CN114106281B - Method for modifying recycled polyol and application of modified polyol - Google Patents
Method for modifying recycled polyol and application of modified polyol Download PDFInfo
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- CN114106281B CN114106281B CN202111449452.4A CN202111449452A CN114106281B CN 114106281 B CN114106281 B CN 114106281B CN 202111449452 A CN202111449452 A CN 202111449452A CN 114106281 B CN114106281 B CN 114106281B
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- alcoholysis
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- 229920005862 polyol Polymers 0.000 title claims abstract description 79
- 150000003077 polyols Chemical class 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims description 25
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 35
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 28
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 5
- 238000004064 recycling Methods 0.000 claims abstract description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 20
- 150000004982 aromatic amines Chemical group 0.000 claims description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 14
- -1 aldehyde compound Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000005187 foaming Methods 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- PDVFSPNIEOYOQL-UHFFFAOYSA-N (4-methylphenyl)sulfonyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OS(=O)(=O)C1=CC=C(C)C=C1 PDVFSPNIEOYOQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 38
- 229920002635 polyurethane Polymers 0.000 abstract description 27
- 239000004814 polyurethane Substances 0.000 abstract description 27
- 239000000463 material Substances 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 229920006264 polyurethane film Polymers 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010169 landfilling Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a polyurethane rigid foam which is prepared by taking polyurethane foam as a raw material, obtaining recycled polyol through alcoholysis, and then obtaining modified polyol through acetal reaction modification, wherein the polyol is mixed with polyether polyol in a proportion of 20% -60% to be used as a combined white material, and reacts with black polymeric MDI. The foam can be hot pressed into a film for reuse in the field of polyurethane films, and the foam also has the advantages of low cost and high recovery rate in the aspect of alcoholysis recovery. According to the invention, the polyurethane foam is recycled through alcoholysis for the first time, and is modified and applied to the polyurethane foam again, so that the recycling of materials in the polyurethane industry is realized, and the recycling prospect of the polyurethane foam is wider.
Description
Technical Field
The invention relates to a method for modifying recycled polyol and application of the modified polyol in preparing polyurethane foam.
Background
The Otto Bayer doctor in 1937 Germany and the team thereof first found that the polyurethane can be prepared by the polymerization reaction of polyisocyanate and polyol, which lays the foundation for the vigorous development of the polyurethane industry. The polyurethane foam products have three types of soft foam, semi-hard foam and hard foam, and the application fields of different forms are also quite different. The soft foam is mainly used for automobile seats and carpets, the semi-rigid foam is used for automobile roofs and engine heat insulation pads, and the rigid foam is used as a heat insulation material, such as buildings, refrigerators and the like.
Polyurethane foam is increasingly used in various industries due to its excellent physical properties and good processability, but at the same time, the treatment of waste polyurethane is also a major problem. Polyurethane materials are extremely difficult to decompose under natural conditions, and if deeply buried, they can be decomposed only for decades. The treatment method commonly adopted at present is incineration, but a great deal of toxicity is generated in the incineration processHarmful gases such as NO 2 Hydrocyanic acid (HCN), and the like. Thus, neither landfilling nor incineration is a suitable treatment, neither environmentally friendly nor economical.
The chemical recovery of polyurethane foam can re-degrade the foam to obtain recovery liquid, and the chemical recovery method mainly comprises an alkaline solution, an ammonolysis method, a hydrolysis method, an alcoholysis method and the like, and the alcoholysis method is mainly an alcoholysis method due to simple process and convenient application of the recovery liquid. The application number 201310651447.0 patent prepares a mixture of regenerated polyol and aromatic amine by alcoholysis of waste polyurethane products, and prepares combined polyether with polyether polyol and polyester polyol for foaming to prepare the novel polyurethane rigid foam. The patent CN105418878A is to carry out alcoholysis on polyurethane foam to obtain regenerated polyether polyol, then mix the regenerated polyether polyol with other two non-regenerated polyether polyols in a certain proportion to be used as a polyol combination material, and foam the polyol combination material with black polymeric MDI to form polyurethane foam. However, with strict environmental protection requirements, the polyurethane industry has limitations on aromatic amine, and the recycled polyol cannot be used in industries such as household appliances, foam coatings and the like.
The alcoholysis of polyurethane is based on an equilibrium reaction, which requires more than a stoichiometric amount of hydroxyl groups of the alcoholysis agent (small diol molecule) to cleave the urethane groups, and if no diol is used in excess in the alcoholysis, the alcoholysis reaction stays at the high molecular weight fraction level, so that the recovery solution obtained from the alcoholysis mainly comprises the hydroxyl-terminated oligomer and the unreacted complete alcoholysis agent. At the same time, small amounts of aromatic amine compounds are produced during the alcoholysis process, which are harmful to the human body. The use of various additives for the removal of amines during or after the alcoholysis reaction is described in the patents DE-B4116700, DE-A4215014 and DE-A4234335. The use of additives increases the production costs on the one hand and has a negative effect on the mechanical properties of the polyurethane, on the other hand, since the reaction products remain in the product. Therefore, a new process for removing aromatic amine without reducing the mechanical properties of polyurethane materials is needed.
Disclosure of Invention
The invention aims to provide a method for modifying recycled polyol, which only needs to add a modifying auxiliary agent to an alcoholysis reaction kettle for reaction, and does not need other purifying equipment.
Another object of the present invention is to provide a use of the modified polyol for polyurethane foaming, which improves recycling efficiency, and more importantly, thermoplastic processability of the foam, compared with a use of the modified polyol as a filler after ordinary physical pulverization of the foam.
In order to achieve the above object, the present invention has the following technical scheme:
the regenerated polyol is derived from an alcoholysis product of polyurethane foam, and the alcoholysis product of the polyurethane foam is modified by an aldehyde compound to finally obtain modified polyol, wherein the obtained modified polyol has no aromatic amine residue and contains an acetal structure in a molecule.
As a preferred embodiment, a method for recovering a regenerated polyol modification comprises the steps of:
s1: the polyurethane rigid foam undergoes alcoholysis reaction in small molecular dihydric alcohols (alcoholysis agents) such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol to obtain regenerated polyol;
s2: in the regenerated polyol in S1, aldehyde modification auxiliary agents such as furfural or benzaldehyde are added, organic acid such as p-toluenesulfonic acid is used as a catalyst, and the regenerated polyol is modified, so that on one hand, aromatic amine in a system is consumed, and on the other hand, the regenerated polyol can react with alcohol in the system to obtain modified polyol.
In the invention, the reaction of S1 is an alcoholysis reaction of polyurethane.
In the invention, the alcoholysis reaction is carried out to obtain an alcoholysis agent containing short-chain polyol, aromatic amine and small molecules; according to the invention, the high polymers of the starting polyurethane are generally alcoholyzed to polyols of 700-1500 molecular weight. The hydroxyl value is 300-550mgKOH/g, the viscosity is 2000-3500 mPa.s, and the mass content of aromatic amine is 2% -5%.
In the invention, the polyurethane rigid foam in the S1 is selected from leftover materials or wastes in the production process of polyurethane heat insulation materials such as refrigerators, water heaters, heat insulation pipelines and the like.
In the invention, the temperature of the S1 reaction is 150-250 ℃, preferably 170-210 ℃; too low reaction temperature affects production efficiency, high reaction temperature and more byproducts, and affects the appearance and downstream application of the product.
In the present invention, the reaction time of S1 is 1h to 20h, preferably 2h to 5h.
In the invention, the catalyst in S1 is selected from hydroxide of alkali metal such as potassium hydroxide and sodium hydroxide or organic amine compound such as dimethylamine, triethylamine and triethanolamine, and the dosage is 0.5-2 percent based on the total mass of the alcoholysis agent.
The alcoholysis process is described in detail in patent CN 10539985A and CN 107955206A, both of which are incorporated herein by reference.
In the invention, the modifying auxiliary aldehyde compound of S2 is selected from one or more of furfural and benzaldehyde.
In the invention, the addition amount of the aldehyde modification auxiliary agent in the S2 is 10-50%, preferably 15-30%, based on the total mass of the recovered regenerated polyol.
The modified polyol obtained by modification has a hydroxyl value of 380-420mgKOH/g, a viscosity of 1500-6000 mPa.s and an aromatic amine content of less than 1ppm.
In the invention, the modified catalyst in the S2 is organic acid such as benzoic acid, p-toluenesulfonic acid anhydride and the like and anhydride thereof, and the addition amount is 0.1 to 5 percent, preferably 2 to 3 percent, based on the total mass of the recovered and regenerated polyol
In the invention, after the aldehyde compound is added into the S2, the reaction is carried out for 3 to 12 hours at the temperature of 80 to 130 ℃.
The use of the modified polyols according to the invention for producing polyurethane foams. Foaming polymeric MDI and combined polyether to prepare polyurethane foam, wherein the mass ratio of the polymeric MDI to the combined polyether is 1.1-1.5:1, and the combined polyether comprises 20-60% of modified polyol and 40-80% of fresh combined polyether by mass fraction. The NCO content of the polymeric MDI is between 28 and 31 percent
The fresh combined polyether comprises polyether polyol, a flame retardant, silicone oil, an organic amine catalyst and water. Common brands are: mo Huarong, WF RCB6130, WF RCB6158, WF RCM6003, RCM6005, RCP5019, and the like.
The method has obvious advantages that the content of aromatic amine in the alcoholysis product of the polyurethane foam is reduced to below 1ppm due to the use of the furfural or benzaldehyde modifier, the environmental protection requirements of various industries are met, and particularly, the furfural compound reacts with the polyol to form an acetal structure, so that the foam prepared from the polyol has the plasticity and the repeatability of processing.
The invention has the positive effects that:
a) After the alcoholysis of the polyurethane foam, the aromatic amine content of the obtained recovered polyol is reduced to below 1ppm in the modification process, and the recovered polyol is used as a polyurethane white material, is not limited by downstream application, and can be continuously used in the fields of household appliances such as refrigerators and the like.
b) The prepared modified recycled polyol contains an acetal structure, and the polyurethane foam prepared by using the modified recycled polyol as a white material has the characteristic of plasticity and repeated processing, so that the service life of the foam is prolonged.
c) The furfural can be prepared from renewable energy sources such as corncob or straw, and the recycled polyol is modified by using a furfural compound and reused as polyurethane white material, so that the sustainability of polyurethane is improved.
Detailed Description
The present invention is further illustrated by the following examples, although the scope of the invention is not limited to the following examples. Raw materials:
polyurethane rigid foam and heat-insulating foam for waste sea refrigerator body
Diethylene glycol, microphone, 98%;
potassium hydroxide, micin, AR;
furfural, 98.5% of Hangzhou Zheqiagenic chemical industry;
benzaldehyde, aledine, 99%;
p-toluenesulfonic anhydride, shanghai tai, 98%;
combined polyether polyol RCP5039, mo Huarong;
cyclopentane, shanghai Ala-dine, 99%;
polymeric MDI (PM-200), NCO content 31%, wanhua chemistry
The test instrument includes: foam grinder (model: ZPP 6045), digital viscometer (model: DV-79), compression tester (model: WDW-10), hot press (model: SY-6210-B-50T)
The hydroxyl number was titrated with potassium hydroxide and the aromatic amine content was determined using high performance liquid chromatography.
Polyurethane foam preparation: the regenerated and recycled polyol or modified polyol is mixed with a combined polyether polyol (RCP 5039) according to the mass ratio to obtain a polyether mixture, and the polyether mixture and cyclopentane serving as a foaming agent according to the mass ratio of 9:1, mixing with polymeric MDI according to a mass ratio of 1:1.3, and foaming under stirring at a rotating speed of 2000rpm to obtain the polyurethane rigid foam.
Compression strength was tested using a compression tester.
Plasticity test: cutting polyurethane foam into 2 x 2cm pieces, shaping in a hot press at 180deg.C under 10Mpa, and observing the shape of the compressed material
Comparative example 1
Firstly, nitrogen is introduced into a 2L reaction kettle provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, air is replaced completely, 600g of diethylene glycol is added as alcoholysis liquid, heating is carried out to 180 ℃, and then 6g of potassium hydroxide is added as a catalyst. Then gradually adding 1000g of crushed waste hard polyurethane foam (the size of the crushed foam is not more than 2cm x 2 cm) into a reaction kettle, reacting for 5 hours at 180 ℃, introducing nitrogen into the bottom after the reaction is finished, bubbling to maintain the temperature between 170 ℃ and 180 ℃ for 1 hour, cooling to 80-90 ℃, and filtering to obtain a wine red transparent liquid, namely the recycled polyol.
The regenerated polyol was combined with a polyether polyol (RCP 5039) at 1:3, mixing the materials according to the mass ratio, foaming the mixture with a foaming agent and polymeric isocyanate to obtain polyurethane rigid foam, and testing the compression strength and the thermoplasticity of the foam.
Example 1
Firstly, nitrogen is introduced into a 2L reaction kettle provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, air is replaced completely, 600g of diethylene glycol is added as alcoholysis liquid, heating is carried out to 180 ℃, and then 6g of potassium hydroxide is added as a catalyst. Then gradually adding 1000g of crushed waste hard polyurethane foam (the size of the crushed foam is not more than 2cm x 2 cm) into a reaction kettle, reacting for 5 hours at 180 ℃, cooling to 120 ℃ after the reaction is finished, adding 1.6g of p-toluenesulfonic acid and 160g of furfural, maintaining the temperature between 125 ℃ and 130 ℃ for 8 hours, then introducing nitrogen at the bottom for maintaining the temperature between 120 ℃ and 130 ℃ for 1 hour, cooling to 80 ℃ to 90 ℃, and filtering to obtain a wine red transparent liquid, namely the modified polyol.
The modified polyol was combined with a polyether polyol (RCP 5039) at 3: and mixing the materials according to the mass ratio of 2, foaming the mixture with a foaming agent and polymeric isocyanate to obtain the polyurethane rigid foam, and testing the compression strength and the thermoplasticity of the foam.
Example 2
Firstly, nitrogen is introduced into a 2L reaction kettle provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, air is replaced completely, 600g of diethylene glycol is added as alcoholysis liquid, heating is carried out to 180 ℃, and then 6g of potassium hydroxide is added as a catalyst. Then gradually adding 1000g of crushed waste hard polyurethane foam (the size of the crushed foam is not more than 2cm x 2 cm) into a reaction kettle, reacting for 5 hours at 180 ℃, cooling to 120 ℃ after the reaction is finished, adding 48g of p-toluenesulfonic anhydride and 320g of furfural, maintaining the temperature between 100 ℃ and 105 ℃ for 5 hours, then introducing nitrogen to the bottom, maintaining the temperature between 120 ℃ and 130 ℃ for 1 hour, cooling to 80 ℃ to 90 ℃, and filtering to obtain a wine red transparent liquid, namely the modified polyol.
The modified polyol was combined with a polyether polyol (RCP 5039) at 1: and mixing the materials according to the mass ratio of 2, foaming the mixture with a foaming agent and polymeric isocyanate to obtain the polyurethane rigid foam, and testing the compression strength and the thermoplasticity of the foam.
Example 3
Firstly, nitrogen is introduced into a 2L reaction kettle provided with a stirrer, a heating temperature control device, a cooling device and a pressure sensor, air is replaced completely, 600g of diethylene glycol is added as alcoholysis liquid, heating is carried out to 180 ℃, and then 6g of potassium hydroxide is added as a catalyst. Then gradually adding 1000g of crushed waste hard polyurethane foam (the size of the crushed foam is not more than 2cm x 2 cm) into a reaction kettle, reacting for 5 hours at 180 ℃, cooling to 120 ℃ after the reaction is finished, adding 80g of benzoic acid and 800g of benzaldehyde, maintaining the temperature between 80 ℃ and 85 ℃ for 4 hours, then introducing nitrogen to the bottom, maintaining the temperature between 120 ℃ and 130 ℃ for 1 hour, cooling to 80 ℃ to 90 ℃, and filtering to obtain a wine red transparent liquid, namely the modified polyol.
The modified polyol was combined with a polyether polyol (RCP 5039) at 1:4, mixing the materials according to the mass ratio, foaming the mixture with a foaming agent and polymeric isocyanate to obtain polyurethane rigid foam, and testing the compression strength and the thermoplasticity of the foam.
The test results of the regenerated polyol and the modified polyol and the foam performance test prepared by the same are shown in table 1, and the comparative example shows that the regenerated polyol contains a small amount of aromatic amine under the non-modified condition, so that the application of the regenerated polyol is influenced. While the examples show that the aromatic amine content in the modified polyol is reduced to below 1ppm using furfural, benzaldehyde. Compared with the comparative example, the compressive strength of the foam prepared from the modified polyol is slightly improved, and the foam can be remolded after hot pressing and has certain plasticity.
Table 1 comparison of test data for each product
Claims (10)
1. The method for modifying recycled and regenerated polyol is characterized in that the recycled and regenerated polyol is an alcoholysis product of polyurethane foam, the alcoholysis product of the polyurethane foam is modified by an aldehyde compound to finally obtain modified polyol, the obtained modified polyol has no aromatic amine residue, and an acetal structure is contained in molecules; the aldehyde compound is furfural or benzaldehyde.
2. The method according to claim 1, wherein the recycled polyol is obtained by alcoholysis and recycling of polyurethane foam, the hydroxyl value is 300-550mgKOH/g, the viscosity is 2000-3500 mPa.s, and the mass content of aromatic amine is 2% -5%.
3. The method of claim 1, wherein the aldehyde compound is present in an amount of 10 to 50% by mass of the regenerated polyol.
4. A method according to any one of claims 1-3, characterized in that the catalyst used for the modification is benzoic acid, p-toluene sulphonic acid or p-toluene sulphonic anhydride, said catalyst being used in an amount of 0.1-5% by mass of the regenerated polyol.
5. A method according to any one of claims 1-3, characterized in that the reaction temperature of the modification is 80-130 ℃ and the reaction time is 3-12h.
6. A process according to any one of claims 1 to 3, wherein the modified polyol obtained by modification has a hydroxyl value of 380-420mgKOH/g, a viscosity of 1500-6000 mPa-s and an aromatic amine content of less than 1ppm.
7. Use of a modified polyol prepared according to the method of any one of claims 1-6 in the preparation of a polyurethane foam.
8. Use according to claim 7, characterized in that polyurethane foam is produced by foaming polymeric MDI and a combined polyether, wherein the mass ratio of polymeric MDI and combined polyether is 1.1-1.5:1, the combined polyether comprises 20-60% by mass of modified polyol, 40-80% by mass of fresh combined polyether.
9. The use according to claim 8, wherein the fresh combined polyether comprises polyether polyol, flame retardant, silicone oil, organic amine catalyst, water.
10. Use according to claim 8 or 9, characterized in that the NCO content of the polymeric MDI is between 28 and 31%.
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| CN1060853A (en) * | 1991-06-22 | 1992-05-06 | 胜利石油管理局油建二公司 | Use extracting coating resin from waste polyester foam |
| DE4116700C1 (en) * | 1991-05-22 | 1993-01-14 | Gunter Prof. Dr. 7080 Aalen De Bauer | Redn of content of aromatic amine(s), in prodn. of polyurethane(s) - by reacting with either carbonyl or glucose, fructose, maleic or fumaric acids or derivs. |
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| CN106380567A (en) * | 2016-08-30 | 2017-02-08 | 浙江华江科技股份有限公司 | Polyurethane high resilience foam prepared from recovered recycled polyol as raw material |
| CN113402770A (en) * | 2021-07-08 | 2021-09-17 | 上海鹤城高分子科技有限公司 | Method for degrading, recycling and reusing polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4116700C1 (en) * | 1991-05-22 | 1993-01-14 | Gunter Prof. Dr. 7080 Aalen De Bauer | Redn of content of aromatic amine(s), in prodn. of polyurethane(s) - by reacting with either carbonyl or glucose, fructose, maleic or fumaric acids or derivs. |
| CN1060853A (en) * | 1991-06-22 | 1992-05-06 | 胜利石油管理局油建二公司 | Use extracting coating resin from waste polyester foam |
| CN105418878A (en) * | 2015-12-21 | 2016-03-23 | 浙江华江科技股份有限公司 | High-density and high-toughness polyurethane foam produced by using regenerated polyether polyol as raw material and preparation method therefor |
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