CN105384637A - Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster - Google Patents

Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster Download PDF

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CN105384637A
CN105384637A CN201510888145.4A CN201510888145A CN105384637A CN 105384637 A CN105384637 A CN 105384637A CN 201510888145 A CN201510888145 A CN 201510888145A CN 105384637 A CN105384637 A CN 105384637A
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polysubstituted
metal oxygen
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oxygen cluster
pet
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吕兴梅
方鹏涛
董陶
张锁江
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Institute of Process Engineering of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

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Abstract

The invention relates to a novel method for preparing bis-hydroxyethyl terephthalate (BHET) through high-activity catalytic alcoholysis of polyethylene glycol terephthalate. The method is characterized in that alcoholysis of PET is carried out under the conditions that a polysubstituted sandwiched heteropolyacid salt of a transition metal Mn, Co, Zn, Cu or Ni is used as a catalyst, glycol is used as a solvent; the usage amount of the catalyst is 0.2 to 10% of the mass of a reactant, reaction temperature is 140 to 188 DEG C, reaction pressure is 1 atm, and reaction time is 5 to 120 min The method has the advantages of low cost, better catalytic activity, friendliness to environment, mild reaction conditions, recyclability, etc.

Description

A kind of method of polysubstituted sandwich-like multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate
Technical field
The present invention utilizes the polysubstituted sandwich-like multi-metal oxygen cluster of transition metal for catalyst alcoholysis polyethylene terephthalate.Relate to polymer chemistry and catalysis technical field.
Background technology
Polyethylene terephthalate (PET) is as a kind of thermoplastic macromolecule material of excellent property, there is much excellent characteristic, such as odorless, tasteless, nontoxic, quality is light, intensity is large, resistance to air loss is good, transparency is high, and possess antifatigue, ageing-resistant, rub resistance, insulativity are outstanding, production energy consumption is low, the processibility good and physical and chemical stability advantageous property such as well, is thus widely used in the fields such as food product pack, synthon, plastics film, medicine, sensitive film, finishing material and insulating material.According to the research report display of announcing, the demand of 2012-2017 whole world PET packaging market, because the growth of the demand of emerging market and transition economies, increases fast by with the speed exceeding 5% every year.Within 2013, global PET resin market value is about 314.7 hundred million dollars.During estimating 2014-2019, the compound annual growth rate with 7.3% goes up by this kind of resin market requirement.
Along with the development of Plastics Industry, advanced manufacturing technology, the ratio of plastics shared by Industrial materials is also increasing, PET product consumption also increases year by year, the generation of waste PET is huge, this is a kind of huge wastes to the physical resources of the mankind, and especially the production of PET is what to consume non-renewable oil be cost.Moreover, although waste PET does not produce direct pollution to environment, because its quality is light, bulky, and because of it, there is extremely strong unreactiveness, be difficult to be degraded by microorganisms under field conditions (factors), therefore can cause very large impact to environment.So in the resource benign cycle how realizing producing, processing, recycle, namely changed into by " white pollution " in " white resource ", the recovery and utilization technology of waste and old polyester obtained to the attention of increasing country and investigator.
At present, the recovery method for PET mainly contains physiochemical mutagens and chemical recovery.Physiochemical mutagens and waste PET, through separation, fragmentation, washing and drying treatment granulation or film-making again, can be used for spinning, membrane and engineering plastics etc. as secondary shelves product, realize recycling.Compared with chemical recovery method, though physiochemical mutagens has, recovery method is simple, less investment, can use existing equipment and to advantages such as environmental influence are little, but because the plastics performance after process is deteriorated, and along with the decline of mechanical property and the generation of a large amount of carboxyl, and not being allowed for food service industry, these unfavorable factors make chemical process day by day receive publicity.
Conventional chemical recovery method mainly contains hydrolysis method, Methanolysis method, glycolysis method, ammonolysis process, aminolysis and supercritical methanol technology etc.Wherein hydrolysis method often uses soda acid as catalyzer, can bring the problem of corrosion or contaminate environment, therefore high to equipment requirements, is not easy to scale operation; The solvent used in Methanolysis method is volatile, easily causes environmental pollution, and severe reaction conditions, product is not easily separated; Supercritical methanol technology has higher speed of reaction, and the reaction times is short, and PET per pass conversion is high, good product selectivity, and does not need the advantages such as catalyzer, but operational condition is harsh, high especially to equipment requirements, is unfavorable for commercial operation.Glycolysis method has clear superiority compared with other method, and as reaction conditions is relatively gentle, solvent boiling point is high, stable and not volatile, is conducive to industrial continuous production, environmentally friendly etc.In the exploitation of glycolysis method catalyzer, take zinc acetate as the more of catalyst research, achieve certain achievement, and in order to increase its catalytic efficiency, add overcritical, other subsidiary conditions such as microwave, other salts, as metal acetate salt (Cobaltous diacetate, plumbic acetate, manganese acetate) and metal chloride (zinc chloride, lithium chloride, Manganous chloride tetrahydrate, iron(ic) chloride) etc. also report all to some extent, but the catalyzer of these salts is difficult to be separated with degraded product, the quality of product may be affected, and this is a complicated reversible reaction, reacted resultant is comparatively complicated.Therefore, the catalyzer of some other types is also developed, and as solid acids, conventional ionic liquid and functionalized ion liquid etc. are used to catalyzed degradation PET as catalyzer.Catalyzer more in the past, the catalyzer developed now is at reaction conditions, and selectivity, the main performance index such as transformation efficiency has had larger progress, but still can not meet industrialized requirement.Therefore, the development and utilization for catalyzer still needs to do large quantity research, wishes to obtain a kind of catalytic performance good, the catalyzer of reaction conditions gentleness.This seminar has synthesized a kind of mono-substituted multi-metal oxygen cluster catalyst in early stage, has proved to show good catalytic performance in the process of alcoholysis PET, and has had the selectivity of higher BHET and the transformation efficiency of PET.Therefore, the present invention, in conjunction with the structure designability of multi-metal oxygen cluster, has synthesized polysubstituted multi-metal oxygen cluster catalyst, to increase active site, cost of development is cheap, and catalytic activity is more excellent, environmentally friendly, reaction conditions is gentle, for the purpose of the high activated catalyst of reusable edible.
Summary of the invention
The present invention's research is with a kind of efficient stable and the polysubstituted multi-metal oxygen cluster of the sandwich-like of reusable edible is catalyzer, take ethylene glycol as solvent, ethylene glycol terephthalate (BHET) is prepared in the degraded under mild conditions for polyethylene terephthalate.
Reaction expression of the present invention is:
Multi-metal oxygen cluster catalyst of the present invention is Mn, Co, Zn, Cu or Ni five kinds of polysubstituted multi-metal oxygen clusters of the polysubstituted sandwich-like of transition metal.
The preparation method of this multi-metal oxygen cluster catalyst is: tungstate and zinc nitrate or zinc sulfate are prepared trisubstituted sandwich-like multi-metal oxygen cluster parent under sour environment, and then with containing the salt of transition metal by Transition metal substituted on the parent of sandwich-like multi-metal oxygen cluster, obtain the sandwich-like multi-metal oxygen cluster catalyst of transition metal disubstituted.
Multi-metal oxygen cluster catalyst of the present invention for the detailed process of the PET that degrades is: the catalyzer of corresponding for difference ratio, solvent and PET are reacted the regular hour at a certain temperature, if there is unreacted PET particle, be separated, abundant washes clean is also dry, then being dissolved by BHET monomer with a large amount of water makes it be separated with oligopolymer, then by the solution condensing crystal of BHET and drying obtains BHET monomer.
Described catalyzer is Mn, Co, Zn, Cu or Ni five kinds of polysubstituted multi-metal oxygen clusters of the polysubstituted sandwich-like of transition metal, and described catalyst levels is polyethylene terephthalate quality 0.1% ~ 10%.
The described temperature of reaction being catalyst degradation polyethylene terephthalate with the polysubstituted multi-metal oxygen cluster of sandwich-like is 140 DEG C ~ 188 DEG C.
Described with the polysubstituted multi-metal oxygen cluster of sandwich-like for the reaction pressure of catalyst degradation polyethylene terephthalate is without particular requirement, normal pressure.
The described reaction times being catalyst degradation polyethylene terephthalate with the polysubstituted multi-metal oxygen cluster of sandwich-like is for 5min – 120min.
After reaction terminates, the degradation rate of PET polyester and the selectivity of product are pressed formula (1) (2) respectively and are calculated:
Wherein, A represents the initial mass of the PET added, and B represents undegradable PET quality.
The method reaction conditions of the present invention is gentle, catalytic activity height consumption is few, selectivity of product is high and easily separated without color, can recycle etc., is easy to realize large-scale industrial production.
Embodiment
The present invention's following examples are described, but the present invention is not limited in following embodiment, and under the scope of aim belonging to before and after not departing from, change is included in technical scope of the present invention.
Embodiment 1
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.2% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 78.13%, monomers B HET is 62.05%.
Embodiment 2
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then BHET monomer is separated with oligopolymer by water, and BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, the selectivity of monomers B HET is 84.34%.
Embodiment 3
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 1% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 100%, monomers B HET is 83.98%.
Embodiment 4
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 2% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 100%, monomers B HET is 83.70%.
Embodiment 5
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 140 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 3.25%, monomers B HET is 0%.
Embodiment 6
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 160 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 19.25%, monomers B HET is 64.11%.
Embodiment 7
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 170 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 15min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 44.33%, monomers B HET is 69.07%.
Embodiment 8
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 5min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 39.33%, monomers B HET is 78.00%.
Embodiment 9
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 188 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 25min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 90.00%, monomers B HET is 81.14%.
Embodiment 10
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 50min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 100%, monomers B HET is 83.95%.
Embodiment 11
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the dibasic multi-metal oxygen cluster catalyst of 0.5% transition metal Co (WZnCO in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 99.83%, monomers B HET is 84.61%.
Embodiment 12
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the dibasic multi-metal oxygen cluster catalyst of 0.5% transition metal Ni (WZnNi in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 98.13%, monomers B HET is 77.48%.
Embodiment 13
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the dibasic multi-metal oxygen cluster catalyst of 0.5% transition metal Ni (WZnNi in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 98.13%, monomers B HET is 77.48%.
Embodiment 14
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the dibasic multi-metal oxygen cluster catalyst of 0.5% transient metal Mn (WZnMn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 99.90%, monomers B HET is 82.88%.
Embodiment 15
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the dibasic multi-metal oxygen cluster catalyst of 0.5% transition metal Cu (WZnCu in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 99.18%, monomers B HET is 78.42%.
Embodiment 16
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Co (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(CoW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 66.90%, monomers B HET is 69.88%.
Embodiment 17
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 0.5% transition metal Co (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(CoW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 120min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 100%, monomers B HET is 82.42%.
Embodiment 18
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and the polysubstituted multi-metal oxygen cluster catalyst of 10% transition metal Zn (WZn in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3(H 2o) 2(ZnW 9o 34) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 100%, monomers B HET is 79.95%.
Comparative example 1
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and 0.5% zinc nitrate (Zn (NO in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 3) 2).Controlling temperature of reaction is 185 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 64.61%, monomers B HET is 58.02%.
Comparative example 2
Implementation method: add 5.0gPET particle (40-60 order), 20.0g ethylene glycol and 2% zinc acetate (Zn (AC) in the 50ml there-necked flask being furnished with thermometer, reflux condensing tube successively 2).Controlling temperature of reaction is 188 DEG C, and pressure is 1atm, is chilled to room temperature after condensing reflux reaction 40min.Isolate undegradable PET particle, fully wash drying, weigh and obtain the quality of undegradable PET particle.Then with water, BHET monomer is separated with oligopolymer, BHET solution condensing crystal is obtained BHET monomer.With this understanding, the degradation rate of PET polyester is the selectivity of 96.17%, monomers B HET is 72.62%.

Claims (6)

1. a method for catalyzed degradation polyethylene terephthalate, is characterized in that taking ethylene glycol as solvent, and with polysubstituted multi-metal oxygen cluster for catalyzer, described polysubstituted multi-metal oxygen cluster is polysubstituted sandwich-like multi-metal oxygen cluster.
2. method according to claim 1, is characterized in that polysubstituted multi-metal oxygen cluster catalyst used is Mn, Co, Zn, Cu or Ni five kinds of polysubstituted multi-metal oxygen clusters of the polysubstituted sandwich-like of transition metal.
3. method according to claim 1, is characterized in that catalyst levels is 0.2% ~ 10% of polyethylene terephthalate quality.
4. method according to claim 1, is characterized in that the temperature of reaction of polysubstituted sandwich-like multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is 140 DEG C ~ 188 DEG C.
5. method according to claim 1, is characterized in that the reaction pressure of polysubstituted sandwich-like multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is normal pressure.
6. method according to claim 1, is characterized in that the reaction times of polysubstituted sandwich-like multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is 5min ~ 120min.
CN201510888145.4A 2015-12-07 2015-12-07 Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster Pending CN105384637A (en)

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CN114225966A (en) * 2021-12-31 2022-03-25 郑州中科新兴产业技术研究院 Preparation method of layered heteropoly acid ionic liquid catalyst and method for accurately catalyzing alcoholysis of PET (polyethylene terephthalate) by using layered heteropoly acid ionic liquid catalyst
CN114989400A (en) * 2022-07-05 2022-09-02 河南源宏高分子新材料有限公司 Preparation method of chemically regenerated PETG polyester

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CN108250481A (en) * 2018-02-28 2018-07-06 兰州理工大学 A kind of method of catalyst alcoholysis waste PET production polyester polyol
CN108250481B (en) * 2018-02-28 2023-05-02 兰州理工大学 Method for producing polyester polyol by catalytic alcoholysis of waste PET (polyethylene terephthalate) by using catalyst
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CN114225966B (en) * 2021-12-31 2024-04-09 郑州中科新兴产业技术研究院 Preparation method of layered heteropolyacid ionic liquid catalyst and method for accurately catalyzing PET alcoholysis
CN114989400A (en) * 2022-07-05 2022-09-02 河南源宏高分子新材料有限公司 Preparation method of chemically regenerated PETG polyester

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Application publication date: 20160309