CN117603043A - Method for upgrading polyester material into dicarboxylic acid ester and ethylene carbonate - Google Patents
Method for upgrading polyester material into dicarboxylic acid ester and ethylene carbonate Download PDFInfo
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- CN117603043A CN117603043A CN202311581833.7A CN202311581833A CN117603043A CN 117603043 A CN117603043 A CN 117603043A CN 202311581833 A CN202311581833 A CN 202311581833A CN 117603043 A CN117603043 A CN 117603043A
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- polyester
- ethylene carbonate
- dicarboxylic acid
- upgrading
- acid ester
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 42
- -1 dicarboxylic acid ester Chemical class 0.000 title claims abstract description 40
- 229920000728 polyester Polymers 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 59
- 239000002699 waste material Substances 0.000 claims abstract description 37
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 78
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 56
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 13
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000012691 depolymerization reaction Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920000921 polyethylene adipate Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 35
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 4
- 238000006140 methanolysis reaction Methods 0.000 abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000000269 nucleophilic effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 abstract description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 abstract 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 14
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 14
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 description 1
- 240000006890 Erythroxylum coca Species 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000008957 cocaer Nutrition 0.000 description 1
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a method for upgrading polyester materials into dicarboxylic acid ester and ethylene carbonate, and relates to comprehensive utilization of waste resources and cascade utilization of raw materials. According to the method, a plurality of green ionic liquid catalysts are used for catalyzing PET methanolysis reaction, then ethylene glycol generated by in-situ capture of dimethyl carbonate is subjected to nucleophilic cyclization to form five-membered cyclic ethylene carbonate, and the equilibrium of the pulling reaction moves forward to completely depolymerize PET waste. The products of the process of the invention are dimethyl terephthalate and five-membered cyclic ethylene carbonate. The invention can be used for depolymerizing and upgrading waste PET materials, and can also be used for other similar polyesters, such as polyethylene glycol succinate, polyethylene glycol adipate and polyethylene 2, 5-furandicarboxylate, and the products are corresponding dimethyl succinate, dimethyl adipate and 2, 5-furandicarboxylate.
Description
Technical Field
The invention relates to a method for producing dimethyl terephthalate and ethylene carbonate by depolymerizing and upgrading high-selectivity PET, which relates to comprehensive utilization of waste resources and cascade utilization of raw materials. More particularly, the present invention relates to a process for the methanolic depolymerization of a wide variety of polyester feedstocks including PET and to obtain high yields of dicarboxylic acid esters and ethylene carbonate.
Background
Landfill, incineration, mechanical recovery and chemical recovery are four main methods for treating waste plastics at present. In general, landfill and incineration treatment do not produce value-added products, and secondary ecological environmental pollution of the atmosphere and soil is easily caused. The mechanical physical recycling waste has certain economic value, but the quality and performance of the derivative materials gradually decrease with the increase of the recycling times. Compared with the above strategy, chemical recovery can cut off chemical bonds in waste plastics at a molecular level, reconstruct a molecular structure, extend a material value chain, and have a milder treatment mode and lower productivity consumption than other recovery methods. And the strategy focuses on realizing the recovery of monomers, petroleum fuels and chemicals, is a feasible strategy with both economy and environment, and enables the plastic circulating value chain to have stronger market sustainability. However, ethylene glycol produced in the reaction is difficult to separate and recover due to its high boiling point property, and is generally discarded. The ethylene glycol units of PET, however, also have a great potential for conversion to high value chemicals, and have been used for conversion of precursor materials to higher value-added small molecule carboxylic acids and light olefins. The innovative recycling of ethylene glycol units is therefore an important problem to be solved in the field of PET depolymerization at present.
The relatively high contamination resistance of methanolysis systems makes it a cost-effective option for the treatment of complex PET-based waste materials. However, generally, the methanol decomposition requires a higher temperature (generally more than or equal to 200 ℃) to promote the depolymerization reaction of the slowly decomposed PET, the DMT yield of the product is only between 80 and 85 percent, and in order to pursue the high DMT yield, a small amount of research projects of supercritical methanol or microwave-assisted methanol decomposition systems exist at present, but the research projects are not advocated in consideration of the factors such as equipment operation, economic benefit and the like. In addition, the need for excess methanol or methanol as a solvent to facilitate the reaction is one of the limitations in the current art.
The ionic liquid is a good green catalyst which is not easy to volatilize, has good thermal stability and strong solubility, has designability and has been widely applied to the separation and catalysis fields. Therefore, developing a mild and efficient methanol decomposition strategy using ionic liquids is important.
Ethylene Carbonate (EC), an excellent organic solvent, can dissolve a variety of polymers and is widely used in organic synthesis. Typically, ethylene carbonate is obtained from nucleophilic reaction of ethylene glycol and dimethyl carbonate, and because of its five-membered ring stable structure, the equilibrium of the PET depolymerization reaction is promoted to proceed forward, so that EG components can be captured from waste PET with orientation of ethylene carbonate, thereby achieving high-value conversion of ethylene glycol while solving the problem of ethylene glycol separation. The high-value recycling strategy is beneficial to complete comprehensive utilization on the molecular level of PET waste, is beneficial to alleviating petroleum resource consumption to a certain extent, and improves the regeneration value of PET waste.
Disclosure of Invention
Aiming at the requirements of PET waste plastic depolymerization and product directional upgrading and the defects existing in the prior art, the invention provides a method for upgrading polyester materials into dicarboxylic acid ester and ethylene carbonate. As typified by PET, this process uses an ionic liquid catalyst to catalyze the methanolysis of PET, capturing depolymerization in situ from dimethyl carbonate to produce the product ethylene glycol, followed by nucleophilic cyclization to form ethylene carbonate.
The specific technical scheme adopted by the invention is as follows:
a method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate, comprising:
s1, placing crushed polyester materials, methanol, an ionic liquid catalyst and dimethyl carbonate into a reaction kettle to form a reaction system; wherein the polyester material is polyethylene terephthalate (PET), polyethylene succinate, polyethylene adipate and polyethylene 2, 5-furandicarboxylate; the ionic liquid catalyst is imidazole ionic liquid [ Bmim ] [ Cl ], [ Emim ] [ Br ], [ Mmim ] [ I ], [ Emim ] [ Ac ] or [ Bmim ] [ Ac ], and the structural formula is as follows:
s2, placing the reaction kettle containing the reaction system at a depolymerization temperature of 100-140 ℃ for a depolymerization reaction for 2-4 hours, and cooling to room temperature after the reaction is completed to obtain a depolymerization product containing dicarboxylic acid ester and ethylene carbonate.
Preferably, the amount of dimethyl carbonate added in the reaction system is 2 to 4mL/mmol of the polyester-based material, and more preferably, the amount of dimethyl carbonate added is 3.5mL/mmol of the polyester-based material.
Preferably, the ionic liquid catalyst is added to the reaction system in an amount of 3 to 10mol%, more preferably 5mol%, based on the polyester-based material.
Preferably, the methanol solvent is added in an amount of 4 to 30 times the molar amount of the polyester-based material in the reaction system.
Preferably, the polyester material is waste of polyethylene terephthalate material.
Further, the waste is in the form of waste bottles made of polyethylene terephthalate, waste films of matrixes, color binding ropes or non-woven fabrics.
Furthermore, the waste is required to be crushed into centimeter-level slices, particles or powder before being added into the reaction kettle, so that the recycling effect of the waste PET material can be ensured, and the dimethyl terephthalate and the ethylene carbonate can be obtained in a directional upgrading and high yield.
Preferably, the depolymerization temperature is 130 ℃.
Preferably, the depolymerization time is preferably 2 hours.
Preferably, the ionic liquid catalyst is preferably [ Emim ] [ Ac ].
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the bottleneck problem that the PET depolymerization is limited to react incompletely due to thermomechanical limitation is overcome by capturing the ethylene glycol coupling PET depolymerization by adopting the dimethyl carbonate, and the complete depolymerization of PET and the directional upgrading recovery of ethylene glycol at 130 ℃ can be realized by adopting the ionic liquid as a transesterification catalyst and combining hydrogen bond promotion and ethylene glycol coupling reaction.
(2) The waste plastic PET methanol depolymerization strategy developed by the invention has the advantages of short reaction time, mild condition and high catalytic efficiency, and the strategy has wide application range, various waste PET raw material types and various waste PET materials such as: various PET waste bottles, PET matrix waste films, PET color binding ropes and PET non-woven fabrics can be used for efficiently finishing directional upgrading conversion in a short time.
(3) The PET waste plastic matrix material of the invention can be replaced by various polyesters with similar glycol units such as: the polyethylene glycol succinate, the polyethylene glycol adipate and the polyethylene 2, 5-furandicarboxylate show the high applicability range of the strategy to a certain extent, further widen the field range of waste plastic treatment materials, and can finish corresponding conversion to obtain dicarboxylic acid ester and ethylene carbonate on the premise of ensuring high depolymerization efficiency and rapid reaction time.
Detailed Description
The foregoing objects, features and advantages of the invention will be more readily apparent from the following detailed description of the invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
The invention provides a method for upgrading polyester materials into dicarboxylic acid esters and ethylene carbonate, which uses a plurality of green ionic liquid catalysts to catalyze PET methanolysis reaction, then dimethyl carbonate captures generated ethylene glycol in situ, and the ethylene glycol is nucleophilic cyclized to form five-membered cyclic ethylene carbonate, so that the balance of the pulling reaction moves forward, and PET waste is completely depolymerized. The method comprises the following specific steps:
s1, placing crushed polyester materials, methanol, an ionic liquid catalyst and dimethyl carbonate into a reaction kettle to form a reaction system;
s2, placing the reaction kettle containing the reaction system at a depolymerization temperature of 100-140 ℃ for a depolymerization reaction for 2-4 hours, and cooling to room temperature after the reaction is completed to obtain a depolymerization product containing dicarboxylic acid ester and ethylene carbonate.
In the following examples, the raw materials in the above reaction system are as follows: the polyester material is polyethylene terephthalate (PET), polyethylene succinate, polyethylene adipate and polyethylene 2, 5-furandicarboxylate; the ionic liquid catalyst is [ Bmim ]][Cl]、[Emim][Br]、[Mmim][I]、[Emim][SO 3 ]、[EMIm][BF 4 ]、[Emim][Ac]Or [ Bmim ]][Ac]The structural formula is as follows:
if the polyester material is PET, pure PET or PET waste can be used. The waste is in the form of PET waste bottles, PET matrix waste films, PET color strapping ropes or PET non-woven fabrics. But the waste is crushed into centimeter-level flakes, granules or powder before being added into the reaction kettle.
The reaction results under the different starting materials and parameters are shown below by way of example.
Example 1
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Bmim ] [ Cl ] (10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 95% and the yield of ethylene carbonate was 69% in this example.
Example 2
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Emim ] [ Br ] (10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 92% and the yield of ethylene carbonate was 60% in this example.
Example 3
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Mmim ] [ I ] (10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 93% and the yield of ethylene carbonate was 65% in this example.
Example 4
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Emim ] [ Ac ] (10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 94% and the yield of ethylene carbonate was 82% in this example.
Example 5
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Bmim ] [ Ac ] (10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 95% and the yield of ethylene carbonate was 69% in this example.
Example 6
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Emim ] [ Ac ] (10 mol%), 1mL of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 98% and the yield of ethylene carbonate was 84% in this example.
Example 7
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Emim ] [ Ac ] (10 mol%), 8mmol of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 99% and the yield of ethylene carbonate was 87% in this example.
Example 8
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a temperature control program was charged with 0.192 g of CR-purity PET powder (1 mmol), [ Emim ] [ Ac ] (5 mol%), 8mmol of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 99% and the yield of ethylene carbonate was 91% in this example.
Example 9
Waste PET plastic bottles (brands such as cola, coca dubia and farmer mountain spring) are crushed in centimeter level in advance, then an autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a program temperature controller is filled with centimeter level crushed materials (1 mmol) of 0.192 g PET plastic bottle, [ Emim ] [ Ac ] (5 mol%), 8mmol methanol and 3.5mL dimethyl carbonate, and after the autoclave reactor is placed, stirring and heating are started. The reaction system was warmed to 130℃and reacted at that temperature for 3 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 99% and the yield of ethylene carbonate was 91% in this example.
Example 10
Into an autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a program temperature controller were charged 0.144g of polyethylene succinate (1 mmol), [ Emim ] [ Ac ] (5 mol%), 8mmol of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, the obtained mixed solution is the product, the yield is measured by HNMR, and mesitylene is taken as an internal standard, and the result shows that the yield of the dimethylsuccinyl formate of the embodiment is 99% and the yield of the ethylene carbonate is 95%.
Example 11
An autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a program temperature controller was charged with 0.172 g of polyethylene adipate (1 mmol), 5mol% of Emim Ac, 8mmol of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The yield was determined by H NMR and mesitylene was used as an internal standard, which indicated that this example gave 99% yield of dimethyl adipate and 75% yield of ethylene carbonate.
Example 12
Into an autoclave reactor equipped with an electromagnetic stirrer, a thermocouple and a program temperature controller were charged 0.192 g of ethylene 2, 5-furandicarboxylate (1 mmol), [ Emim ] [ Ac ] (5 mol%), 8mmol of methanol and 3.5mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2.5 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The yield was determined by H NMR and mesitylene was found to be an internal standard, which indicated that the yield of dimethyl furan-2, 5-dicarboxylate of this example was 99% and that of ethylene carbonate was 80%.
Comparative example 1
Into an autoclave reactor equipped with an electromagnetic stirrer, a thermocouple, and a temperature-programmed instrument, 0.192 g of CR-purity PET powder (1 mmol) [ Emim ] was charged][SO 3 ](10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, the temperature is reduced to room temperature, and the obtained mixed solution is the product. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 0% and the yield of ethylene carbonate was 0% in this example.
Comparative example 2
Into an autoclave reactor equipped with an electromagnetic stirrer, a thermocouple, and a temperature-programmed apparatus, 0.192 g of CR-purity PET powder (1 mmol) was charged, [ EMIm ]][BF 4 ](10 mol%), 1mL of methanol and 3mL of dimethyl carbonate, and after the autoclave reactor was set, stirring and heating were started. The reaction system was warmed to 130℃and reacted at that temperature for 2 hours. After the reaction is completed, cooling to room temperature to obtain a mixed solutionThe product is obtained. The resulting mixture was diluted with methylene chloride, and the yield of the diluted solution was measured by GC, and mesitylene was used as an internal standard, which indicated that the yield of dimethyl terephthalate was 0% and the yield of ethylene carbonate was 0% in this example.
Examples 1 to 12 and comparative examples 1 to 2 show that not all ionic liquids can be used as catalysts for the depolymerization reaction, and that the five ionic liquid catalysts [ Bmim ] [ Cl ], [ Emim ] [ Br ], [ Mmim ] [ I ], [ Emim ] [ Ac ] or [ Bmim ] [ Ac ] have extremely high catalytic performance in catalyzing the depolymerization of polyesters to carboxylic esters and boric esters, compared to the other ionic liquid catalysts.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.
Claims (10)
1. A method for upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate, comprising:
s1, placing crushed polyester materials, methanol, an ionic liquid catalyst and dimethyl carbonate into a reaction kettle to form a reaction system; wherein the polyester material is polyethylene terephthalate (PET), polyethylene succinate, polyethylene adipate and polyethylene 2, 5-furandicarboxylate; the ionic liquid catalyst is imidazole ionic liquid [ Bmim ] [ Cl ], [ Emim ] [ Br ], [ Mmim ] [ I ], [ Emim ] [ Ac ] or [ Bmim ] [ Ac ], and the structural formula is as follows:
s2, placing the reaction kettle containing the reaction system at a depolymerization temperature of 100-140 ℃ for a depolymerization reaction for 2-4 hours, and cooling to room temperature after the reaction is completed to obtain a depolymerization product containing dicarboxylic acid ester and ethylene carbonate.
2. The method for upgrading a polyester material to a dicarboxylic acid ester and a vinyl carbonate according to claim 1, wherein the amount of dimethyl carbonate added in the reaction system is 2-4 mL/mmol of the polyester material.
3. The method for upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 1, wherein the ionic liquid catalyst is added in an amount of 3 to 10mol% of the polyester-based material in the reaction system.
4. The method for upgrading a polyester-based material to a dicarboxylic acid ester and a vinyl carbonate according to claim 1, wherein the methanol solvent is added in an amount of 4 to 30 times by mole of the polyester-based material in the reaction system.
5. The method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 1, wherein the polyester-based material is a waste of polyethylene terephthalate material.
6. The method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 5, wherein the waste is in the form of polyethylene terephthalate waste bottles, matrix waste films, color ropes or nonwoven fabrics.
7. The method for upgrading polyester-based materials to dicarboxylic acid esters and ethylene carbonate according to claim 6, wherein the waste is pre-crushed into centimeter-sized flakes, granules or powder before being fed into the reactor.
8. The method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 1, wherein the depolymerization temperature is preferably 130 ℃.
9. The method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 1, wherein the depolymerization time is preferably 2 hours.
10. The method of upgrading a polyester-based material to a dicarboxylic acid ester and a ethylene carbonate according to claim 1, wherein the ionic liquid catalyst is preferably [ Emim ] [ Ac ].
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117986094A (en) * | 2024-03-15 | 2024-05-07 | 浙江大学 | Method for directionally preparing bisphenol A dimethyl ether by PC plastic polymerization one-step method |
| CN117986114A (en) * | 2024-03-15 | 2024-05-07 | 浙江大学 | Alkylation method of polyester material with participation of carbonic ester or carboxylic ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117986094A (en) * | 2024-03-15 | 2024-05-07 | 浙江大学 | Method for directionally preparing bisphenol A dimethyl ether by PC plastic polymerization one-step method |
| CN117986114A (en) * | 2024-03-15 | 2024-05-07 | 浙江大学 | Alkylation method of polyester material with participation of carbonic ester or carboxylic ester |
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