CN102731310B - Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid - Google Patents
Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid Download PDFInfo
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- CN102731310B CN102731310B CN201110090618.8A CN201110090618A CN102731310B CN 102731310 B CN102731310 B CN 102731310B CN 201110090618 A CN201110090618 A CN 201110090618A CN 102731310 B CN102731310 B CN 102731310B
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- polyethylene terephthalate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a polyethylene terephthalate (PET) alcoholysis method with the catalysis of a first transition series metal ionic liquid. The method is characterized by taking the first transition series metal ionic liquid as a catalyst, taking one or the mixture of several from glycol, diethylene glycol, propanediol, butanediol, pentanediol, hexanediol, 1,7-heptandiol as a solvent, and under the conditions of the catalyst amount being 0.1% to 20% of the solvent mass, the reaction temperature being 80 DEG C to 250 DEG C, the pressure being 1 atm, and the reaction time being 1 min to 9 h, carrying out alcoholysis on the polyethylene terephthalate. The method has the advantages of mild reaction condition, high speed and high efficiency, high degradation rate, high catalytic activity, good selectivity, readily releasable products, environmental protection and energy saving, etc.
Description
Technical field:
The present invention relates to green, clean catalysis technical field, specifically refer to the novel method of the first transition metal ion liquid catalyst alcoholysis polyethylene terephthalate.
Background technology:
That polyethylene terephthalate (PET) has is odorless, tasteless, nontoxic, quality is light, intensity is large, resistance to air loss is good, transparency high and be widely used in the fields such as beverage bottle, fiber, film, sheet base and electrical apparatus insulation material, especially the soda pop in field of food, mineral water, the edible wet goods packing of product are nearly all polyester bottles, and its Application Areas is in continuous expansion.At present, the approximately tens million of ton of whole world polyester annual production, and its consumption is still increasing with annual 11% speed.If being directly discharged in environment with the waste and old polyester of crossing, not only contaminate environment, and waste resource.Therefore, recycle PET polyester, protection of the environment, the crisis of alleviation world resource are significant.
The method of recycled PET is mainly that physics reclaims and chemical recovery at present.Because the ageing of plastics after physics recycling is serious and degradation, and the problem such as traditional chemical recovery method often needs High Temperature High Pressure and exist catalyzer and product is not easily separated, therefore the present invention take exploitation high conversion, highly selective, product is easily separated, reaction conditions is gentle, the catalyzer of energy-saving and environment friendly is object.
Summary of the invention:
The present invention research take the first transition metal ion liquid as catalyzer, take dibasic alcohol as solvent, under gentle condition, realize the catalyzed alcoholysis PET polyester of green high-efficient, high degradation rate and highly selective for the process of ethylene glycol terephthalate monomer (BHET).
Reaction expression of the present invention is (ethylene glycol of take is example as solvent):
The method of the first transition metal ion liquid catalyst alcoholysis polyethylene terephthalate, is characterized in that take that dibasic alcohol is as solvent, take the first transition metal ion liquid as catalyst degradation polyethylene terephthalate.
Described diol solvent is ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, 1, the mixture of one or more in 7-heptanediol.
The molecular weight of the polyethylene terephthalate of degrading is 1.8～7.5 * 10
4g/mol.
The negatively charged ion of ionic-liquid catalyst used is that First Transition is metal halide complex ion, i.e. TiX
5 -, VX
4 -, CrX
4 -, MnX
3 -, FeX
3 -, FeX
4 -, CoX
3 -, CoX
4 2-, NiX
3 -, NiX
4 2-, CuX
2 -, CuX
3 -or ZnX
3 -(X=F, Cl, Br or I).
The positively charged ion of the first transition metal ion liquid used is imidazol ion (1), pyridinium ion (2), season phosphine ion (3), quaternary ammonium ion (4), guanidine class ion (5), sulfonium salt ion (6), choline type ion (7) or morpholine ion (8).
Described catalyzer can be one or more the mixture in the first transition metal ion liquid, can be also the mixture of the first transition metal ion liquid and other ionic liquids.
Described catalyst levels is 0.1 ‰～20% of solvent quality.
Describedly take the temperature of reaction that the first transition metal ion liquid is catalyst degradation polyethylene terephthalate and be 80 ℃～250 ℃.
Describedly take ethylene glycol as solvent, the temperature of reaction that the imidazoles the first transition metal ion liquid of take is prepared ethylene glycol terephthalate (BHET) as catalyst degradation polyethylene terephthalate is 100 ℃～220 ℃.
It is described that to take the reaction times that the first transition metal ion liquid is catalyst degradation polyethylene terephthalate be 1min-9h.
The preferred TiCl of the present invention
5 -, VCl
4 -, CrCl
4 -, MnCl
3 -, FeCl
4 -, CoCl
3 -, NiCl
3 -, CuCl
2 -, CuCl
3 -and ZnCl
3 -the synthetic ionic liquid of negatively charged ion and alkyl imidazolium cation is catalyzer.
The temperature of reaction of preparing the first transition metal ion liquid is 10 ℃～80 ℃, and the reaction times is 10min～12h.
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.
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: adding successively 5.0gPET particle, PET granular size in 50ml there-necked flask is 30 orders, 20.0g ethylene glycol and 0.5g 1-butyl-3-Methylimidazole tri-chlorination zinc salt ([bmim] ZnCl
3).Controlling temperature of reaction is 170 ℃, and pressure is 1atm, after condensing reflux reaction 1.5h, is chilled to room temperature.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 80.8%, and in product, the quality percentage composition of monomer is 90.0%.
Embodiment 2
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole manganic chloride salt ([bmim] MnCl
3).With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 78.4%, and in product, the quality percentage composition of monomer is 89.0%.
Embodiment 3
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole tri-chlorination cobalt salt ([bmim] CoCl
3), the PET granular size adding is 30 orders.With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 80.9%, and in product, the quality percentage composition of monomer is 90.2%.
Embodiment 4
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole tri-chlorination nickel salt ([bmim] NiCl
3).With this understanding, the degradation rate of PET polyester is 47%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 67.3%, and in product, the quality percentage composition of monomer is 75.1%.
Embodiment 5
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole tri-chlorination chromic salts ([bmim] CrCl
3).With this understanding, the degradation rate of PET polyester is 17%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 59.1%, and in product, the quality percentage composition of monomer is 68.7%.
Embodiment 6
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole tri-chlorination mantoquita ([bmim] CuCl
3).With this understanding, the degradation rate of PET polyester is 14.4%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 64.1%, and in product, the quality percentage composition of monomer is 74.7%.
Embodiment 7
Other condition is with embodiment 1, and the catalyzer adding is 0.5g 1-butyl-3-Methylimidazole titanium tetrachloride salt ([bmim] FeCl
4).With this understanding, the degradation rate of PET polyester is 100%, and the selectivity of monomers terephthalic acid glycol ester (BHET) is 73.1%, and in product, the quality percentage composition of monomer is 84.7%.
Claims (3)
1. the method for the first transition metal ion liquid catalyst alcoholysis polyethylene terephthalate, is characterized in that take that dibasic alcohol is as solvent, take the first transition metal ion liquid as catalyzer, and described ionic liquid negatively charged ion is MnCl
3 -, CoCl
3 -or ZnCl
3 -, positively charged ion is 1-butyl-3-Methylimidazole ion, i.e. [bmim]
+, catalyst levels is solvent quality 0.1 ‰～2.5%, and temperature of reaction is 80 ℃～170 ℃, and the reaction times is 1min-1.5h.
2. method according to claim 1, is characterized in that described diol solvent is ethylene glycol, Diethylene Glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, 1, the mixture of one or more in 7-heptanediol.
3. method according to claim 1, the molecular weight that it is characterized in that degraded polyethylene terephthalate is 1.8～7.5 * 10
4g/mol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110090618.8A CN102731310B (en) | 2011-04-12 | 2011-04-12 | Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid |
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| CN201110090618.8A CN102731310B (en) | 2011-04-12 | 2011-04-12 | Polyethylene terephthalate alcoholysis method with catalyst of first transition series metal ionic liquid |
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| CN102731310A CN102731310A (en) | 2012-10-17 |
| CN102731310B true CN102731310B (en) | 2014-11-05 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584594B (en) * | 2011-01-11 | 2015-06-03 | 中国科学院过程工程研究所 | Method for catalyzing alcoholysis performed on polyethylene glycol terephthalate (PET) by using CoCl42-/NiCl42-type ionic liquid |
| CN104774153A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院过程工程研究所 | Recycling method for catalytic degradation of waste PET |
| CN104774154A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院过程工程研究所 | Method for catalytic alcoholysis of polyethylene glycol terephthalate with super-strong alkaline ionic liquid |
| CN104327259B (en) * | 2014-11-03 | 2016-02-10 | 东华大学 | A kind of preparation method of low melting point regeneration copolyesters |
| CN104447341B (en) * | 2014-11-03 | 2016-02-10 | 东华大学 | A kind of polyester alcoholysis method |
| CN104327260B (en) * | 2014-11-03 | 2016-04-06 | 东华大学 | A kind of preparation method of biodegradable recycled polyester |
| CN104357938B (en) * | 2014-11-03 | 2016-06-15 | 东华大学 | A kind of preparation method of Regenerated Polyester Fibres |
| CN104327254B (en) * | 2014-11-03 | 2016-06-29 | 东华大学 | A kind of preparation method of recycled polyester |
| CN105017013B (en) * | 2015-05-16 | 2017-06-09 | 青岛科技大学 | A kind of useless poly-lactic acid material alcoholysis method of liquid Lewis acid catalyst |
| CN107162902A (en) * | 2017-06-08 | 2017-09-15 | 中国科学院过程工程研究所 | A kind of method of homogeneous catalysis degraded polyethylene terephthalate |
| CN114031756B (en) | 2021-10-13 | 2022-08-26 | 国高材高分子材料产业创新中心有限公司 | Method for preparing recycled polyester by closed-loop recycling waste polyester with typical green low-carbon characteristics |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584594A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Method for catalyzing alcoholysis performed on polyethylene glycol terephthalate (PET) by using CoCl42-/NiCl42-type ionic liquid |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584594A (en) * | 2011-01-11 | 2012-07-18 | 中国科学院过程工程研究所 | Method for catalyzing alcoholysis performed on polyethylene glycol terephthalate (PET) by using CoCl42-/NiCl42-type ionic liquid |
Non-Patent Citations (2)
| Title |
|---|
| Fe-containing magnetic ionic liquid as an effective catalyst for the glycolysis of poly(ethylene terephthalate);Hui Wang et al;《Catalysis Communications》;20100212;第11卷(第8期);第763-767页 * |
| Hui Wang et al.Fe-containing magnetic ionic liquid as an effective catalyst for the glycolysis of poly(ethylene terephthalate).《Catalysis Communications》.2010,第11卷(第8期),第763-767页. * |
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