CN113717434B - Method for degrading polyurethane flexible foam by using acidic ionic liquid - Google Patents
Method for degrading polyurethane flexible foam by using acidic ionic liquid Download PDFInfo
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- CN113717434B CN113717434B CN202110931531.2A CN202110931531A CN113717434B CN 113717434 B CN113717434 B CN 113717434B CN 202110931531 A CN202110931531 A CN 202110931531A CN 113717434 B CN113717434 B CN 113717434B
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- ionic liquid
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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
- C08J11/10—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
- C08J11/22—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 oxygen-containing compounds
- C08J11/26—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 oxygen-containing compounds containing carboxylic acid groups, their anhydrides or esters
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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
- 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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- 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
Abstract
A method for degrading polyurethane flexible foam by using acidic ionic liquid comprises the following steps: mixing a degrading agent and acidic ionic liquid, heating to 100-180 ℃, adding the recycled waste polyurethane foam fragments for degradation, stirring until polyurethane foam particles in a system disappear, stopping heating, standing for layering, and separating an upper layer from a lower layer; adding an acidolysis neutralizing agent into the upper layer, and carrying out a neutralization reaction for 1-8 h at a negative pressure of 50-80 ℃ to obtain a recovered product polyether polyol; taking the lower layer as the recovered acidic ionic liquid; the invention further improves the degradation rate and the degradation degree of the waste polyurethane foam, the added acidic ionic liquid has the characteristic of being recyclable and reusable, and meanwhile, the invention has no steam pressure and can not cause pollution to the environment; the recycled polyether polyol obtained by degradation in the invention can be used for being added into polyether polyol for polyurethane soft foam, thereby further improving the commercial value of polyurethane foam degradation.
Description
Technical Field
The invention relates to a method for recovering polyurethane foam, in particular to a method for degrading polyurethane foam by using acidic ionic liquid with high catalytic activity.
Background
The polyurethane material has excellent performance, wide application and various varieties, is one of the fastest-developing polymer materials in recent years, and is the sixth most synthetic material in the world. Polyurethane is a polymer having a repeating structural unit of a urethane segment, which is prepared by reacting isocyanate with polyol, and is a block copolymer comprising a soft segment mainly composed of polyisocyanate and a small-molecule chain extender and a hard segment composed of oligomer polyol (usually polyether or polyester polyol). The functionality, relative molecular mass and molecular structure of the polyols have a decisive influence on the properties of the polyurethane articles. The polyurethane foam has good chemical and physical stability, so the waste polyurethane foam is difficult to recycle or expensive in recycling cost, and the environmental pressure is increasingly heavy. Therefore, the development of efficient chemical degradation recycling treatment of polyurethane foam has become extremely urgent.
The recycled products after the degradation of the polyurethane foam are commonly used for polyurethane rigid foam, elastomers or used as fillers, and the commercial value is generally not high. Improving the commercial value of the reclaimed materials of the waste polyurethane foam is an effective way for solving the problem of high reclaiming cost. In a conventional polyurethane foam degradation system, degradation efficiency is often insufficient due to poor compatibility of a degradation agent and polyurethane foam, and degradation products with low quality can only be used for preparing rigid polyurethane foam due to high content of side reaction products and oligomers in the degradation products. In order to improve the wetting property of the degradation agent to the foam in the polyurethane foam degradation system and improve the degradation efficiency of the degradation agent, the acidic ionic liquid with certain catalytic performance is prepared and added into the polyurethane foam degradation system, and can be used as an effective component after degradation is completed.
In the degradation process, the solvent is used, so that the wettability of the degradation agent in polyurethane foam can be improved, the degradation speed is improved, but the use of the solvent is often more disadvantageous. Due to the reactivity of the degradation agent, the solvent also participates in the reaction, so that the consumption of the degradation agent and the increase of the hydroxyl value or acid value of the degradation product are caused, and the foaming of the later-period product is not facilitated. The ionic liquid has good chemical stability, can be separated and recycled after degrading polyurethane foam, and can be recycled without affecting the quality of degradation products. Meanwhile, the problems of difficult foam infiltration and low degradation speed in the early stage of degradation are solved by the excellent solubility of the polyurethane foam degradation agent, and compared with the traditional solid degradation agent, the chemical reaction area is greatly increased and the reaction speed is further increased in the process of degrading the polyurethane foam by the ionic liquid.
Disclosure of Invention
In order to solve the problem of insufficient degradation efficiency caused by poor wettability of a degradation agent and foam in polyurethane foam degradation in the prior art, the invention provides the ionic liquid with high catalytic degradation capability, the ionic liquid is added into a polyurethane foam degradation system to improve the degradation capability of the degradation agent, and can be recycled after degradation is finished.
The technical scheme of the invention is as follows:
a method for degrading polyurethane flexible foam by using acidic ionic liquid comprises the following steps:
mixing a degrading agent and acidic ionic liquid, heating to 100-180 ℃, adding the recycled waste polyurethane foam fragments for degradation, stirring until polyurethane foam particles in a system disappear, stopping heating, standing for layering, and separating an upper layer from a lower layer; adding an acidolysis neutralizing reagent into the upper layer, and carrying out neutralization reaction for 1-8 h at the temperature of 50-80 ℃ under negative pressure (-0.01-0.07 Mpa) to obtain a recovered product polyether polyol; taking the lower layer as the recovered acidic ionic liquid (the lower layer can be continuously used for degradation reaction without treatment);
the mass ratio of the degrading agent to the acidic ionic liquid is 1: 10-25;
the mass ratio of the waste polyurethane foam fragments to the degrading agent is 1-10: 1;
the mass ratio of the acidolysis neutralizing agent to the degrading agent is 1-10: 1000, parts by weight;
the degradation agent is R3COOH、HOOCR4COOH、HOOCR5One or more of OH, wherein R3、R4、R5Each independently is a C1-C10 alkyl group;
the acidic ionic liquid is represented by the following formula:
wherein R is1、R2Each independently is a C1-C3 alkyl group; x-To ionize H in the system+Anions of (e.g. HSO)4 -、H2PO4 -、AlCl4 -、FeCl4 -、ZnCl3 -Or PF6 -；
The acidolysis neutralizing agent is one or more of diethanolamine, ethylenediamine, triethanolamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.
The acidic ionic liquid provided by the invention serves as a solvent of a degradation system in the degradation and recovery process of polyurethane foam, provides degradation catalytic activity for a degradation agent, can be recycled, and has the characteristic of green solvent. The recycled polyether polyol obtained by the invention can be directly used for foaming of polyurethane soft foam (by adopting a polyurethane foam preparation method known in the field), and the addition amount is up to 30-50%. The invention carries out continuous deepening on the recycling technical route of the waste polyurethane foam, introduces the acidic ionic liquid with catalytic activity, improves the degradation quality of the recycled polyether polyol, and has low content of the obtained recycled polyether polyol oligomer and low hydroxyl value.
The invention has the following beneficial effects:
(1) the invention carries out continuous deepening on the technical route of degrading and recycling the waste polyurethane foam to obtain the recycled polyether, further improves the degradation rate and the degradation degree, and provides an effective way for industrialization of degrading a large amount of polyurethane foam;
(2) the added acidic ionic liquid has the characteristic of being recyclable and reusable, and simultaneously has no vapor pressure and no pollution to the environment;
(3) the recycled polyether polyol obtained by degradation in the invention can be used for being added into polyether polyol for polyurethane soft foam, not only can be used for preventing the degradation of polyurethane foam, but also can be used for further improving the commercial value of the degradation of polyurethane foam.
Detailed Description
The invention is further described below by means of specific examples, without the scope of protection of the invention being limited thereto.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
Adding 1000g of degradation agent and 10000g of acidic ionic liquid into a 10L reaction kettle provided with a mechanical stirring, heating, temperature controlling and pressurizing device to prepare degradation liquid, wherein the degradation agent is adipic acid and acetic acid with the mass ratio of 10:1, and the anion in the acidic ionic liquid is HSO4 -After preheating the solution to 100 ℃, adding 5000g of polyurethane foam blocks into a reaction kettle for continuous reaction for 2 hours by adopting a one-step feeding method until polyurethane foam particles disappear, standing for 6 hours for layering, adding 5g of triethylamine and sodium bicarbonate with the mass ratio of 1:1 into an upper layer product, and carrying out neutralization reaction for 1 hour at the temperature of 80 ℃ under negative pressure to obtain the final recovered product polyether polyol.
The chemical structural formula of the acidic ionic liquid is as follows:
Example 2
Adding 1000g of degradation agent and 15000g of acidic ionic liquid into a 10L reaction kettle provided with a mechanical stirring, heating, temperature controlling and pressurizing device to prepare degradation liquid, wherein the degradation agent is adipic acid and acetic acid with the mass ratio of 10:1, and the anion in the acidic ionic liquid is H2PO4 -Preheating the solution to 140 ℃, adding 8000g of polyurethane foam block into a reaction kettle for continuous reaction for 2h by adopting a one-step feeding method until polyurethane foam particles disappear, standing for 6h for layering, and taking out10g of ethylenediamine and sodium hydroxide with the mass ratio of 1:4 are added into the obtained upper layer product to carry out neutralization reaction for 1h at the temperature of 60 ℃, and finally the recovered product polyether polyol is obtained.
The chemical structural formula of the acidic ionic liquid is as follows:
Example 3
Adding 1000g of degradation agent and 20000g of acidic ionic liquid into a 10L reaction kettle equipped with a mechanical stirring, heating temperature control and pressurizing device to prepare degradation liquid, wherein the degradation agent is adipic acid and acetic acid with the mass ratio of 10:1, and the anion in the acidic ionic liquid is AlCl4 -After preheating the solution to 160 ℃, adopting a one-time feeding method to feed 10000g of polyurethane foam blocks into a reaction kettle for continuous reaction for 2 hours until polyurethane foam particles disappear, standing for 6 hours for layering, adding 10g of sodium bicarbonate into an upper-layer product, and performing neutralization reaction for 1 hour at 50 ℃ under negative pressure to obtain a final recovered product polyether polyol.
The chemical structural formula of the acidic ionic liquid is as follows:
Example 4
1000g of degradation agent and 25000g of acidic ionic liquid are added into a 10L reaction kettle provided with a mechanical stirring, heating, temperature controlling and pressurizing device to prepare degradation liquid, wherein the degradation agent is adipic acid and acetic acid with the mass ratio of 10:1, and anions in the acidic ionic liquid are ZnCl3 -After preheating the solution to 180 ℃, adopting a one-time feeding method to feed 4000g of polyurethane foam block into the reaction kettle for continuous reaction for 2 hours until the reaction is finishedAnd standing for 6h for layering after the polyurethane foam particles disappear, adding 10g of diethanolamine into the obtained upper-layer product, and performing neutralization reaction for 1h at 50 ℃ under negative pressure to obtain the final recovered product polyether polyol.
The chemical structural formula of the acidic ionic liquid is as follows:
Comparative example 1
Adding 1000g of degradation agent into a 10L reaction kettle equipped with a mechanical stirring, heating temperature control and pressurizing device, wherein the degradation agent is adipic acid and acetic acid in a mass ratio of 10:1, preheating the solution to 160 ℃, feeding 8000g of polyurethane foam blocks in batches by adopting a one-time feeding method, feeding 1000g of polyurethane foam blocks every 30min, continuing to react for 10h after all feeding is finished until polyurethane foam particles disappear, standing for 6h for layering, adding 10g of sodium bicarbonate into an upper layer product, and neutralizing and reacting for 2h at 50 ℃ under negative pressure to obtain the final recovered product polyether polyol.
The recycled polyether polyol products obtained in examples 1 to 4 can be used directly for the preparation of flexible polyurethane foams.
Comparing examples 1, 2, 3, 4 and comparative example 1, it was found that the system without adding acidic ionic liquid has greatly prolonged feeding time and degradation time, while the degradation system with adding acidic ionic liquid can degrade polyurethane foam to number average molecular weight of less than 6000 within 2h by adopting a one-time feeding method, and compared with 10h of comparative example 1, the energy consumption and time cost are greatly reduced.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A method for degrading polyurethane flexible foam by using acidic ionic liquid is characterized by comprising the following steps:
mixing a degrading agent and acidic ionic liquid, heating to 100-180 ℃, adding the recycled waste polyurethane foam fragments for degradation, stirring until polyurethane foam particles in a system disappear, stopping heating, standing for layering, and separating an upper layer from a lower layer; adding an acidolysis neutralizing agent into the upper layer, and carrying out a neutralization reaction for 1-8 h at a negative pressure of 50-80 ℃ to obtain a recovered product polyether polyol; taking the lower layer as the recovered acidic ionic liquid;
the degradation agent is R3COOH、HOOCR4COOH、HOOCR5One or more of OH, wherein R3、R4、R5Each independently is a C1-C10 alkyl group;
the acidic ionic liquid is represented by the following formula:
wherein R is1、R2Each independently is C1-C3 alkyl, X-is HSO4 -、H2PO4 -、AlCl4 -、FeCl4 -、ZnCl3 -Or PF6 -；
The acidolysis neutralizing agent is one or more of diethanolamine, ethylenediamine, triethanolamine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate.
2. The method for degrading the polyurethane flexible foam by using the acidic ionic liquid as claimed in claim 1, wherein the mass ratio of the degrading agent to the acidic ionic liquid is 1: 10 to 25.
3. The method for degrading the polyurethane flexible foam by using the acidic ionic liquid as claimed in claim 1, wherein the mass ratio of the waste polyurethane foam fragments to the degradation agent is 1-10: 1.
4. the method for degrading the polyurethane flexible foam by using the acidic ionic liquid as claimed in claim 1, wherein the mass ratio of the acidolysis neutralizing agent to the degrading agent is 1-10: 1000.
5. the method for degrading the polyurethane flexible foam by using the acidic ionic liquid as claimed in claim 1, wherein the negative pressure is in a range of-0.01 to-0.07 Mpa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024013423A1 (en) * | 2022-07-14 | 2024-01-18 | Universidad De Murcia | Method for polyurethane depolymerization |
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| CN113999428A (en) * | 2021-10-19 | 2022-02-01 | 河北工程大学 | Green catalytic degradation method for amide bond/ester bond-containing high polymer material |
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| US10323116B2 (en) * | 2013-03-15 | 2019-06-18 | Imperial Sugar Company | Polyurethanes, polyurethane foams and methods for their manufacture |
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Patent Citations (3)
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| DE102010028583A1 (en) * | 2009-05-11 | 2011-01-05 | Basf Se | Degradation of polyurethanes in the presence of special ionic liquids and a low water content |
| CN107286369A (en) * | 2017-08-02 | 2017-10-24 | 江苏世丰新材料有限公司 | A kind of method that acidolysis soft polyurethane foam discarded object generates polyalcohol |
| CN113999428A (en) * | 2021-10-19 | 2022-02-01 | 河北工程大学 | Green catalytic degradation method for amide bond/ester bond-containing high polymer material |
Non-Patent Citations (1)
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| 离子液体催化降解PET相关体系物性研究;张志博;《中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑)》;20150415;B027-178 * |
Cited By (1)
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| WO2024013423A1 (en) * | 2022-07-14 | 2024-01-18 | Universidad De Murcia | Method for polyurethane depolymerization |
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