CN103012838A - Waste polyurethane foam aminolysis recycling method - Google Patents
Waste polyurethane foam aminolysis recycling method Download PDFInfo
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- CN103012838A CN103012838A CN2011102803307A CN201110280330A CN103012838A CN 103012838 A CN103012838 A CN 103012838A CN 2011102803307 A CN2011102803307 A CN 2011102803307A CN 201110280330 A CN201110280330 A CN 201110280330A CN 103012838 A CN103012838 A CN 103012838A
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- waste polyurethane
- aminolysis
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- polyurethane
- waste
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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
The invention relates to a waste polyurethane foam aminolysis recycling method, which comprises: a, removing surface attachments of waste polyurethane products; b, carrying out cutting or mechanical crushing on the surface attachment-removed waste polyurethane products into small blocks; c, preparing a mixture of regeneration polyol and aromatic amine; and d, preparing the mixture of the regeneration polyol and the aromatic amine into combination polyether for hard foam, and carrying out foaming. According to the present invention, a chemical recovery method is adopted to decompose waste polyurethane products, and processing utilization is performed, such that an environment pollution problem caused by the polyurethane foam is solved.
Description
Technical field:
The present invention relates to the polyurethanes technology field, reclaim and utilize method more specifically to the aminolysis that produces the waste polyurethane goods in the productions such as urethane chemical industry, polyurethane product.
Background technology:
The recycling of polyurethane product more and more is subject to the attention of world government, and in the U.S., the urethane circulation recovery council (PURRC) that is arranged by the urethane branch of U.S. association of plastics industry (SPI) promotes; In Japan, jointly pulled together to promote by Japanese polyurethane TIA (PUII), urethane raw TIA and porous plastics TIA; In Europe, promoted hand in hand by European isocyanic ester association (ISOPA) and European Society of Chemical Industry.
At present, be used widely at China's polyurethane material every profession and trade, the industry urethane consumptions such as refrigerator, refrigerator-freezer, solar water heater, electric water heater, building heat preservation sheet material, freezer, automobile, furniture are huge, reached 5,500,000 tons in 2009, reached 6,040,000 tons in 2010, the scrap rate that produces in the production process of these products calculates the annual waste polyurethane goods that will produce more than 18000 tons by 3 ‰, and the useless foam that in fact produces in the production process is far above this numeral! But because polyurethane foam is heat cured, difficulty is larger in recycling, does not perhaps have effective measures to go to deal carefully with at all, and the generation of useless foam has caused great pollution to environment.
Traditional physics absorption method, pyrolysis method, hydrolysis method all can not be utilized the waste polyurethane goods fully, such as: the recycling of polyurethane flexible foam, economic angle from antenatal input, better with the physical recovering method utilization, but the poor-performing of goods can only be made low-grade articles for use, and no matter be to adopt Bonding pressure moulding or extrusion moulding, the foamy structure of urethane has produced the destruction of certain degree, causes the mechanical property of regenerate to reduce, and causes thus eliminating fast of waste material.The waste material that hard polyurethane foams and elastomerics produce there is no effective recoverying and utilizing method at present.The US6759260B2 patent is addressed the technique that a kind of polyurethane foam is recycled, carry out alcoholysis or the amine method is come the dissolve polyurethane foam in the effect of potassium hydroxide or sodium hydroxide, but the purified solution separation industries input after decomposing is difficult to too greatly realize, restricted very large to the use of reclaiming raw material simultaneously.The US3117940 patent has been described the aminolysis method of flexible PU foam, how not to use the problem of solution behind the aminolysis but touch upon.
Summary of the invention:
Purpose of the present invention is exactly the deficiency for prior art, and provide a kind of waste polyurethane foam aminolysis recoverying and utilizing method, it decomposes the waste polyurethane goods and carries out processing and utilization by chemical recovery method, solve the pollution problem that polyurethane foam is brought to environment, generation hard polyurethane foam, semi-rigid foam, flexible foam, elastomerics are decomposed, and are recycled to reach the purpose of " turning waste into wealth " cost efficiency when making polyurethane foam production.
Technology solution of the present invention is as follows:
A kind of waste polyurethane foam aminolysis recoverying and utilizing method,
A, waste polyurethane product surface dirt settling is removed;
B, the waste polyurethane goods cutting that will remove surface attachments or mechanical disintegration frustillatum obtain fritter shape waste polyurethane, and the maximum length of fritter shape waste polyurethane is for being not more than 200mm;
C, fritter shape waste polyurethane is slowly joined in the compound of amino-contained, do not having catalyzer to exist or adding in an amount of catalyzer situation, stirring and temperature of reaction is controlled under the 150-250 ℃ of condition and carried out aminolysis reaction 1～20 hour, getting final product to get the mixture of regenerating polyol and aromatic amine;
The adding proportioning of described waste polyurethane goods, aminolysis agent and catalyst feed is the waste polyurethane goods by weight: the aminolysis agent: catalyzer=0.1～5: 1: 0～1;
Described aminolysis agent is adopted to have-aminated compounds of NH structure, and the aminolysis agent is diethanolamine trolamine or their mixture more than two kinds;
Described catalyzer is acetate, the titanic acid ester of metal base or alkaline-earth metal;
D, the regenerating polyol that obtains and mixture, polyether glycol and the polyester polyol of aromatic amine are mixed with respectively hard foam combined polyether, and foam.
The described compound that contains amido is diethanolamine, trolamine or their mixture more than two kinds.
Described waste polyurethane goods are hard polyurethane foams or flexible PU foam or polyurethane elastomer.
Effect of the present invention is: 1, it decomposes the waste polyurethane goods and carries out processing and utilization by chemical recovery method, solve the pollution problem that polyurethane foam is brought to environment, generation hard polyurethane foam, semi-rigid foam, flexible foam, elastomerics are resolved into the mixture of regenerating polyol and aromatic amine, and are recycled to reach the purpose of " turning waste into wealth " cost efficiency when making polyurethane foam production.
2, the mixture of regenerating polyol and aromatic amine is directly added to carry out frothing test in the rigid foam combined polyether, obtain foam and have good intensity, thinner abscess, splendid dimensional stability;
Embodiment:
Embodiment 1: a kind of waste polyurethane foam aminolysis recoverying and utilizing method, 500 gram trolamines are joined in 1500 milliliters of three-necked bottles with stirring, heating and temperature-control device, and adding tetrabutyl titanate 2.5 grams, be heated to 150-250 ℃, again the 500 gram waste and old regenerant of urethane (hard polyurethane foams) cutting and grinding are become fritter, slowly add in the trolamine, the limit adds stirring, foam all dissolves after about 12 hours, the low molecule of vacuum removal 30 minutes gets regenerant A 940 grams.
Embodiment 2: a kind of waste polyurethane foam aminolysis recoverying and utilizing method, and above embodiment 1, gained A regenerant are mixed with conjugate polyether for hard polyurethane foam and carry out frothing test, it the results are shown in Table one.
Table one: embodiment 2 test-results
Claims (3)
1. waste polyurethane foam aminolysis recoverying and utilizing method is characterized in that:
A, waste polyurethane product surface dirt settling is removed;
B, the waste polyurethane goods cutting that will remove surface attachments or mechanical disintegration frustillatum obtain fritter shape waste polyurethane, and the maximum length of fritter shape waste polyurethane is for being not more than 200mm;
C, fritter shape waste polyurethane is slowly joined in the compound that contains amido, do not having catalyzer to exist or adding in an amount of catalyzer situation, stirring and temperature of reaction is controlled under the 150-250 ℃ of condition and carried out alcoholysis reaction 1～20 hour, getting final product to get the mixture of regenerating polyol and aromatic amine;
Described by weight fritter shape waste polyurethane: contain the compound of amido=1: 0.6～1.5; The adding proportioning of described waste polyurethane goods, aminolysis agent and catalyst feed is the waste polyurethane goods by weight: the aminolysis agent: catalyzer=0.1～5: 1: 0～1;
Described aminolysis agent is adopted to have-the amine organic compound of NH structure, and the aminolysis agent is diethanolamine, trolamine or their mixture more than two kinds;
Described catalyzer is acetate, the titanic acid ester of metal base or alkaline-earth metal;
D, the regenerating polyol that obtains and mixture, polyether glycol and the polyester polyol of aromatic amine are mixed with respectively hard foam combined polyether, and foam.
2. a kind of waste polyurethane foam aminolysis recoverying and utilizing method according to claim 1, it is characterized in that: the described compound that contains amido is diethanolamine, trolamine or their mixture more than two kinds.
3. a kind of waste polyurethane foam aminolysis recoverying and utilizing method according to claim 1, it is characterized in that: described waste polyurethane goods are hard polyurethane foams or flexible PU foam or polyurethane elastomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102803307A CN103012838A (en) | 2011-09-21 | 2011-09-21 | Waste polyurethane foam aminolysis recycling method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102803307A CN103012838A (en) | 2011-09-21 | 2011-09-21 | Waste polyurethane foam aminolysis recycling method |
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| CN103012838A true CN103012838A (en) | 2013-04-03 |
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| CN2011102803307A Pending CN103012838A (en) | 2011-09-21 | 2011-09-21 | Waste polyurethane foam aminolysis recycling method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3098257A1 (en) | 2015-05-12 | 2016-11-30 | Politechnika Gdanska | Method of glicerolysis of polyurethane waste product and glycerolysates obtained by the method |
| CN106273074A (en) * | 2016-08-15 | 2017-01-04 | 浙江首想科技有限公司 | A kind of waste and old sponge reprocessing technique of band anion |
| CN114805972A (en) * | 2022-05-05 | 2022-07-29 | 青岛科技大学 | Method for preparing reclaimed rubber by using polyurethane chemical catalytic degradation product as regeneration auxiliary agent |
| LU501979B1 (en) | 2022-04-29 | 2023-10-30 | Kemijski Inst | Chemical recycling of polyurethane foams with amines |
| WO2024050749A1 (en) * | 2022-09-08 | 2024-03-14 | 上纬创新育成股份有限公司 | Self-catalytic directional degradation method for polyurethane material, polyol prepared thereby, and polyurethane material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117940A (en) * | 1960-11-14 | 1964-01-14 | Mobay Chemical Corp | Method of dissolving polyurethanes |
-
2011
- 2011-09-21 CN CN2011102803307A patent/CN103012838A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117940A (en) * | 1960-11-14 | 1964-01-14 | Mobay Chemical Corp | Method of dissolving polyurethanes |
Non-Patent Citations (1)
| Title |
|---|
| 陈海平等: ""聚氨酯材料的化学降解机理"", 《辽宁化工》, vol. 36, no. 8, 20 August 2007 (2007-08-20), pages 535 - 539 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3098257A1 (en) | 2015-05-12 | 2016-11-30 | Politechnika Gdanska | Method of glicerolysis of polyurethane waste product and glycerolysates obtained by the method |
| CN106273074A (en) * | 2016-08-15 | 2017-01-04 | 浙江首想科技有限公司 | A kind of waste and old sponge reprocessing technique of band anion |
| LU501979B1 (en) | 2022-04-29 | 2023-10-30 | Kemijski Inst | Chemical recycling of polyurethane foams with amines |
| WO2023209022A1 (en) | 2022-04-29 | 2023-11-02 | Kemijski Institut | Recycling of polyurethanes by aminolysis with reagents comprising primary and/or secondary and tertiary amino groups in the structure |
| CN114805972A (en) * | 2022-05-05 | 2022-07-29 | 青岛科技大学 | Method for preparing reclaimed rubber by using polyurethane chemical catalytic degradation product as regeneration auxiliary agent |
| WO2024050749A1 (en) * | 2022-09-08 | 2024-03-14 | 上纬创新育成股份有限公司 | Self-catalytic directional degradation method for polyurethane material, polyol prepared thereby, and polyurethane material |
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Application publication date: 20130403 |