CN103951564A - Method for carrying out catalytic degradation on polyethylene glycol terephthalate (PET) by utilizing multi-metal oxygen cluster - Google Patents

Method for carrying out catalytic degradation on polyethylene glycol terephthalate (PET) by utilizing multi-metal oxygen cluster Download PDF

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CN103951564A
CN103951564A CN201410166733.2A CN201410166733A CN103951564A CN 103951564 A CN103951564 A CN 103951564A CN 201410166733 A CN201410166733 A CN 201410166733A CN 103951564 A CN103951564 A CN 103951564A
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pet
metal oxygen
bhet
oxygen cluster
catalyst
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CN103951564B (en
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吕兴梅
耿艳荣
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 new method for preparing bis(2-hydroxyethyl) terephthalate (BHET) by carrying out high activity alcoholysis on polyethylene glycol terephthalate (PET). The new method for preparing BHET by carrying out high activity alcoholysis on PET is characterized in that transition metal Mn, Co, Zn, Cu or Ni monosubstituted Keggin type polyoxometallate is taken as a catalyst, ethylene glycol is taken as a solvent, and alcoholysis is carried out on PET under the conditions that usage amount of the catalyst is 0.5-10% of the mass of a reactant, a reaction temperature is 70-250 DEG C, pressure is one atmosphere, reaction time is 10 minutes to 2 hours. The new method for preparing BHET by carrying out high activity alcoholysis on PET has the advantages of mild reaction condition, high catalytic activity, good selectivity, no colour and cyclic utilization, the catalyst is easy to prepare, and products are easily separated.

Description

A kind of method of multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate
Technical field
The present invention utilizes the mono-substituted 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 a kind of thermoplastic macromolecule material of excellent property, have odorless, tasteless, nontoxic, quality is light, intensity is large, resistance to air loss is good, transparency high, thereby is widely used in the especially field such as mineral water bottle and beverage bottle, synthon, plastics film and insulating material of food product pack.The research report of announcing according to Pira international corporation of market research agency shows, 2012-2017 whole world PET packaging market demand is by exceed every year 5% speed rapid growth, mainly by the sustainable growth demand at emerging market and transition economies, drive, by 2017, global PET packaging market will reach approximately 1,910 ten thousand tons/year, focus in Asia-Pacific, Central and South America, Central and Eastern Europe, the Middle East and area, Africa, the share of West Europe and North America PET packaging market will decline.Report and point out simultaneously, between 2007-2012, PET market in the Asian-Pacific area has surpassed North America and market, West Europe.According to estimates, PET market, the Asian-Pacific area in 2012 accounts for approximately 30% of global PET package consumer amount, and North America will account for approximately 24%, and West Europe will account for nearly 20%.
Along with increasing sharply of polyester material volume of production and marketing, the amount of the waste and old polyester material producing is more and more.Although waste PET does not produce direct pollution to environment, but because its quality is light, bulky, and because it has extremely strong unreactiveness, be difficult to be degraded by microorganisms under field conditions (factors), therefore can cause very large impact to environment, and can cause the waste of resource.Waste and old polyester salvage material is re-used as the important channel of turning waste into wealth and solving ecological environmental pollution, therefore the recovery and utilization technology of waste and old polyester has been obtained increasing country and investigator's attention.Late 1960s is to the beginning of the seventies, along with non-fine with PET and other packing articles universal in developed country, PET is reclaimed and the technology of reprocessing occurs in a large number.At present, developed country pays close attention to the expansion of new technology development, produce market, the exploitation of high value added product more in regenerative PET reprocessing field.
Recovery method for PET mainly contains physics recovery and chemical recovery.It is that waste PET is through separated, fragmentation, washing and drying treatment granulation or film-making again that physics reclaims.Compare with chemical recovery method, though have that recovery method is simple, less investment, can use existing equipment and to advantages such as environmental influence are little, but because of the plastics performance variation after physics recycling, its limiting viscosity declines approximately 38% in circulation after four times, and be accompanied by the decline of mechanical property and the generation of a large amount of carboxyl end groups, and be not allowed for food service industry, these unfavorable factors receive publicity chemical process day by day, although chemical process is comparatively expensive.
Chemical recovery is the depolymerization of waste PET process, transfers small molecules, industrial chemicals or monomer to.Chemical recovery method mainly contains hydrolysis, methyl alcohol alcoholysis, glycolysis, ammonia solution, aminolysis and the method such as overcritical.Glycolysis method is compared and is had clear superiority with other method.As having, less reactive material, reaction conditions are relatively gentle, solvent is not volatile, can produce continuously etc.Because zinc acetate has significant catalytic effect in PET alcoholysis reaction, people have carried out more research, and in order to increase its catalytic efficiency, increased the subsidiary conditions such as overcritical, microwave, other salts, as metal acetate salt and metal chloride etc. also reports to some extent all, but the catalyzer of these salts is difficult to separated with degraded product, may affect the quality of product, and this is a complicated reversible reaction, reacted resultant is comparatively complicated.As required, the catalyzer of some other types is also developed, and as solid acids, conventional ion liquid and functionalized ion liquid etc. are used to catalyzed degradation PET as catalyzer.Although the catalyzer of having developed catalyzer has than before been made significant headway, but still can not meet the demands,, for the exploitation of its catalyzer, still there is very large demand in the problem such as long in the reaction times, selectivity is low, quality product is low, catalyzer is unstable.Therefore, scientific circles still pay close attention to and seek new, low-volatile, to reduce reaction conditions PET degradation catalyst.Therefore the present invention take develop cheap and easy to get, transformation efficiency is high, selectivity good, be easy to product separation, reaction conditions gentle and high activated catalyst that can recycle is object.
Summary of the invention
The present invention research is that to take the multi-metal oxygen cluster of a kind of efficient stable and reusable edible be catalyzer, take ethylene glycol as solvent, under gentle condition, for the degraded of polyethylene terephthalate, prepares ethylene glycol terephthalate (BHET).
Reaction expression of the present invention is:
Multi-metal oxygen cluster catalyst of the present invention is Mn, Co, Zn, Cu or the five kinds of mono-substituted Keggin type of transition metal multi-metal oxygen clusters of Ni.
The preparation method of this multi-metal oxygen cluster catalyst is: tungstate and silicate are prepared to single vacant Keggin type multi-metal oxygen cluster parent under sour environment, and then with containing the salt of transition metal by Transition metal substituted to the parent of Keggin type multi-metal oxygen cluster, obtain the mono-substituted Keggin type of transition metal multi-metal oxygen cluster catalyst.
Multi-metal oxygen cluster catalyst of the present invention for the detailed process of the PET that degrades is: the catalyzer of corresponding ratio, solvent and PET are reacted to certain hour at a certain temperature, if there is unreacted PET particle, be isolated out, fully wash and be dried, then water dissolves BHET monomer to make it separated with oligopolymer, then by the solution condensing crystal of BHET the dry BHET monomer that obtains.
Described catalyzer is Mn, Co, Zn, Cu or the five kinds of mono-substituted Keggin type of transition metal multi-metal oxygen clusters of Ni, and described catalyst levels is polyethylene terephthalate quality 0.1%～10%.
Describedly take the temperature of reaction that multi-metal oxygen cluster is catalyst degradation polyethylene terephthalate and be 150 ℃～190 ℃.
Describedly take reaction pressure that multi-metal oxygen cluster is catalyst degradation polyethylene terephthalate without particular requirement, normal pressure.
It is described that to take the reaction times that multi-metal oxygen cluster is catalyst degradation polyethylene terephthalate be 10min-2h.
After reaction finishes, the degradation rate of PET polyester and the selectivity of product are pressed respectively formula (1) (2) and are calculated:
Wherein, A represents the initial mass of the PET that adds, and B represents undegradable PET quality.
The method reaction conditions of the present invention is gentle, catalyzer is easily prepared, catalytic activity is high, selectivity good, product is easily separated and without color, can recycle etc., be easy to realize large-scale industrial production.
Embodiment
The present invention describes by following examples, but the present invention is not limited in following embodiment, and before and after not departing from, under the scope of affiliated aim, change is included in technical scope of the present invention.
Embodiment 1
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.15g transition metal Co (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11co (H 2o)O 39).Controlling temperature of reaction is 185 ℃, and pressure is 1atm, after condensing reflux reaction 50min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 82.9%.
Embodiment 2
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transient metal Mn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11mn (H 2o)O 39).Controlling temperature of reaction is 185 ℃, and pressure is 1atm, after condensing reflux reaction 50min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 81.5%.
Embodiment 3
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 150 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Isolate undegradable PET particle, fully washing is dry, weighs and obtains the quality of undegradable PET particle.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 76.28%, and the selectivity of monomers B HET is 1.67%.
Embodiment 4
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 86.70%.
Embodiment 5
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.025g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 95.77%, and the selectivity of monomers B HET is 60.29%.
Embodiment 6
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.15g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 85.07%.
Embodiment 7
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 15min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 90.58%, and the selectivity of monomers B HET is 69.42%.
Embodiment 8
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 55min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 82.58%.
Embodiment 9
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 40min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 83.83%.
Embodiment 10
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11zn (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 35min, is chilled to room temperature.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers B HET is 84.38%.
Embodiment 11
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Cu (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11cu (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Isolate undegradable PET particle, fully washing is dry, weighs and obtains the quality of undegradable PET particle.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 27.61%, and the selectivity of monomers B HET is 22.46%.
Embodiment 12
Implementation method: add successively 5.0g PET particle (40-60 order), 20.0g ethylene glycol and the mono-substituted multi-metal oxygen cluster catalyst of 0.10g transition metal Zn (K in being furnished with the 50ml there-necked flask of thermometer, reflux condensing tube 6siW 11ni (H 2o)O 39).Controlling temperature of reaction is 188 ℃, and pressure is 1atm, after condensing reflux reaction 30min, is chilled to room temperature.Isolate undegradable PET particle, fully washing is dry, weighs and obtains the quality of undegradable PET particle.Then water is separated with oligopolymer by BHET monomer, and BHET solution condensing crystal is obtained to BHET monomer.With this understanding, the degradation rate of PET polyester is 13.86%, and the selectivity of monomers B HET is 11.73%.

Claims (6)

1. a method for catalyzed degradation polyethylene terephthalate, is characterized in that take that glycol is as solvent, take multi-metal oxygen cluster as catalyst degradation polyethylene terephthalate.
2. method according to claim 1, it is characterized in that multi-metal oxygen cluster catalyst used is Mn, Co, Zn, Cu or the five kinds of mono-substituted Keggin type of transition metal multi-metal oxygen clusters of Ni, preferably Mn, Co or the tri-kinds of mono-substituted Keggin type of transition metal multi-metal oxygen clusters of Zn.
3. method according to claim 1, is characterized in that catalyst levels is 0.1%～10% of polyethylene terephthalate quality.
4. method according to claim 1, the temperature of reaction that it is characterized in that multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is 150 ℃～190 ℃.
5. method according to claim 1, the reaction pressure that it is characterized in that multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is normal pressure.
6. method according to claim 1, the reaction times that it is characterized in that multi-metal oxygen cluster catalyzed degradation polyethylene terephthalate is 10min～2h.
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CN105384637A (en) * 2015-12-07 2016-03-09 中国科学院过程工程研究所 Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster
CN107417492A (en) * 2017-06-28 2017-12-01 中国科学院山西煤炭化学研究所 A kind of method of controlled degradation recovery pet material
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
CN114230857A (en) * 2021-12-31 2022-03-25 郑州中科新兴产业技术研究院 Method for rapidly degrading PET through high-temperature swelling effect
US20230076330A1 (en) * 2021-07-27 2023-03-09 Jilin University Near-infrared photothermal catalyst and preparation method and use thereof
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CN117943127A (en) * 2024-03-26 2024-04-30 德州学院 Alkoxy coordinated manganese oxide cluster crystal catalytic material and preparation method and application thereof
CN115770617B (en) * 2022-12-06 2024-07-12 现代纺织技术创新中心(鉴湖实验室) Solution catalyst for recycling polyethylene glycol terephthalate and preparation method thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105384637A (en) * 2015-12-07 2016-03-09 中国科学院过程工程研究所 Method for degrading polyethylene glycol terephthalate under catalysis of polysubstituted sandwiched multi-metal oxygen cluster
CN107417492A (en) * 2017-06-28 2017-12-01 中国科学院山西煤炭化学研究所 A kind of method of controlled degradation recovery pet material
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
US20230076330A1 (en) * 2021-07-27 2023-03-09 Jilin University Near-infrared photothermal catalyst and preparation method and use thereof
US11826744B2 (en) * 2021-07-27 2023-11-28 Jilin University Near-infrared photothermal catalyst and preparation method and use thereof
CN114230857A (en) * 2021-12-31 2022-03-25 郑州中科新兴产业技术研究院 Method for rapidly degrading PET through high-temperature swelling effect
CN114230857B (en) * 2021-12-31 2023-12-01 郑州中科新兴产业技术研究院 Method for rapidly degrading PET (polyethylene terephthalate) through high-temperature swelling effect
CN115770617A (en) * 2022-12-06 2023-03-10 现代纺织技术创新中心(鉴湖实验室) Solution type catalyst for recovering polyethylene glycol terephthalate and preparation method thereof
CN115770617B (en) * 2022-12-06 2024-07-12 现代纺织技术创新中心(鉴湖实验室) Solution catalyst for recycling polyethylene glycol terephthalate and preparation method thereof
CN117943127A (en) * 2024-03-26 2024-04-30 德州学院 Alkoxy coordinated manganese oxide cluster crystal catalytic material and preparation method and application thereof
CN117943127B (en) * 2024-03-26 2024-05-28 德州学院 Alkoxy coordinated manganese oxide cluster crystal catalytic material and preparation method and application thereof

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