CN113214077A - Method for degrading thermoplastic polyethylene terephthalate - Google Patents
Method for degrading thermoplastic polyethylene terephthalate Download PDFInfo
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- CN113214077A CN113214077A CN202110484485.6A CN202110484485A CN113214077A CN 113214077 A CN113214077 A CN 113214077A CN 202110484485 A CN202110484485 A CN 202110484485A CN 113214077 A CN113214077 A CN 113214077A
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- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 104
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 23
- 230000000593 degrading effect Effects 0.000 title claims abstract description 11
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 5
- 239000004416 thermosoftening plastic Substances 0.000 title description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 23
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 22
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 4
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 125000004076 pyridyl group Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 46
- 239000000706 filtrate Substances 0.000 description 42
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 27
- 239000000126 substance Substances 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 17
- LKUDPHPHKOZXCD-UHFFFAOYSA-N 1,3,5-trimethoxybenzene Chemical compound COC1=CC(OC)=CC(OC)=C1 LKUDPHPHKOZXCD-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 9
- 239000002608 ionic liquid Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000034659 glycolysis Effects 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013501 data transformation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GNVILSSSAMKPLR-UHFFFAOYSA-N methyl ethaneperoxoate Chemical compound COOC(C)=O GNVILSSSAMKPLR-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- 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
- B01J31/0287—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 atoms other than nitrogen as cationic centre
- B01J31/0288—Phosphorus
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for degrading thermoplastic plastic polyethylene terephthalate, belonging to the technical field of polyester degradation. The catalyst used in the method has the advantages that the raw materials are simple and easy to obtain, the catalyst can be synthesized by a one-step method, no metal residue exists in the whole reaction system, and even if the catalyst load is lower than 2%, a good catalytic effect (the degradation rate is more than or equal to 90%) can be obtained. In addition, the invention expands the solvent range of PET alcoholysis, and under the condition of the catalyst, the PET degradation rate of more than 90 percent is obtained by using ethylene glycol, propylene glycol, butanediol, hexanediol, butanediamine, hexamethylenediamine, monoethanolamine and diethanolamine as solvents.
Description
Technical Field
The invention belongs to the technical field of polyester degradation, and relates to a method for degrading polyethylene terephthalate (PET) by using ionic liquid synthesized by taking trioctylphosphine and diester as raw materials.
Background
Polyethylene terephthalate (PET) is a thermoplastic polymer. Because of its high chemical stability, strong chemical strength and good biological safety, it is widely used in synthetic fiber, plastic film and food and beverage packaging (Macromol. Mater. Eng.,2007,292, 128-146). However, also due to these excellent physical properties, PET is difficult to naturally degrade by microorganisms, and the resulting white contamination has many adverse effects on the environment (Science,2016,351, 1196-1199). Despite this, the worldwide demand for PET is still high, and only in 2017, the global PET production has exceeded 3000 million tons, while PET recycled by processing does not exceed 15% on average (polym. Therefore, efficient recycling of waste PET has been very slow.
The current treatment of waste PET mainly includes physical and chemical methods. The physical method mainly comprises an embedding method and an incineration treatment, and the chemical method mainly comprises hydrolysis, ammonolysis and alcoholysis. The present invention will focus on alcoholysis of PET, particularly ethylene glycol, and the equations involved are shown in the above equation. Because the glycolysis of PET generally needs high temperature (180 ℃ C. and 200 ℃ C.), the current report of using glycol as a raw material in the chemical industry to degrade PET mainly focuses on designing a catalyst with good thermal stability. In 2018, Haritz Sardon proposed a heat stable protonated ionic salt [ HTBD ] [ MSA ], which can be completely degraded in 3h by catalyzing PET degradation at 180 ℃, and the yield of the obtained degraded monomer ethylene terephthalate (BHET) can reach 91%, however, TBD, one of the catalyst raw materials, is expensive and is not favorable for mass synthesis (Green chem.,2018,20, 1205). Because of their unique thermal stability, and their low volatility, non-flammability (Catal. today,2002,74, 157-) 189), large quantities of ionic liquids such as 1-butyl-3-methylimidazolium salt [ Bmim ] Cl, [ Bmim ] [ OH ], [ Amim ] [ ZnCl3], ([ Bmim ] [ CoCl4] are used in succession for PET degradation, although these catalysts are simple to synthesize, too high a catalyst loading has also limited their industrial application (Green chemistry, 2020,22, 3122-) 3131).
The glycolysis of PET is essentially a transesterification reaction in which both Lewis acids and Lewis bases can in principle achieve a catalytic effect. Taken together with previous reports, Lewis bases appear to work better for the depolymerization of PET with ethylene glycol, which may be the formation of hydrogen bonds between the Lewis base and the hydroxyl group of ethylene glycol, thereby increasing the nucleophilic action of ethylene glycol, while Lewis acids may not play a major role in the activation of the PET ester group. Therefore, the search for ionic liquids that are sufficiently basic is the key to efficiently degrade PET.
Disclosure of Invention
Aiming at the defects of difficult catalyst obtaining, difficult synthesis, more metal residues, long reaction time and the like in the prior art, the invention aims to develop an ionic liquid which is easy to synthesize and raw materials are easy to obtain as a catalyst for efficiently degrading PET, and establish a set of conventional method for catalyzing and degrading PET based on the characteristics of the ionic liquid catalyst. The raw materials of the catalyst used in the method are commercial and easily available Trioctylphosphine (TAP) and dimethyl carbonate (DMC), the required catalyst can be obtained by one-step reaction, and the conversion rate is as high as 98%. The catalyst is used for catalyzing PET glycolysis, and can achieve higher PET degradation rate and BHET monomer yield even if the catalyst is loaded at 1 mol%. The catalyst expands the scope of a depolymerization solvent, and the degradation rate can reach 90% under the condition that ethylene glycol, other diols and ethanolamine are used as solvents. In addition, the reaction system has no metal residue, short reaction time and certain industrial application value.
The invention aims to design a strong-basicity ionic liquid catalyst, and establishes a set of conventional method for catalyzing PET depolymerization based on ionic liquid characteristics. The solvent used is not limited to ethylene glycol, but includes propylene glycol, butylene glycol, hexylene glycol, butylene diamine, hexamethylene diamine, monoethanolamine, and diethanolamine.
The technical scheme for realizing the purpose is as follows:
a method for degrading PET by using an ionic liquid catalyst comprises the following steps:
general procedure for the synthesis of the ionic liquid catalyst: with trioctylphosphine [ P (C)8H17)3]And diesters (R)1OCOOR1) The catalyst is obtained by reacting the raw material at 140 ℃ for 20h (yield 98%). The structure of the synthesized catalyst is shown as a formula I.
In the presence of dihydric alcohol, BG80 PET is subjected to reverse esterification reaction under the catalysis of a catalyst shown in formula I, and is depolymerized into BHET. The compound of formula I has the following structure:
r in formula I1A linear aliphatic alkyl selected from C1-C4; or is selected from para-substituted phenyl or pyridyl, and the substituent is hydrogen or amino;
or from trifluoromethyl or from methoxy.
Preferably, when R is1The catalyst is ethyl, phenyl and methoxyl, namely when the synthesized trioctylphosphite anion is acetate, benzoate and methoxyl acetate, the effect of catalyzing PET depolymerization is better than that of trifluoroacetate ion, which accords with the design idea of the catalyst, namely the stronger the basicity of the anion is, the better the catalysis effect is.
The preferred catalyst structure is shown in the following structure:
preferably, the solvent for degrading and catalyzing PET is dihydric alcohol, diamine and alcohol amine. The solvent comprises ethylene glycol, propylene glycol, butanediol, hexanediol, butanediamine, hexanediamine, monoethanolamine and diethanolamine.
Preferably, the specific reaction temperature of the catalyst for catalyzing PET depolymerization is 140-200 ℃;
preferably, the specific reaction time of the catalyst for catalyzing PET depolymerization is 0.5-4 h;
preferably, the catalyst shown catalyzes the depolymerization of PET specifically used at a catalyst to PET mole ratio of 1/50 to 1/20;
preferably, the catalyst shown catalyzes depolymerization of PET specifically using a molar ratio of ethylene glycol to PET of from 10/1 to 20/1;
further preferably, the specific reaction temperature for depolymerization of the PET is 180 ℃;
further preferably, the catalyst to PET molar ratio used is 1/50;
it is further preferred that the ethylene glycol to PET molar ratio used is 15/1.
After the reaction is finished, the degradation rate calculation formula of PET
Conv.％＝W0-W1/W0
Wherein, W0For the quality of the PET charge, W1The quality of the undegraded PET is shown.
Formula for calculating monomer conversion rate
Yield％＝N1/N0
Wherein N is1Molar amount of monomer BHET to degrade, N0The molar weight of PET is fed.
Advantageous effects
The technical scheme of the invention can at least achieve one of the following beneficial effects:
(1) the catalyst shown as the formula I adopted by the invention has the advantages that the raw materials are commercially available, the catalyst is easy to synthesize, and the quantitative conversion can be almost realized in one-step reaction;
(2) the catalyst shown in formula I adopted by the invention has high PET depolymerization catalytic activity, the degradation rate can reach 100% or more under the optimized condition, and the nuclear magnetic yield of monomer BHET obtained by degradation can also reach 80% or more;
(3) the catalyst shown in the formula I is used for catalyzing the PET depolymerization process, the required equipment is simple and convenient, and the possibility of industrial application is realized;
(4) the catalyst shown in formula I is used for catalyzing the PET depolymerization, the dosage of the catalyst is less, and the molar ratio of the catalyst to PET is not more than 2%;
(5) the organic catalyst shown in the formula I is used for catalyzing PET depolymerization, so that no metal residue is generated, and the condition is safe.
Compared with the existing catalyst, the invention has the obvious advantages of easily obtained raw materials, simple and convenient synthesis, higher activity, biological safety and the like.
Drawings
Embodiments of the present invention will be described in detail with reference to the accompanying drawings, in which
FIG. 1: preparation of catalyst 4c prepared in example 11H NMR chart;
FIG. 2: preparation of catalyst 4c prepared in example 113C NMR chart;
FIG. 3: of catalyst 4b prepared in example 21H NMR chart;
FIG. 4: of catalyst 4b prepared in example 213C NMR chart;
FIG. 5: preparation of ethylene glycol depolymerizing monomer BHET prepared in examples 3-61H NMR chart;
FIG. 6: preparation of ethylene glycol depolymerizing monomer BHET prepared in examples 3-613C NMR chart;
FIG. 7: preparation of propylene glycol depolymerization monomer prepared in example 71H NMR chart;
FIG. 8: method for depolymerizing monomer of butanediamine prepared in example 81H NMR chart;
FIG. 9: process for depolymerizing monomers of hexamethylene diamine as prepared in example 91H NMR chart;
FIG. 10: method for depolymerizing monomers with monoethanolamine prepared in example 101H NMR chart;
FIG. 11: method for depolymerizing monomers with monoethanolamine prepared in example 111H NMR chart.
Detailed Description
The invention is further illustrated by the following examples, which are intended to be illustrative and not limiting. It will be understood by those of ordinary skill in the art that these examples are not intended to limit the present invention in any way and that suitable modifications and data transformations may be made without departing from the spirit and scope of the present invention.
The PET raw material sources used in the examples are two: a method for preparing the beverage comprises cutting commercial Onhaha beverage bottle, mechanically grinding, sieving, and oven drying; the other PET raw material is purchased from China petrochemical characterization chemical fiber responsibility Co., Ltd, the PET brand is BG80, the detected intrinsic viscosity is 0.8, and the molecular weight is 2.4-2.5 ten thousand.
The ethylene glycol (99%), trioctylphosphine (97%), dimethyl carbonate (99.5%), acetic acid (98%), trifluoroacetic acid (98%) and phenol (99%) used in the examples were purchased from Nanjing Deming chemical technology, Inc.
The NMR spectra referred to in the examples were determined using a NMR spectrometer model Bruker Ascend TM-400 from Bruker, Inc. (Bruker), using deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d)6)。
The catalysts used in the examples are those of formula I, the structures of which are shown below:
treatment of raw materials:
cutting PET Vietnam with scissors, mechanically grinding, sieving (40-60 mesh), and drying the obtained white powder with vacuum drying oven for 12 hr; BG80 was mechanically ground, sieved through a 40 mesh sieve and dried in vacuo for 12 h.
First, catalyst Synthesis example
The catalyst used in the example is prepared by mixing and stirring trioctylphosphine and dimethyl carbonate, reacting at 140 ℃ for 20h, removing the byproduct methanol by rotary evaporation, and almost completely converting the substrate (98%). The other acid radical ion replacement can be carried out by directly adding equivalent acid into the reaction product of the trioctylphosphine and the dimethyl carbonate, reacting for 2h at 50 ℃, and removing the byproduct methanol by rotary evaporation to obtain the corresponding trioctylphosphine acetate, trioctylphosphine benzoate and trioctylphosphine trifluoroacetate.
Example 1:
measuring 2.48mL (5mmol) of trioctylphosphine, and adding the trioctylphosphine into a 25mL pressure-resistant pipe (the pressure-resistant pipe is dried in advance); weighing 3mL of methanol, and uniformly mixing and stirring; 2.54mL (30mmol) of dimethyl carbonate were added. The reaction is carried out for 20h at 140 ℃, and after the reaction is finished, excessive dimethyl carbonate and a byproduct methanol can be removed by low-pressure rotary evaporation. The resulting salt was a colorless oily liquid (2.25g, 98%), which1The HNMR map is shown in FIG. 1. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 3: 6: 3: 6: 6: 24: 9, consistent with expectations, with no significant miscellaneous peaks1H NMR and13the structure of the catalyst (4C) was confirmed to be correct by C NMR analysis (FIG. 2).
Example 2:
0.921g (2mmol) of the product obtained in example 1 was weighed out, and the product was put into a 25mL eggplant-shaped bottle, and 0.2442g (2mmol) of benzoic acid was weighed out and added thereto. The reaction was carried out at 50 ℃ for 2h, after completion of the reaction, by-produced methanol was removed by low-pressure rotary evaporation to obtain a main product as a colorless oily liquid (1.09g, 98%), which was1The HNMR map is shown in FIG. 3. The deuteration agent is CDCl3The chemical shift is 7.26, the peak area ratio is 2: 1: 2: 6: 3: 12: 24: 9, consistent with expectations, with no significant miscellaneous peaks1H NMR and13the structure of the catalyst (4b) was confirmed to be correct by C NMR analysis (FIG. 4).
Second, example of degradation reaction of PET
Example 3:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.11mL of ethylene glycol and 0.05g of catalyst 4c were measured, and the mixture was added in this order. The reaction was carried out at 180 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 87.93% nuclear magnetic yield of depolymerized monomer BHET. The hot reaction solution is filtered, and the obtained filter cake is unreturnedWashing PET with 70 deg.C water for 3 times, drying in vacuum drying oven for 12 hr, and weighing to obtain powder with a mass of 0.024g (W)1) The PET degradation rate was calculated to be 95.2%. The filtrate is BHET, oligomer, catalyst and ethylene glycol, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, monomer BHET is crystallized and separated out, and the mass of the filtrate is 0.3914g (N is obtained after filtration and drying12.04mmol), the isolated yield of BHET (monomer conversion) was calculated to be 78.28%. The resulting BHET monomer1The HNMR map is shown in FIG. 5. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 2: 4: 4, consistent with expectations, with no significant miscellaneous peaks1H NMR and13c NMR (FIG. 6) analysis confirmed that the structure of BHET was correct.
Example 4:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.11mL of ethylene glycol was measured, and 0.05g of catalyst 4a was added in this order. The reaction was carried out at 180 ℃ for 2 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 84.33% nuclear magnetic yield of depolymerized monomeric BHET. The hot reaction solution was filtered to obtain a filter cake of unreacted PET, which was washed with 70 deg.C water for 3 times and dried in a vacuum oven for 12h, weighing 0.038g (W)1) The PET degradation rate was calculated to be 92.4%. The filtrate is BHET, oligomer, catalyst and ethylene glycol, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, monomer BHET is crystallized and separated out, and the mass of the filtrate is 0.3765g (N is obtained after filtration and drying11.96mmol), the isolated yield of BHET was calculated to be 75.3%. The resulting BHET monomer1The HNMR map is shown in FIG. 5. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 2: 4: 4, consistent with expectations, with no significant miscellaneous peaks1H NMR and13c NMR (FIG. 6) analysis confirmed that the structure of BHET was correct.
Example 5:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.11mL of ethylene glycol and 0.1g of catalyst 4b were measured, and the mixture was added in this order. The reaction was carried out at 200 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 92.34% nuclear magnetic yield of depolymerized monomeric BHET. The hot reaction solution was filtered to obtain a filter cake of unreacted PET, which was washed with 70 deg.C water for 3 times and dried in a vacuum oven for 12h, weighing 0.001g (W)1) The PET degradation rate was calculated to be 99.8%. The filtrate is BHET, oligomer, catalyst and ethylene glycol, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, monomer BHET is crystallized and separated out, and the mass of the filtrate is 0.4365g (N is obtained after filtration and drying12.27mmol), the isolated yield of BHET was calculated to be 87.3%. The resulting BHET monomer1The HNMR map is shown in FIG. 5. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 2: 4: 4, consistent with expectations, with no significant miscellaneous peaks1H NMR and13c NMR (FIG. 6) analysis confirmed that the structure of BHET was correct.
Example 6:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.11mL of ethylene glycol and 0.025g of catalyst 4d were measured, and the mixture was successively added. The reaction was carried out at 140 ℃ for 0.5 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 54.7% nuclear magnetic yield of depolymerized monomeric BHET. The hot reaction solution was filtered, the obtained filter cake was unreacted PET, which was washed with 70 ℃ water 3 times and dried in a vacuum oven for 12 hours, weighing 0.204g (W)1) The PET degradation rate was calculated to be 59.2%. The filtrate is BHET, oligomer, catalyst and ethylene glycol, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, monomer BHET is crystallized and separated out, and the mass of the filtrate is 0.223g (N is measured after filtration and drying)11.16mmol), the isolated yield of BHET was calculated to be 44.6%. The resulting BHET monomer1The HNMR map is shown in FIG. 5.The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 2: 4: 4, consistent with expectations, with no significant miscellaneous peaks1H NMR and13c NMR (FIG. 6) analysis confirmed that the structure of BHET was correct.
Example 7:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.8mL of propylene glycol and 0.05g of catalyst 4c were measured, and the mixture was added in this order. The reaction was carried out at 180 ℃ for 4 h. The hot reaction solution was filtered, the obtained filter cake was unreacted PET, which was washed 3 times with methanol and dried in a vacuum oven for 12h, weighing 0.0456g (W)1) The PET degradation rate was calculated to be 91.2%. The filtrate is propylene glycol degradation monomer, oligomer, catalyst and propylene glycol, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, monomer BHET is crystallized and separated out, the mass of the filtrate is weighed as 0.432g after the filtrate is filtered and dried, and the separation yield of the BHET is calculated to be 86.4%. The obtained propylene glycol degradation monomer1The HNMR map is shown in FIG. 7. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 2: 4: 4: 4, consistent with expectations, with no significant miscellaneous peaks1HNMR analysis confirmed the correct structure of the propylene glycol degrading monomer.
Example 8:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, and 3.9mL of butanediamine and 0.05g of catalyst 4c were weighed out and added in this order. The reaction was carried out at 180 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 68.2% nuclear magnetic yield of depolymerized monomer. Filtering the hot reaction solution to obtain a filter cake of unreacted PET, washing the PET with methanol for 3 times, and drying the PET in a vacuum drying oven for 12 hours, wherein the mass of the PET is called as<0.01g(W1) The PET degradation rate was calculated to be 100%. The filtrate is butanediamine depolymerized monomer, oligomer, catalyst and butanediamine, 20mL water is added into the filtrate, the mixture is stirred at 70 ℃ for 30min, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, and the butanediamine depolymerized monomer is addedCrystallizing to separate out the obtained butanediamine depolymerized monomer1The HNMR map is shown in FIG. 8. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 2: 4: 4: 4: 4: 4, consistent with expectations, with no significant miscellaneous peaks1HNMR analysis confirmed the structure of the succinamide depolymerization monomer.
Example 9:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 5.3mL of hexamethylenediamine and 0.05g of catalyst 4c were measured, and the resultant mixture was added in this order. The reaction was carried out at 180 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 40.0% nuclear magnetic yield of the hexamethylenediamine depolymerized monomer. Filtering the hot reaction solution to obtain a filter cake of unreacted PET, washing the PET with methanol for 3 times, and drying the PET in a vacuum drying oven for 12 hours, wherein the mass of the PET is called as<0.01g(W1) The PET degradation rate was calculated to be 100%. The filtrate is hexamethylenediamine depolymerized monomer, oligomer, catalyst and hexamethylenediamine, 20mL of water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ for cooling for 24h, the hexamethylenediamine depolymerized monomer is crystallized and separated out, and the obtained hexamethylenediamine depolymerized monomer1The HNMR map is shown in FIG. 9. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 2: 4: 4: 4: 16, as expected, with no significant peaks, was1HNMR analysis confirmed the structure of the hexamethylenediamine depolymerization monomer.
Example 10:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was put into a 10mL schlenk tube, 2.3mL of monoethanolamine and 4c0.05g of a catalyst were measured and added in this order. The reaction was carried out at 180 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated a monoethanolamine depolymerized monomer nuclear magnetic yield of 81.6%. Filtering the hot reaction solution to obtain a filter cake of unreacted PET, washing the PET with methanol for 3 times, and drying the PET in a vacuum drying oven for 12 hours, wherein the mass of the PET is called as<0.01g(W1) CalculatingThe PET degradation rate is 100%. The filtrate is monoethanolamine depolymerized monomer, oligomer, catalyst and monoethanolamine, 20mL water is added into the filtrate, the mixture is stirred for 30min at 70 ℃, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ for cooling for 24h, monomer BHET is crystallized and separated out, and the obtained monoethanolamine depolymerized monomer1The HNMR map is shown in FIG. 10. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 2: 4: 2: 4: 4, consistent with expectations, with no significant miscellaneous peaks1HNMR analysis confirmed the structure of the monoethanolamine depolymerizing monomer.
Example 11:
BG80 PET 0.5g (W) was weighed0,N02.6mmol), the mixture was charged into a 10mL schlenk tube, and 3.73mL of diethanolamine and 4c0.05g of a catalyst were weighed and added in this order. The reaction was carried out at 180 ℃ for 4 h. After the reaction is finished, 0.1g of internal standard substance 1,3, 5-trimethoxybenzene is weighed and directly added into the reaction liquid, the mixture is stirred for 30min, and then sampling is carried out1H NMR analysis calculated 29% nuclear magnetic yield of diethanolamine depolymerized monomer. Filtering the hot reaction solution to obtain a filter cake of unreacted PET, washing the PET with methanol for 3 times, and drying the PET in a vacuum drying oven for 12 hours, wherein the mass of the PET is called as<0.01g(W1) The PET degradation rate was calculated to be 100%. The filtrate is diethanolamine depolymerized monomer, oligomer, catalyst and diethanolamine, 20mL water is added into the filtrate, the mixture is stirred at 70 ℃ for 30min, the hot filtrate is filtered for 3 times, the filtrate is directly placed in a refrigerator at 0 ℃ to be cooled for 24h, the diethanolamine depolymerized monomer is crystallized and separated out, and the obtained diethanolamine depolymerized monomer1The HNMR map is shown in FIG. 11. The deuterated reagent is DMSO-d6The chemical shift is 2.5, the peak area ratio is 4: 4: 4: 4: 4: 4, consistent with expectations, with no significant miscellaneous peaks1HNMR analysis confirmed the structure of the diethanolamine depolymerization monomer.
Claims (9)
1. A method for degrading thermoplastic plastic polyethylene terephthalate is characterized in that ethylene glycol is used as an alcoholysis raw material, and a catalyst shown in a formula I is used for catalyzing and degrading the polyethylene terephthalate and the polyethylene terephthalate;
r in formula I1A linear aliphatic alkyl selected from C1-C4; or is selected from para-substituted phenyl or pyridyl, and the substituent is hydrogen or amino; or from trifluoromethyl or from methoxy.
2. The method of claim 1, wherein: r1Selected from methyl, ethyl, propyl, butyl; phenyl, p-aminopyridyl or methoxy.
3. The method of claim 1, wherein: the preparation method of the catalyst comprises the following steps: with trioctylphosphine and R of formula II1OCOOR1The diester is used as a raw material to react to obtain the catalyst shown in the formula I.
4. The method of claim 3, wherein: the preparation method of the catalyst can obtain the catalyst after reacting for 20 hours at 140 ℃.
5. The process of claim 1, wherein the catalyst of formula I is of formula a, b, c, d:
6. the method as claimed in claim 1, wherein the specific reaction temperature of the synthesis method is 100-200 ℃; and/or the molar ratio of ethylene glycol to polyethylene terephthalate is from 10/1 to 20/1; and/or the molar ratio of the catalyst of formula I to the polyethylene terephthalate is from 1/50 to 1/20; and/or the reaction time is 0.5 to 4 hours.
7. The method of claim 1, wherein the specific reaction temperature of the synthetic method is 180 ℃; and/or using a molar ratio of ethylene glycol to PET of 15/1; and/or the molar ratio of catalyst used to PET is 1/50; and/or the reaction time is 1.5 h.
8. The process according to claim 1, characterized in that the specific reaction temperature of the synthesis process is 180 ℃, the molar ratio of ethylene glycol to PET used is 15/1, the molar ratio of catalyst used is 1/50, and the reaction time used is 4 h.
9. The method according to claim 1, wherein the PET degradation method employs an organic alcohol, and the organic alcohol comprises one of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, butylene diamine, hexamethylene diamine, monoethanolamine, and diethanolamine.
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| CN101249456A (en) * | 2008-03-14 | 2008-08-27 | 中国科学院过程工程研究所 | Catalyst for alcoholysis polyethylene glycol terephthalate |
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| CN114426483A (en) * | 2022-01-19 | 2022-05-03 | 南京工业大学 | Method for degrading polyethylene terephthalate |
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