiency swelling and dissolution of waste polyurethane and quick recovery of solvent under low energy consumption. The method has the advantages of simple process, mild conditions and low energy consumption for recovery, greatly reduces the cost for recovering and treating the waste polyurethane, and is easy to realize the industrial production of the recovered waste polyurethane.
Detailed Description
The following examples are given to illustrate preferred embodiments of the present invention, it should be noted that the following examples are not to be construed as limiting the scope of the present invention, and that those skilled in the art may make insubstantial modifications and adaptations of the present invention based on the present disclosure. Any simple modifications and equivalent changes made to the following embodiments in accordance with the technical idea of the present invention fall within the scope of the present invention.
Example 1
Shearing the waste polyurethane elastomer into a particle sample with the size of 0.5cm to obtain a pre-treatment sample; putting 1g of the pretreated polyurethane sample into 50g of chloroform solvent, and stirring at normal temperature to swell and dissolve for 50 h; carrying out surface treatment on the glass material by using the swelled and dissolved polyurethane, heating the glass material by using air, and evaporating a chloroform solvent at the temperature of 35 ℃ to prepare a modified glass material with a hydrophobic surface; the evaporated chloroform solvent is condensed and recycled.
Example 2
Shearing waste polyurethane into a particle sample with the size of 5cm to obtain a pretreatment sample; putting 10g of the pretreated polyurethane sample into 5g of acetic acid solvent, and then stirring, swelling and dissolving for 100 hours at 25 ℃; carrying out surface treatment on the iron plate material by using the polyurethane which is swelled and dissolved, heating by using air, and evaporating an acetic acid solvent at the temperature of 85 ℃ to prepare the iron plate material with the hydrophobically modified surface; the distilled acetic acid solvent is recycled after condensation.
Example 3
Shearing the waste polyurethane elastomer into a particle sample with the size of 10cm to obtain a pre-treatment sample; putting 5g of the pretreated polyurethane sample into 500g of formic acid solvent, and then stirring, swelling and dissolving for 3h at the temperature of 60 ℃; carrying out surface treatment on the resin material by using the swelled and dissolved polyurethane, heating by using air, and evaporating the solvent at 50 ℃ to prepare a resin material with the surface subjected to hydrophobic modification; the distilled formic acid solvent is recycled after condensation.
Example 4
Shearing waste polyurethane foam into a particle sample with the size of 1cm to obtain a pretreatment sample; putting 10g of the pretreated polyurethane sample into 20g of a mixed solvent of chloroform and acetic acid, and stirring, swelling and dissolving for 8 hours at the temperature of 50 ℃; carrying out surface treatment on the glass material by using the swelled and dissolved polyurethane, and steaming the solvent at 50 ℃ by adopting microwave heating to prepare the glass material with the surface subjected to hydrophobic modification; the distilled mixed solvent is condensed and recycled.
Example 5
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 10g of dichloromethane solvent, and stirring, swelling and dissolving for 5 hours at the temperature of 30 ℃; putting the swelled and dissolved polyurethane into a mold, and quickly evaporating a dichloromethane solvent at the temperature of 55 ℃ by microwave heating to prepare polyurethane foam; the distilled dichloromethane solvent is recovered and reused after condensation.
Example 6
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 50g of a mixed solvent of acetone and chloroform, and swelling and dissolving for 100 hours at normal temperature; putting the swelled and dissolved polyurethane into a grinding tool, and quickly removing acetone and chloroform solvent at 50 ℃ by microwave heating to prepare polyurethane foam; the distilled mixed solvent is condensed and recycled.
Example 7
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 50g of diethylenetriamine solvent, and stirring, swelling and dissolving for 0.1h at the heating temperature of 200 ℃; carrying out surface treatment on the glass material by using the dissolved polyurethane, and dissolving and extracting diethylenetriamine in the dissolved polyurethane by using an aqueous solvent to prepare a modified glass material with a hydrophobic surface; and purifying the extracted mixed solution and recycling.
Example 8
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 40g of a mixed solvent of ethyl acetate and acetic acid, and stirring, swelling and dissolving for 8 hours at a heating temperature of 50 ℃; mixing the dissolved polyurethane with the recovered glass fiber, and dissolving and extracting acetic acid and ethyl acetate in the dissolved polyurethane by adopting an aqueous solvent to prepare a polyurethane composite material; and purifying the extracted mixed solution and recycling.
Example 9
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 40g of ethyl acetate and acetic acid solvent, and stirring, swelling and dissolving for 10 hours at the heating temperature of 40 ℃; mixing the dissolved polyurethane with the recovered carbon fibers, and dissolving and extracting ethyl acetate and acetic acid in the dissolved polyurethane by adopting an aqueous solvent to prepare a polyurethane composite material; and purifying the extracted mixed solution and recycling.
Example 10
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 40g of acetic acid solvent, and stirring, swelling and dissolving for 10 hours at the heating temperature of 80 ℃; mixing the dissolved polyurethane and the conductive carbon powder, and dissolving and extracting acetic acid in the dissolved polyurethane by adopting an ethanol solvent to prepare the pressure-sensitive material; and purifying the extracted mixed solution and recycling.
Example 11
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 50g of chloroform solvent, and stirring, swelling and dissolving for 0.5h at the heating temperature of 60 ℃; mixing the dissolved polyurethane with the recovered glass fiber, and quickly removing a chloroform solvent at the temperature of 45 ℃ by microwave heating to prepare a polyurethane composite material; the evaporated chloroform solvent is condensed and recycled.
Example 12
Shearing waste polyurethane foam into a particle sample with the size of 1cm to obtain a pretreatment sample; putting 10g of the pretreated polyurethane sample into 10g of chloroform solvent, and soaking for 48h at normal temperature; then stirring at the normal temperature of 20 ℃ for swelling and dissolving for 3h, carrying out surface treatment on the glass by using the swollen and dissolved polyurethane, heating by air, and evaporating a chloroform solvent at the temperature of 40 ℃ to prepare a glass material with the surface subjected to hydrophobic modification; the evaporated chloroform solvent is condensed and recycled.
Example 13
Shearing the waste polyurethane composite material into a particle sample with the size of 2cm to obtain a pretreatment sample; putting 10g of the pretreated polyurethane sample into 20g of acetic acid solvent, and soaking for 72h at normal temperature; then stirring and swelling for dissolving for 5h under the condition of conventional heating at 65 ℃, and removing insoluble solid fiber parts; carrying out surface treatment on the glass material by using the dissolved polyurethane, heating the glass material by using air, and removing an acetic acid solvent at 85 ℃ to prepare the glass material with the surface subjected to hydrophobic modification; the removed acetic acid solvent is condensed and recycled.
Example 14
Shearing a waste polyurethane material into a particle sample with the size of 1cm to obtain a pretreatment sample; 1g of the pretreated polyurethane sample is put into 5g of chloroform solvent and soaked for 72 hours at normal temperature; then stirring and swelling for dissolving for 5 hours under the condition of conventional heating at 50 ℃; putting the swelled and dissolved polyurethane into a plane grinding tool, heating by microwave for 0.1h at 65 ℃ to remove the chloroform solvent, and preparing a porous polyurethane film; the removed chloroform solvent is condensed and recycled.
Example 15
Shearing the waste polyurethane elastomer into a particle sample with the size of 1cm to obtain a pre-treatment sample; 1g of the pretreated polyurethane sample is put into 20g of chloroform solvent and soaked for 100 hours at normal temperature; then stirring at normal temperature to swell and dissolve for 5h, keeping the temperature of the swelled and dissolved polyurethane constant at 20 ℃ for 100h, and removing the chloroform solvent to obtain a high-elasticity polyurethane film; the removed chloroform solvent is condensed and recycled.
Example 16
Shearing a mixture of waste polyurethane foam and waste polyurethane elastomer to obtain a particle sample with the size of 1cm, so as to obtain a pre-treatment sample; putting 10g of the pretreated polyurethane sample into 20g of acetic acid solvent, and soaking for 100h at normal temperature; then stirred and swelled for dissolving for 5h under the condition of conventional heating at 80 ℃. Putting the polyurethane after swelling and dissolving into a plane grinding tool, heating for 0.5h at the temperature of 150 ℃ by microwave heating to remove the acetic acid solvent, and preparing a high-elasticity polyurethane film; the removed acetic acid solvent is condensed and recycled.
Claims (10)
1. A method for recycling waste polyurethane is characterized by comprising the following steps:
step 1: carrying out crushing pretreatment on waste polyurethane to prepare a polyurethane sample with a certain size;
step 2: putting the pretreated polyurethane sample into a swelling and dissolving solvent, and swelling and dissolving for 0.1-100 h at the temperature of 20-200 ℃;
and step 3: separating the swelling and dissolving solvent from the polyurethane sample treated in the step 2 at the temperature of between 20 and 200 ℃, condensing or purifying the swelling and dissolving solvent obtained by separation, and returning the condensed swelling and dissolving solvent to the step 2 for recycling;
and 4, step 4: preparing a functional material by using the polyurethane obtained in the step 3 after the swelling solvent is removed; the functional material is prepared into a solid surface hydrophobic material or a polyurethane foam material, or is mixed with a characteristic powder material and/or a fiber material to prepare a composite material.
2. The method for recycling waste polyurethane according to claim 1, wherein the method for pretreating waste polyurethane comprises the step of preparing a polyurethane sample with the size of 0.5 cm-10 cm from waste thermoplastic polyurethane through mechanical crushing treatment.
3. The method for recycling waste polyurethane according to claim 1, wherein the swelling solvent is at least one of organic acid, organic ester, organic amine, organic ketone and halogenated hydrocarbon solvent.
4. The method for recycling waste polyurethane according to claim 1, wherein in the step 2, the mass ratio of the waste polyurethane to the swelling solvent is 1 (0.5-100).
5. The method for recycling waste polyurethane according to claim 1, wherein in the step 3, the swelling solvent is separated by extracting the swelling solvent with an extraction solvent; the extraction solvent comprises at least one of water and alcohol; the alcohol is an alcohol solvent with a boiling point lower than 200 ℃.
6. The method for recycling waste polyurethane as claimed in any one of claims 1 to 5, wherein the solid surface hydrophobic material is prepared by performing surface treatment on a solid material with polyurethane after removing a swelling and dissolving solvent to obtain a solid surface hydrophobic material containing a solid surface hydrophobic film.
7. The method for recycling waste polyurethane according to claim 6, wherein the solid material comprises any one of glass material, polymer material and steel material.
8. The method for recycling waste polyurethane according to any one of claims 1 to 5, wherein the polyurethane foam material is prepared by placing the polyurethane after swelling and dissolving in a mold, and heating to remove the swelling and dissolving solvent to prepare the polyurethane foam.
9. The method for recycling waste polyurethane according to any one of claims 1 to 5, wherein the composite material containing the characteristic powder material and/or the fiber material is prepared by mixing the polyurethane after swelling and dissolving with the characteristic powder material and the fiber material, and removing the swelling and dissolving solvent.
10. The method for recycling waste polyurethane according to any one of claims 1 to 5, wherein the waste polyurethane comprises at least one of thermoplastic polyurethane foam, polyurethane elastomer and polyurethane-containing composite or mixed material.
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| US3954681A (en) * | 1973-05-25 | 1976-05-04 | Whittaker Corporation | Method of reclaiming cured polyurethane elastomers |
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| US3954681A (en) * | 1973-05-25 | 1976-05-04 | Whittaker Corporation | Method of reclaiming cured polyurethane elastomers |
| US20050096399A1 (en) * | 2003-10-30 | 2005-05-05 | Mobius Technologies, Inc. | Method for recycling polyurethane and a composition comprising recycled polyurethane |
| CN101701073A (en) * | 2009-11-05 | 2010-05-05 | 吉林大学 | Method for functionally remolding waste polystyrene |
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