CN116814712A - Method for producing amine monomer by degrading polyurethane through chemical biological method - Google Patents
Method for producing amine monomer by degrading polyurethane through chemical biological method Download PDFInfo
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- CN116814712A CN116814712A CN202310749902.4A CN202310749902A CN116814712A CN 116814712 A CN116814712 A CN 116814712A CN 202310749902 A CN202310749902 A CN 202310749902A CN 116814712 A CN116814712 A CN 116814712A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 83
- 239000004814 polyurethane Substances 0.000 title claims abstract description 83
- 239000000178 monomer Substances 0.000 title claims abstract description 31
- 239000000126 substance Substances 0.000 title claims abstract description 15
- 230000000593 degrading effect Effects 0.000 title claims abstract description 12
- 238000010170 biological method Methods 0.000 title claims abstract description 10
- 150000001412 amines Chemical class 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 23
- 108090000371 Esterases Proteins 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007853 buffer solution Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 3
- 229920003023 plastic Polymers 0.000 claims description 28
- 239000004033 plastic Substances 0.000 claims description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 27
- 108090000790 Enzymes Proteins 0.000 claims description 16
- 102000004190 Enzymes Human genes 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- -1 amine compound Chemical class 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000008363 phosphate buffer Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 2
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 33
- 229920000728 polyester Polymers 0.000 description 20
- 239000004721 Polyphenylene oxide Substances 0.000 description 17
- 229920000570 polyether Polymers 0.000 description 17
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000002699 waste material Substances 0.000 description 11
- 238000011084 recovery Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 108091005804 Peptidases Proteins 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000012258 culturing Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
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- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- HJXPGCTYMKCLTR-UHFFFAOYSA-N 2-bromo-9,9-diethylfluorene Chemical compound C1=C(Br)C=C2C(CC)(CC)C3=CC=CC=C3C2=C1 HJXPGCTYMKCLTR-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 230000034659 glycolysis Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 239000002054 inoculum Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- BPHPUYQFMNQIOC-NXRLNHOXSA-N isopropyl beta-D-thiogalactopyranoside Chemical compound CC(C)S[C@@H]1O[C@H](CO)[C@H](O)[C@H](O)[C@H]1O BPHPUYQFMNQIOC-NXRLNHOXSA-N 0.000 description 1
- SBUJHOSQTJFQJX-NOAMYHISSA-N kanamycin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N SBUJHOSQTJFQJX-NOAMYHISSA-N 0.000 description 1
- 229930027917 kanamycin Natural products 0.000 description 1
- 229960000318 kanamycin Drugs 0.000 description 1
- 229930182823 kanamycin A Natural products 0.000 description 1
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Classifications
-
- 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
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for producing amine monomers by degrading polyurethane through a chemical biological method, which comprises the following steps: (1) Under the action of a catalyst, carrying out an alcoholysis reaction on polyurethane and an alcoholysis agent to obtain an alcoholysis product; (2) In a buffer solution, performing enzymolysis reaction on the obtained alcoholysis product by using esterase to obtain an amine monomer; the esterases include esterases Aes72. According to the invention, polyurethane is degraded by combining a chemical method and a biological method, the preparation of TDA/MDA monomer is realized while the energy consumption is reduced, and the monomer generated after enzymolysis can be synthesized into isocyanate again, so that the recycling of raw materials is realized.
Description
Technical Field
The invention belongs to the field of biochemical engineering, and relates to a method for producing amine monomers by degrading aromatic polyurethane through a chemical biological method.
Background
Polyurethane (PU) plastic is one of five plastic with the largest production and consumption worldwide, and the product application relates to a plurality of fields of textile, building materials, automobiles, national defense and the like. The global plastic yield in 2019 reaches 3.68 hundred million tons, wherein the PU plastic yield accounts for 6% -7% of the total yield, and the PU plastic is the second largest polyester plastic in global yield, and the yield reaches 1470 ten thousand tons only in 2020 of China, and the consumption is about 1175 ten thousand tons. At present, the method for treating the PU waste plastics mainly comprises landfill, incineration, mechanical recovery, physicochemical reprocessing and the like, however, the traditional methods have the defect of being difficult to solve. Compared with other plastics, the PU waste plastics have smaller density, and the centralized landfill occupies a large amount of land, so that land resources are wasted. Incineration, while simple and does not occupy land, increases carbon emissions and harmful gases generated by incineration cause air pollution. Mechanical recycling has become an important means of waste plastic resource utilization, however, the recycled PU chips can only be used as a filler for toys, pillows and the like or as a substrate in the subsequent process (secondary mechanical recycling and raw material recycling), and the scope of secondary utilization is limited. In contrast, the biological means for realizing the biodegradation of the PU waste is regarded as an environment-friendly waste plastic treatment method with mild reaction conditions, and the high-value recycling of waste plastic resources can be realized.
However, the problems of low efficiency, poor environmental adaptability, poor industrial environment compatibility and the like of the degradation bacteria or enzyme discovered at present in the actual PU plastic degradation process are solved, and the degradation and the high-value recycling of the PU biological method are greatly different from the industrial requirements. The multi-disciplinary intersection realizes reasonable disposal and resource utilization of waste plastics. Due to the special structure and property of the plastic polymer, the biodegradation is taken as the only means, so that the efficient utilization of the waste plastic is difficult to realize. Through the integration of subjects such as chemistry, materialization, biochemical engineering, microbiology and the like, a technical system from plastic pretreatment to application test to engineering amplification and the like is established, so that the method is an effective method for realizing the reutilization of waste plastic resources and solving the environmental pollution and the resource waste of the waste plastic.
In the current raw material recovery of PU, chemical recovery research is the most extensive, and chemical recovery can adopt hydrolysis, acidolysis, ammonolysis, alcoholysis and other processes to realize the recovery of PU plastics to a certain extent. Historically, glycolysis has received the most widespread attention on an industrial scale, although other commercial technologies have recently emerged primarily for the polyol portion, current alcoholysis techniques are directed to separating polyols and diphenylamines to optimize the yield of PU plastics, particularly for polyols. Compared with the recovery of the polyol, the recovery of the diphenylamine needs to be reacted under the conditions of high temperature, high pressure, noble metal catalysts and the like, and the diphenylamine monomer is difficult to be completely converted.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for producing phenylenediamine monomers by degrading polyurethane through chemical and physical combination aiming at the defects of the prior art.
In order to solve the technical problems, the invention discloses a method for producing amine monomers by degrading polyurethane through a chemical biological method, which utilizes alcoholysis to prepare low-component amino acid methyl ester, and utilizes a biological enzyme method to degrade the low-component amino acid methyl ester at normal temperature and normal pressure to obtain diphenylamine monomers, so that the green preparation and recovery of the diphenylamine monomers are realized.
Specifically, the method comprises the steps of:
(1) Carrying out alcoholysis reaction on polyurethane and an alcoholysis agent under the action of a catalyst to obtain alcoholysis products, including polyether or polyester polyol, amino acid methyl ester and the like;
(2) In a buffer solution, performing enzymolysis reaction on the obtained alcoholysis product by using esterase to obtain a diphenylamine monomer; the esterases include esterases Aes72, i.e., the esterases are esterases Aes72, or the esterases Aes72 in combination with other esterases possessing urethane-bond activity.
In the step (1), the reaction is specifically that polyurethane is crushed and dried to obtain blocky drying materials; adding an alcoholysis agent into a reaction system, stirring and heating, exhausting air, adding a catalyst, adding polyurethane block baking materials under stirring for alcoholysis reaction, and cooling to obtain an alcoholysis product.
Wherein, the method of exhausting air is to introduce inert gas; in some embodiments nitrogen is vented.
In the step (1), inert gas is required to protect the reaction process; in some embodiments nitrogen is sparged.
In step (1), the polyurethane comprises polyurethane plastic.
In the step (1), the polyurethane comprises polyester PU, polyether PU and polyester polyether mixed PU; the polyester type PU comprises aromatic polyester type PU.
In step (1), the polyurethane comprises a TDI-based PU and an MDI-based PU.
In some embodiments, the polyurethane is a TDI-based polyester PU, a TDI-based polyether PU, an MDI-based polyester PU, an MDI-based polyether PU.
In step (1), the catalyst includes an amine compound, a tin compound, an alkali metal salt, and an alkali hydroxide.
Wherein the amine compounds include, but are not limited to, diethylamine and ethanolamine.
Wherein the tin compounds include, but are not limited to, dibutyl tin dilaurate, butyl tin oxide and hydroxybutyl tin oxide.
Wherein the alkali metal salts include, but are not limited to, potassium acetate, zinc acetate, and barium acetate.
Wherein the alkaline hydroxides include, but are not limited to, potassium hydroxide and sodium hydroxide.
Preferably, the catalyst is a tin compound, preferably dibutyl tin dilaurate.
In step (1), the catalyst is used in an amount of 0.1 to 5wt%, preferably 0.5 to 3wt%, preferably 1wt% of the polyurethane.
In the step (1), the alcoholysis agent comprises methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol or a mixture thereof, preferably ethanol, ethylene glycol, diethylene glycol, and more preferably diethylene glycol.
In the step (1), the mass ratio of the polyurethane to the alcoholysis agent is 1:1-10, preferably 1:1-6.
In step (1), the temperature of the reaction is 150 to 250 ℃, preferably 180 to 210 ℃.
In the step (1), the reaction is carried out under stirring.
Wherein the stirring speed is 50-1000rpm, preferably 200-500rpm.
In the step (2), the buffer solution comprises a phosphate buffer solution, tris-HCl buffer solution, preferably a phosphate buffer solution with pH of 6.5-7.5, tris-HCl buffer solution, further preferably a phosphate buffer solution (PB buffer solution), 50mM phosphate buffer solution, and pH=7.0.
In step (2), the alcoholysis product is added in an amount of 0.1% to 20% v/v, preferably 0.3% to 10% v/v, and more preferably 0.5% to 1% v/v.
In the step (2), the addition amount of the esterase is 0.1-10mg/mL, preferably 0.5-2mg/mL.
In the step (2), the specific enzyme activity of the esterase Aes72 is 67-75U/mg.
In the step (2), the temperature of the enzymolysis reaction is 25-80 ℃, preferably 37-60 ℃.
In the step (2), the enzymolysis reaction time is 5-72h, preferably 10-36h.
In step (2), the enzymatic hydrolysis is carried out in a shaking table, which is rotated at a speed of 50-1000rpm, preferably 200rpm.
In the step (2), the enzymolysis reaction is finished, and the reaction liquid is filtered by a filter membrane to obtain diphenylamine monomers; preferably, the filter is a 0.22 μm filter.
In the step (2), the diphenylamine monomer comprises 2, 4-diaminotoluene 2,4-TDA, 2, 6-diaminotoluene 2,6-TDA, 4-diaminodiphenylmethane 4,4-MDA and 2, 4-diaminodiphenylmethane 2,4-MDA.
According to the invention, polyurethane is degraded by combining a chemical method and a biological method, the preparation of TDA/MDA monomer is realized while the energy consumption is reduced, and the monomer generated after enzymolysis can be synthesized into isocyanate again, so that the recycling of raw materials is realized.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
according to the invention, through the combination of chemical alcoholysis and enzymolysis, an alcoholysis product containing polyol and carbamate is prepared through alcoholysis reaction, the obtained polyol can be recycled through subsequent purification, meanwhile, the oligomer with carbamate bonds, which is produced through alcoholysis, is completely depolymerized under mild conditions by enzyme Aes72 to produce diamine monomer (MDA/TDA), so that side reaction is reduced, the environment-friendly effect is realized, harmless recovery of plastics is realized, and the problems of high temperature and high pressure environment and high energy consumption in the preparation of the diamine monomer by carbamate in the prior art are effectively solved.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 shows the results of LC-MS analysis of the urethane product components after TDI-based polyether type PU alcoholysis.
FIG. 2 is an HPLC analysis of the change of the TDI-based polyether PU alcoholysis product before and after enzymatic hydrolysis.
FIG. 3 shows the formation of enzymolysis products of alcoholysis products of four aromatic polyurethane plastics (TDI-based polyether PU, TDI-based polyester PU, MDI-based polyether PU, MDI-based polyester PU); the TDA concentration is the total concentration of 2,4-TDA and 2,6-TDA in the undiluted reaction solution, and the MDA concentration is the concentration of 4,4-MDA in the undiluted reaction solution.
Fig. 4 is a FITR characterization of PU plastics for different application scenarios.
FIG. 5 shows the TDA/MDA generated by combining the PU plastics in different application scenes by a chemical biological method through HPLC.
Fig. 6 is a TDA and MDA concentration standard curve.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The TDI-based polyether polyurethane and TDI-based polyester polyurethane described in the examples below were purchased from Nantong university Co., ltd; the MDI-based polyether polyurethane and MDI-based polyester polyurethane are available from soprima, france.
The esterase used for enzymolysis of the alcoholysis product is Aes72; wherein, the enzyme activity of the p-NPB used by the Aes72 is defined as: hydrolysis of p-NPB at 37℃per minute to give 1. Mu. Mol of p-nitrophenol was defined as a protease activity unit.
Wherein, the protease activity formula is: protease activity = a/(B x C), where a is the amount of p-nitrophenol produced (μmol), B is the reaction time (min), and C is the amount of enzyme added to the reaction (mL).
Wherein specific enzyme activity = protease activity (U/mL)/protein concentration (mg/mL).
The specific enzyme activity of Aes72 was detected to be 67U/mg.
The preparation method of Aes72 comprises inoculating Aes72 protein expression strain into LB medium, adding 50 μg/mL of kanamycin, culturing at 37deg.C for 12-16 hr, adding bacterial liquid into liquid LB medium according to 1% v/v inoculum size, culturing at 37deg.C, and culturing until bacterial liquid reaches OD 600 Taking out when the concentration is 0.6-0.8, adding 0.1mM IPTG, and shake culturing at 18deg.C for 24 hr; centrifuging at 8000rpm for 10min to obtain thallus, crushing cells with an ultrasonic crusher, centrifuging at 8000rpm for 10min to obtain supernatant, and obtaining Aes72 protein.
Phosphate buffer (PB buffer), 50mM phosphate buffer, ph=7.0 used in the examples of the present invention.
In the HPLC analysis of the alcoholysis product and the enzymolysis product in the embodiment of the invention, a 1260 Infinicity II high performance liquid chromatograph (Agilent Technologies) is adopted by HPLC, and the specific detection method comprises the following steps:
liquid chromatographic column: agilent 5HC-C18 (2) 150X 4.6mm;
detection wavelength: 240nm;
column temperature: 30 ℃;
flow rate: 1mL/min;
sample injection amount: 10. Mu.L;
the mobile phases are water and acetonitrile respectively;
gradient elution: 0-5min, water volume fraction of 90%, acetonitrile volume fraction of 10%;5-14min, the water volume fraction is changed from 90% to 35%, and the acetonitrile volume fraction is changed from 10% to 65%.
MDA standard curve preparation (comprising 4, 4-MDA): 19.8mg of MDA was weighed out and dissolved in 10mL of ethanol to prepare a mother liquor of 10 mM. They were diluted to 2.5mM, 1mM, 0.5mM, 0.25mM, 0.125mM, 0.06125mM standard samples, respectively. Peak areas corresponding to different concentrations were analyzed by HPLC to produce a plot of MDA concentration, as shown in fig. 6.
TDA standard curve preparation (comprising 2,4-TDA and 2, 6-TDA): 12.2mg of TDA was weighed and dissolved in 10mL of ethanol to prepare a 10mM mother liquor. They were diluted to 10mM, 5mM, 2mM, 1mM, 0.5mM, 0.25mM, 0.125mM, 0.06125mM standard samples, respectively. The peak areas corresponding to the different concentrations were analyzed by HPLC to produce a TDA concentration profile, which is shown in fig. 6.
MDA content measurement: the peak areas determined by HPLC for four experiments were substituted into the standard curve to calculate the corresponding MDA concentrations.
TDA content measurement: the peak areas determined by HPLC for four experiments were substituted into the standard curve to calculate the corresponding TDA concentrations.
In the examples described below, the air was removed by passing an inert gas through the catalyst prior to addition.
The alcoholysis reaction described in the examples below was carried out under the protection of inert gas.
The blank set described in the examples below is one in which no enzyme was added as compared to the experimental set.
Example 1: TDA monomer produced by degrading TDI-based polyether PU
40g of diethylene glycol is weighed and added into a four-neck flask, the mixture is preheated to 200 ℃, 1% w/w of dibutyltin dilaurate is added, 40g of TDI-based polyether PU after crushing is slowly added under the stirring of 300rpm until the TDI-based polyether PU is completely dissolved, the temperature is kept at 200 ℃ for 2 hours, the mixture is cooled to room temperature, and the reaction is finished to obtain an alcoholysis product, wherein the result of LC-MS of the distribution of carbamate components is shown as figure 1, and a carbamate low-molecular compound is produced after chemical alcoholysis.
And (3) carrying out enzymolysis on the alcoholysis product by using a phosphate buffer system, and setting an experimental group and a blank control group. 6mL of the reaction system was used, pH7.0 was used, the amount of enzyme Aes72 added was 0.1mg/mL, and the amount of the alcoholysis product added was 600. Mu.L. Then, after the two reaction solutions were allowed to react for 48 hours at 37℃or 50℃in a shaker at 200rpm, the reaction solutions were appropriately diluted and subjected to a 0.22 μm filter, and the treated samples were subjected to HPLC analysis, the results of which are shown in FIG. 2 (37 ℃) and FIG. 3.
As can be seen from FIG. 2, after 48 hours of the enzymatic hydrolysis reaction, all urethane is enzymatically hydrolyzed to produce TDA monomers, indicating that Aes72 can efficiently hydrolyze polyurethane plastic alcoholysis products to produce TDA monomers, which are all converted to TDA within 48 hours. As can be seen from fig. 3, the full conversion of carbamate was achieved at 20h as the alcoholysis product.
Example 2: TDA monomer produced by degrading TDI-based polyester PU
120g of diethylene glycol is weighed and added into a four-neck flask, the mixture is preheated to 200 ℃, 1% w/w of dibutyltin dilaurate is added, 40g of crushed TDI-based polyester PU is slowly added under the stirring of 250rpm until the TDI-based polyester PU is completely dissolved, the mixture is kept at 200 ℃ for 2 hours, and the mixture is cooled to room temperature, and the reaction is finished to obtain an alcoholysis product.
And (3) carrying out enzymolysis on the alcoholysis product by using a phosphate buffer system, and setting an experimental group and a blank control group. 6mL of the reaction system was used, pH7.0 was used, the amount of enzyme Aes72 added was 0.1mg/mL, and the amount of the alcoholysis product added was 300. Mu.L. Then, after the two groups of reaction solutions were placed in a shaker at 37℃or 50℃and reacted at 200rpm for 48 hours, the reaction solutions were appropriately diluted and subjected to a 0.22 μm filter membrane treatment, and HPLC analysis was performed on the treated samples, and the results are shown in FIG. 3.
Example 3: MDA monomer produced by degrading MDI-based polyether PU
240g of diethylene glycol is weighed and added into a four-neck flask, the mixture is preheated to 200 ℃, 1% w/w of dibutyltin dilaurate is added, 40g of crushed TDI-based polyester PU is slowly added under the stirring of 300rpm until the TDI-based polyester PU is completely dissolved, the mixture is kept at 200 ℃ for 2 hours, the mixture is cooled to room temperature, and the reaction is finished to obtain an alcoholysis product.
And (3) carrying out enzymolysis on the alcoholysis product by using a phosphate buffer system, and setting an experimental group and a blank control group. 6mL of the reaction system was used, pH7.0 was used, the amount of enzyme Aes72 added was 1mg/mL, and the amount of the alcoholysis product added was 300. Mu.L. Then, after the two groups of reaction solutions were placed in a shaker at 37℃or 50℃at 200rpm for 72 hours, the reaction solutions were appropriately diluted and subjected to a 0.22 μm filter treatment, and the treated samples were subjected to HPLC analysis, the results of which are shown in FIG. 3.
Example 4: MDA monomer produced by degrading MDI-based polyester PU
240g of diethylene glycol is weighed and added into a four-neck flask, the mixture is preheated to 210 ℃, 1% w/w of dibutyltin dilaurate is added, 40g of crushed MDI-based polyester PU is slowly added under stirring at 270rpm until the mixture is completely dissolved, the temperature is kept at 200 ℃ for 2 hours, the mixture is cooled to room temperature, and an alcoholysis product is obtained after the reaction is finished.
And (3) carrying out enzymolysis on the alcoholysis product by using a phosphate buffer system, and setting an experimental group and a blank control group. 6mL of the reaction system was used, pH7.0 was used, the amount of enzyme Aes72 added was 1mg/mL, and the amount of the alcoholysis product added was 300. Mu.L. Then, after the two groups of reaction solutions were placed in a shaker at 37℃or 50℃at 200rpm for 72 hours, the reaction solutions were appropriately diluted and subjected to a 0.22 μm filter treatment, and the treated samples were subjected to HPLC analysis, the results of which are shown in FIG. 3.
In examples 1-4 above, the carbamate in the alcoholysis product can be efficiently converted to the diamine monomer and is more efficient for the carbamate conversion of TDI-based PU.
Example 5: producing TDA/MDA by degrading PU of different application scenes
FITR analysis is performed on PUs of different application scenarios, the results of which are shown in FIG. 4. 3330cm -1 N-H stretching vibration peak, 1538cm -1 The absorption peak of N-H deformation vibration of the amide II band is 1730cm -1 C=o stretching vibration peak, 1220cm -1 An aromatic C-O absorption band at 1073cm -1 The absorption band of C-O-C group nearby, the type of each PU can be judged from the infrared characteristic peaks of each PU in figure 4, and the protective sleeveThe bowl-washing wiper, the car mat, the mattress is polyether type PU, the heat preservation pipe, the heat preservation board, the adhesive is polyester type PU, the pillow core is polyester polyether type PU.
240g of diethylene glycol is weighed and added into a four-necked flask, preheated to 200 ℃, added with 1% w/w of dibutyltin dilaurate, stirred at 300rpm and slowly added with 40g of crushed commercial PU until the commercial PU is completely dissolved, kept at 200 ℃ for 2 hours, cooled to room temperature and subjected to reaction to obtain an alcoholysis product.
And (3) carrying out enzymolysis on the alcoholysis product by using a phosphate buffer system, and setting an experimental group and a blank control group. 6mL of the reaction system was used, pH7.0 was used, the amount of enzyme Aes72 added was 1mg/mL, and the amount of the alcoholysis product added was 300. Mu.L.
Then, the two reaction solutions were placed in a shaking table at 37℃and 200rpm for 48 hours, and then the reaction solutions were diluted appropriately and treated with a 0.22 μm filter, and HPLC analysis was performed on the treated samples.
The results are shown in FIG. 5, where all of the carbamate in the TDI-based PU alcoholysis product is converted to TDA and most of the carbamate in the MDI-based PU alcoholysis product is converted to MDA. From FIG. 5, it can be seen that the Aes72 enzyme can act effectively on urethane or ester linkages and release TDA/MDA monomers; proved by chemical alcoholysis and biological Aes72 enzymolysis, the TDA/MDA monomer can be effectively prepared, and closed-loop recovery of the monomer is promoted.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A method for producing amine monomers by degrading polyurethane through a combination of chemical and biological methods, which is characterized by comprising the following steps:
(1) Under the action of a catalyst, carrying out an alcoholysis reaction on polyurethane and an alcoholysis agent to obtain an alcoholysis product;
(2) In a buffer solution, performing enzymolysis reaction on the obtained alcoholysis product by using esterase to obtain an amine monomer; the esterases include esterases Aes72.
2. The method according to claim 1, wherein in step (1), the catalyst comprises an amine compound, a tin compound, an alkali metal salt, and an alkali hydroxide; preferably, the amine compound comprises diethylamine and ethanolamine; preferably, the tin compound comprises dibutyl tin dilaurate, butyl tin oxide and hydroxybutyl tin oxide; preferably, the alkali metal salts include potassium acetate, zinc acetate and barium acetate; preferably, the alkaline hydroxide comprises potassium hydroxide and sodium hydroxide.
3. The method of claim 1, wherein in step (1), the polyurethane comprises polyurethane plastic.
4. The method of claim 1, wherein in step (1), the alcoholysis agent comprises methanol, ethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, or mixtures thereof; preferably, the mass ratio of the polyurethane to the alcoholysis agent is 1:1-10.
5. The process of claim 1, wherein in step (1), the temperature of the reaction is 150-250 ℃.
6. The method according to claim 1, wherein in the step (1), the reaction is performed in a stirred state; preferably, the stirring is at a rate of 50-1000rpm.
7. The method of claim 1, wherein in step (2), the buffer comprises a phosphate buffer, tris-HCl buffer.
8. The process according to claim 1, characterized in that in step (2) the alcoholysis product is added in an amount of 0.1-20% v/v, preferably 0.3-10% v/v, further preferably 0.5-1% v/v.
9. The method according to claim 1, wherein in step (2), the esterase is added in an amount of 0.1-10mg/mL; preferably, the specific enzyme activity of the esterase Aes72 is 67-75U/mg.
10. The method according to claim 1, wherein in step (2), the temperature of the enzymatic hydrolysis reaction is 25-80 ℃; preferably, the enzymolysis reaction time is 5-72h.
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| WO2021032513A1 (en) * | 2019-08-16 | 2021-02-25 | Covestro Intellectual Property Gmbh & Co. Kg | Process for the decomposition of polyether-polyurethane |
| CN113115588A (en) * | 2018-06-21 | 2021-07-13 | 科思创知识产权两合公司 | Novel carbamate hydrolase for enzymatic decomposition of polyurethane |
| CN115896193A (en) * | 2023-02-03 | 2023-04-04 | 南京工业大学 | Method for complete depolymerization of thermoplastic polyester type polyurethane plastic by double enzymes |
| CN115975983A (en) * | 2022-11-07 | 2023-04-18 | 北京理工大学 | Application of alkali-resistant broad-spectrum plastic degrading enzyme |
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| CN113115588A (en) * | 2018-06-21 | 2021-07-13 | 科思创知识产权两合公司 | Novel carbamate hydrolase for enzymatic decomposition of polyurethane |
| WO2021032513A1 (en) * | 2019-08-16 | 2021-02-25 | Covestro Intellectual Property Gmbh & Co. Kg | Process for the decomposition of polyether-polyurethane |
| CN114286837A (en) * | 2019-08-16 | 2022-04-05 | 科思创知识产权两合公司 | Method for decomposing polyether polyurethane |
| CN115975983A (en) * | 2022-11-07 | 2023-04-18 | 北京理工大学 | Application of alkali-resistant broad-spectrum plastic degrading enzyme |
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