CN110105621B - Directional degradation method of waste polyurethane material - Google Patents
Directional degradation method of waste polyurethane material Download PDFInfo
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- CN110105621B CN110105621B CN201910346481.4A CN201910346481A CN110105621B CN 110105621 B CN110105621 B CN 110105621B CN 201910346481 A CN201910346481 A CN 201910346481A CN 110105621 B CN110105621 B CN 110105621B
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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- 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
- C08J11/18—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 organic material
- C08J11/28—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 organic material by treatment with organic compounds containing nitrogen, sulfur or phosphorus
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- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention belongs to the field of organic solid waste recycling treatment, and particularly relates to a directional degradation method of a waste polyurethane material. The invention mainly solves the technical problems of low catalytic efficiency, difficult selective bond breaking, difficult product separation after the reaction is finished and incapability of recycling high value-added chemicals. The method comprises the steps of mixing a waste polyurethane material, an organic amine or amide catalyst and a reaction solvent to form a degradation system, adding water after the reaction degradation is finished and cooling, filtering, washing a filter cake and drying to obtain aromatic polyamine substances; extracting and layering the filtrate by using an organic solvent, and drying an organic solvent phase obtained by layering to obtain a long-chain polyether polyol substance; the water phase obtained by layering can be repeatedly used for degrading polyurethane. The method can efficiently activate and degrade urethane bonds and urea bonds in molecules, has no obvious catalytic activity on ether bonds of polyether polyol parts and carbon-carbon bond structures in the molecules, and can separate aromatic polyamine substances and polyether polyol substances with high added values through simple treatment.
Description
Technical Field
The invention belongs to the field of organic solid waste recycling treatment, and particularly relates to a directional degradation method of a waste polyurethane material.
Technical Field
Polyurethane is a high molecular material with huge yield, is widely applied to various fields of life and production due to excellent performance, and is important for harmless and resource treatment of polyurethane wastes due to huge waste yield. For example, the refrigerator heat insulation material is hard polyurethane foam plastic, and thousands of refrigerators are scrapped every year in the peak period of scrapping of waste refrigerators in China. The mass of the hard polyurethane foam accounts for 9 percent of the total mass of the refrigerator, and most of wastes are buried or incinerated, so that not only are a great amount of recyclable resources wasted, but also land waste and atmospheric pollution are caused. Therefore, the recycling of polyurethane becomes one of the great problems which need to be solved urgently in the polyurethane industry, the waste polyurethane is recycled, the environmental pollution is reduced, and the production cost of a new product is reduced, so that the method has practical significance.
Polyether polyol polyurethane is one of polyurethane materials, is mainly applied to refrigerator heat insulation materials, fiber products and sealing materials, is a molecular fragment formed by combining polyether polyol and polyisocyanate (such as TDI or MDI) and can form cross-linked reticular macromolecules through chain extension, and the larger the cross-linking degree is, the more rigorous the conditions required by degradation are. Along with the increase of the crosslinking degree, the steric hindrance is gradually increased, and the solvent molecules are difficult to enter the body, so the solvent molecules cannot bring the degradation agent into the crosslinking molecules, and the degradation is difficult to carry out. The products obtained by the existing degradation mode are not single, the separation is difficult, and the industrialization degree and the utilization degree are not high.
Currently, there are three main methods for recycling polyurethane: physical, chemical, energy methods. There have been many reports and practical techniques for physical processes, and the PU recovered by the process has poor properties and is only suitable for low-grade products. Energy recovery is the recovery of heat by incineration of waste, which causes secondary pollution and is essentially unused. The chemical methods mainly include alcoholysis, hydrolysis, aminolysis and alkaline hydrolysis, and among them, the most commonly used are ethylene glycol decomposition and amine decomposition. The method has the following disadvantages: the urethane resin has chemical bonds such as urethane bonds, ether bonds, ester bonds, and urea bonds, and the diol or amine compound easily cleaves the urethane bonds to form a liquid by an exchange reaction. At this time, the diols and amines used as the decomposing agents form new urethane bonds and urea bonds, and enter into the liquid decomposed product as urethane and urea derivatives, and the products cannot be decomposed to obtain the aromatic polyamine compounds which are the starting materials of the polyurethane resin and are intermediate products of polyether or polyester polyol and polyisocyanate, and recycling is difficult, so that the application of the related art is limited. For example, the national patent publications with publication numbers CN108623784A, CN105801904A, and CN107245162A disclose that small molecular diols are used as degradation agents, acetates are used as catalysts, and the reaction is carried out at 180-: polyurethane sole stock solution, floor primer and plastic track. The reaction temperature of the methods is high, and the degraded products are not easy to separate and can only be directly utilized to be made into some low-grade products.
The polyether polyol polyurethane contains a soft chain formed by polyether polyol and a hard chain formed by aromatic isocyanate in a molecule, ether bonds, urethane bonds and urea bonds exist in the molecule, and if the urethane bonds and the urea bonds in the molecule can be selectively opened under the action of a certain catalyst, polyether polyol and aromatic diamine compounds with high added values are recovered, so that the polyether polyol and the aromatic diamine compound have important value undoubtedly. The national invention patents with publication numbers CN106519292A and CN106565238A disclose a method for recovering high value-added chemicals by catalyzing selective opening of urethane bonds and urea bonds in polyurethane with coordinated unsaturated metal ions, which requires a large amount of metal salts and is easy to cause side reactions in carbon-carbon bond structures of part of compounds.
Disclosure of Invention
The invention aims to provide an economical and efficient method for selectively opening urethane bonds and urea bonds in polyether polyol polyurethane to recover high value-added chemicals, and degradation products such as polyether polyol, aromatic polyamine compounds and the like can be recovered without using metal salts as catalysts.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a directional degradation method of waste polyurethane materials comprises the following steps: mixing the waste polyurethane material with organic amine or amide catalyst and reaction solvent to form a degradation system, adding water after the reaction degradation is finished and cooling, filtering, washing filter cakes and drying to obtain aromatic polyamine substances; extracting and layering the filtrate by using an organic solvent, and drying an organic solvent phase obtained by layering to obtain a long-chain polyether polyol substance; the water phase obtained by layering can be repeatedly used for degrading polyurethane. The method can efficiently activate and degrade urethane bonds and urea bonds in molecules, has no obvious catalytic activity on ether bonds of polyether polyol parts and carbon-carbon bond structures in the molecules, and can separate aromatic polyamine substances and polyether polyol substances with high added values through simple treatment.
Further, the organic amine or amide catalyst is a small molecular organic amine compound, including any one of urea, thiourea, ethylenediamine, hexamethylenediamine, 1, 2-propanediamine, 1, 4-butanediamine, formamide, acetamide, propionamide, N-dimethylformamide, succinimide, piperazine, or 1, 4-dimethylpiperazine. The organic amine or amide catalysts are small in size, can easily enter a polyurethane body, can efficiently open a urethane bond and a urea bond, and are good in selectivity, and the generated product is definite in structure.
Still further, the reaction solvent is a polar solvent or an aqueous solution thereof, and may be an aqueous solution of low molecular weight alcohols or ketones and low molecular weight alcohols or ketones, including: one or more of methanol, ethanol, propanol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, glycerol, acetone, methyl ethyl ketone, and aqueous solutions thereof. The solvent can ensure the dissolution of the organic amine or amide catalyst, realizes the free diffusion of the organic amine or amide catalyst in the polyurethane material, and is beneficial to the subsequent product separation and the recovery process of a degradation system when being cooperated with the organic amine or amide catalyst to catalyze the activation and degradation of a urethane bond and a urea bond.
Further, the mass fraction of the aqueous solution of the reaction solvent is 20% to 100%. Because the aromatic polyamine compound is insoluble in water, the polyamine compound can be directly separated out by adjusting the proportion of the polar solvent and the water, thereby directly obtaining the products such as the aromatic polyamine compound, the long-chain polyether polyol and the like.
Furthermore, the mass ratio of the waste polyurethane material, the organic amine or amide catalyst and the reaction solvent is 1: 0.01-2: 1-50. When the catalyst amount is higher than the ratio, a large amount of catalyst remains after the reaction is finished, and unnecessary waste is caused. In addition, the catalyst of organic diamine can form hydrogen bond with water and alcohol, so that more catalyst is mixed in the separated polyol, which is not beneficial to the separation; when the amount of the catalyst is less than the ratio, incomplete catalysis can be caused, and the catalytic effect is obviously reduced.
Furthermore, the temperature of the reaction degradation is 100-250 ℃, and the time of the reaction degradation is 1-12 h. When the reaction temperature is lower than 100 ℃, the reaction activity is lower, the reaction needs a long time to be carried out, and the efficiency is low; above 250 ℃, other side reactions occur, and the soft chain of polyether polyol is also damaged to a certain extent, so that the yield is reduced. At the temperature, the polyether polyol soft chain can be completely degraded and can be reserved.
Further, the aromatic polyamine substances are separated and dried at room temperature; and the long-chain polyether polyol substance is separated and dried at the temperature of 80-100 ℃. The aromatic polyamine substance can be combined with water and alcohol in a hydrogen bond mode due to the existence of amino, the interaction of the aromatic polyamine substance and the alcohol is enhanced along with the increase of temperature, and the aromatic polyamine compound is dried at room temperature to obtain a purer aromatic polyamine compound. The long-chain polyether polyol exists in the extracted organic solvent phase, the organic solvent can be evaporated and removed at the temperature, the long-chain alcohol is partially lost when the temperature is higher than 100 ℃, the evaporation rate of the organic solvent is slow when the temperature is lower than 80 ℃, and long time is needed for obtaining the pure long-chain alcohol.
Furthermore, the amount of water added into the reaction system is 2-10 times of that of the degradation system, the water is slowly added, and the reaction system is kept stand until the precipitation is completely separated out. The aromatic polyamine substances are insoluble in water, and are precipitated after water is added, and the precipitation process of the water is slow, so that the precipitation process contains many other impurities such as: urea and various alcohols cannot obtain relatively pure aromatic polyamine substances.
Furthermore, the extractant used in the extraction is an organic solvent, and comprises chloroform, ethyl acetate, toluene and petroleum ether. The extractant is immiscible with a reaction system, is easy to remove and has high extraction rate. Because the solubility of the long-chain alcohol in the extractant is higher than that of the reaction system, the extractant can effectively extract the polyether polyol from the reaction system.
Furthermore, the particle size of the waste polyurethane material is 0.01-1 cm. Sufficient crushing can increase the contact area of the powder and the degradation agent, so that the degradation is easier to carry out.
Compared with the prior art, the invention has the following advantages:
1. the solvent used in the invention has low cost and low boiling point, and can be separated and recycled;
2. the degradation agent used in the invention is a conventional catalyst, so the source is wide, the price is low, and the recovery cost can be further reduced;
3. the urea bond and the urethane bond can be selectively broken, the polyurethane is efficiently and directionally degraded, and the soft chain of the polyether polyol is reserved. Aromatic polyamine compounds and long-chain polyether polyol substances can be obtained by simple separation.
Drawings
FIG. 1 is a nuclear magnetic characterization map of aromatic polyamine substances, degradation products of examples 1 to 12 of the present invention;
FIG. 2 is nuclear magnetic spectrum of the degradation product, polyether polyol, of examples 1-4 of the present invention;
FIG. 3 is nuclear magnetic spectrum of the degradation product, polyether polyol, of examples 5-8 of the present invention;
FIG. 4 is nuclear magnetic spectrum of the degradation product, polyether polyol, of examples 9-12 of the present invention;
as can be seen from FIG. 1, the aromatic polyamine substance obtained after degradation has the following (MDI) structure:
as can be seen from FIG. 2, the polyether polyol substance obtained after degradation is poly-1, 2-propylene glycol polyether polyol, and has the following structure:
as can be seen from fig. 3, the polyether polyol substance obtained after degradation is polyethylene glycol polyether polyol, and has the following structure:
as can be seen from fig. 4, the polyether polyol substance obtained after degradation is polytetrahydrofuran polyether polyol, and has the following structure:
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The waste polyurethane material to be degraded in the embodiment is poly 1, 2-propylene glycol polyether polyurethane, and the specific structure is as follows:
mixing 0.4g of crushed waste polyurethane material with the particle size of 0.01cm, 0.004g of urea and 0.4g of 100% ethanol to form a 0.804g degradation system, reacting in a hydrothermal kettle at 100 ℃ for 12h, adding 8g of water into the reaction system after the reaction degradation is finished and cooling, standing after the precipitation is completed, filtering, washing a filter cake, and drying to obtain 0.13g of aromatic polyamine substance; extracting the filtrate with chloroform for layering, and drying the layered chloroform phase at 80 deg.C to obtain 0.25g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 2
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 1
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.05cm, 0.2g of piperazine and 4g of acetone with the mass fraction of 60% to form a 4.6g degradation system, reacting in a hydrothermal kettle at 140 ℃ for 8 hours, adding 20g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing a filter cake, and drying to obtain 0.11g of aromatic polyamine substance; extracting the filtrate with toluene for layering, and drying the layered toluene phase at 100 deg.C to obtain 0.29g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 3
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 1
Mixing 0.4g of crushed waste polyurethane material with the particle size of 1cm, 0.8g of 1, 4-dimethylpiperazine and 20g of 20% methanol by mass fraction to form a 21.2g degradation system, reacting in a hydrothermal kettle at 250 ℃ for 1h, adding 42.4g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing a filter cake, and drying to obtain 0.16g of aromatic polyamine substance; extracting the filtrate with petroleum ether for layering, and drying the layered petroleum ether phase at 85 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 4
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 1
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.2cm, 0.5g of 1, 4-dimethylpiperazine and the water recovered in the embodiment 3 to form a 45g degradation system, reacting in a hydrothermal kettle at 180 ℃ for 2h, adding 100g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after the precipitation is completed, washing and drying a filter cake to obtain 0.16g of aromatic polyamine substance; extracting the filtrate with ethyl acetate for layering, and drying the layered ethyl acetate phase at 80 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 5
The waste polyurethane material to be degraded in the embodiment is polyethylene glycol polyether polyurethane, and the specific structure is as follows:
mixing 0.4g of crushed waste polyurethane material with the particle size of 0.6cm, 0.3g of thiourea and 10g of ethylene glycol with the mass fraction of 70% to form a 10.7g degradation system, reacting in a hydrothermal kettle at 160 ℃ for 5 hours, adding 30g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing a filter cake, and drying to obtain 0.18g of aromatic polyamine substance; extracting the filtrate with chloroform for layering, and drying the layered chloroform phase at 80 deg.C to obtain 0.21g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 6
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 5
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.09cm, 0.2g of ethylenediamine and 5g of methyl ethyl ketone with the mass fraction of 80% to form a degradation system of 5.6g, reacting for 7 hours at 150 ℃ in a hydrothermal kettle, adding 15g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing a filter cake, and drying to obtain 0.11g of aromatic polyamine substance; extracting the filtrate with toluene for layering, and drying the layered toluene phase at 100 deg.C to obtain 0.27g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 7
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 5
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.3cm, 0.7g of formamide and 16g of propanol with the mass fraction of 70% to form a degradation system of 18.1g, reacting in a hydrothermal kettle at 200 ℃ for 1h, adding 50g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing a filter cake, and drying to obtain 0.16g of aromatic polyamine substance; extracting the filtrate with petroleum ether for layering, and drying the layered petroleum ether phase at 80 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 8
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 5
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.3cm, 0.5g of formamide and the water recovered in the embodiment 7 to form a 53g degradation system, reacting in a hydrothermal kettle at 190 ℃ for 2h, adding 130g of water into the reaction system after the reaction degradation is finished and cooling, standing after the precipitation is finished, filtering, washing a filter cake, and drying to obtain 0.2g of aromatic polyamine substance; extracting the filtrate with ethyl acetate for layering, and drying the layered ethyl acetate phase at 80 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 9
The waste polyurethane material to be degraded in the embodiment is polytetrahydrofuran polyether polyurethane, and the specific structure is as follows:
mixing 0.4g of crushed waste polyurethane material with the particle size of 0.7cm, 0.3g of adipamide and 10g of 1, 2-propanol with the mass fraction of 70% to form a 10.7g degradation system, reacting for 5 hours in a hydrothermal kettle at 170 ℃, adding 30g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after the precipitation is completed, washing and drying a filter cake to obtain 0.16g of aromatic polyamine substance; extracting the filtrate with chloroform for layering, and drying the layered chloroform phase at 80 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 10
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 9
Mixing 0.4g of crushed waste polyurethane material with the particle size of 0.4cm, 0.7g of propionamide and 16g of glycerol with the mass fraction of 90% to form a degradation system of 18.1g, reacting for 3 hours in a hydrothermal kettle at 180 ℃, adding 40g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after complete precipitation, washing and drying a filter cake to obtain 0.11g of aromatic polyamine substance; extracting the filtrate with petroleum ether for layering, and drying the layered petroleum ether phase at 80 deg.C to obtain 0.23g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 11
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 9
Mixing 0.4g of crushed waste polyurethane material with the particle size of 1cm, 0.2g of succinimide and 5g of 1, 3-propylene glycol with the mass fraction of 80% to form a degradation system of 5.6g, reacting in a hydrothermal kettle at 180 ℃ for 2 hours, adding 20g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after the precipitation is completed, washing and drying a filter cake to obtain 0.10g of aromatic polyamine substance; extracting the filtrate with toluene for layering, and drying the layered toluene phase at 100 deg.C to obtain 0.27g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
Example 12
The structure of the waste polyurethane material to be degraded in this embodiment is the same as that in embodiment 9
Mixing 0.4g of crushed waste polyurethane material with the particle size of 1cm, 0.5g of succinimide and the recovered water phase in the embodiment 11 to form a 22g degradation system, reacting in a hydrothermal kettle at 130 ℃ for 10h, adding 70g of water into the reaction system after the reaction degradation is finished and cooling, standing, filtering after the precipitation is finished, and washing and drying a filter cake to obtain 0.23g of aromatic polyamine substance; extracting the filtrate with ethyl acetate for layering, and drying the layered ethyl acetate phase at 80 deg.C to obtain 0.30g long chain polyether polyol; and recycling the water phase obtained by layering for degrading the polyurethane.
The catalyst in the above examples may also be: 1, 2-propane diamine, 1, 4-butane diamine, acetamide and N, N-dimethyl formamide.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A directional degradation method of waste polyurethane materials is characterized by comprising the following steps: the method comprises the following steps: mixing the waste polyurethane material with an amide catalyst and a reaction solvent to form a degradation system, adding water after the reaction degradation is finished and cooling, filtering, washing a filter cake and drying to obtain aromatic polyamine substances; extracting and layering the filtrate by using an organic solvent, and drying an organic solvent phase obtained by layering to obtain a long-chain polyether polyol substance; the water phase obtained by layering can be repeatedly used for degrading polyurethane; the mass fraction of the aqueous solution of the reaction solvent is 20% to 100%.
2. The method for directionally degrading the waste polyurethane material according to claim 1, wherein the method comprises the following steps: the amide catalyst comprises any one of urea, thiourea, formamide, acetamide, propionamide, N-dimethylformamide and succinimide.
3. The method for directionally degrading the waste polyurethane material according to claim 2, wherein: the reaction solvent is a polar solvent or an aqueous solution thereof, can be low molecular weight alcohols or ketones and low molecular weight alcohols or ketones aqueous solution, and comprises: one or more of methanol, ethanol, propanol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, glycerol, acetone, methyl ethyl ketone, and aqueous solutions thereof.
4. The method for directionally degrading the waste polyurethane material according to claim 3, wherein the method comprises the following steps: the mass ratio of the waste polyurethane material to the amide catalyst to the reaction solvent is 1: 0.01-2: 1-50.
5. The method for directionally degrading waste polyurethane according to claim 4, wherein the method comprises the following steps: the temperature of the reaction degradation is 100-250 ℃, and the time of the reaction degradation is 1-12 h.
6. The method for directionally degrading waste polyurethane according to claim 5, wherein the method comprises the following steps: the aromatic polyamine substances are separated and dried at room temperature; and the long-chain polyether polyol substance is separated and dried at the temperature of 80-100 ℃.
7. The method for directionally degrading waste polyurethane according to claim 6, wherein the method comprises the following steps: the amount of water added into the reaction system is 2-10 times of that of the degradation system, the water is slowly added, and the reaction system is kept stand until the precipitation is completely separated out.
8. The method for directionally degrading waste polyurethane according to claim 7, wherein the method comprises the following steps: during the extractionIs/are as followsThe extractant is organic solvent including chloroform, ethyl acetate, toluene and petroleum ether.
9. The process for the directional degradation of waste polyurethane materials according to any one of claims 1 to 8, characterized in that: the particle size of the waste polyurethane material is 0.01-1 cm.
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| EP4403589A1 (en) | 2023-01-19 | 2024-07-24 | Basf Se | A process for preparing at least one polyisocyanate from solid material w |
| CN116396188B (en) * | 2023-04-11 | 2024-05-10 | 福州大学 | Polyurethane degradation method |
| CN116284994A (en) * | 2023-04-12 | 2023-06-23 | 四川大学 | Recovery method of waste high polymer material containing ester group/amide bond/imide bond |
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| CA2342464A1 (en) * | 2000-04-04 | 2001-10-04 | Takashi Kumaki | Method of decomposing a polyurethane |
| CN103627024A (en) * | 2012-08-28 | 2014-03-12 | 杨晓林 | Method for recycling waste polyurethane |
| CN103374145B (en) * | 2013-03-21 | 2016-04-20 | 佛山市高明区业晟聚氨酯有限公司 | A kind of recovery process of polyurethane waste material |
| CN105693982B (en) * | 2016-04-12 | 2018-09-04 | 广州聚天化工科技有限公司 | A kind of polyurethane plastic runway second component and preparation method thereof and application based on polyurethane degraded product preparation |
| CN107955206A (en) * | 2017-11-28 | 2018-04-24 | 山东诺威新材料有限公司 | The method of waste polyurethane foam degraded recycling polyether polyol |
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| WO2023161252A1 (en) * | 2022-02-22 | 2023-08-31 | Evonik Operations Gmbh | Depolymerization of polyurethanes with organic amine bases |
| WO2023161251A1 (en) * | 2022-02-22 | 2023-08-31 | Evonik Operations Gmbh | Depolymerization of polyurethanes with organic amine bases |
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