CN109529939A - A kind of eutectic solvent catalyst of alcoholysis PET and preparation method thereof - Google Patents
A kind of eutectic solvent catalyst of alcoholysis PET and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to macromolecule degradation, catalysis technical field, the preparation method for being related to a kind of eutectic solvent catalyst and its application in PET alcoholysis process.The present invention is with urea-based compound 1,3- dimethyl urea, trimethyl-urea and 1,1 dimethyl urea carries out complexation reaction as the hydrogen bond donor and inorganic zinc salt of eutectic solvent and inorganic manganese salt, form a kind of eutectic solvent of metal combination, the eutectic solvent can be used as catalyst applied to PET alcoholysis reaction, with catalytic activity height, the fast advantage of reaction rate has potential application prospect.
Description
Technical field
The invention belongs to macromolecule degradations, catalysis technical field, are related to a kind of preparation method of eutectic solvent catalyst
And its application, it is suitable for PET alcoholysis process.
Background technique
Polyethylene terephthalate (PET) is had good by terephthalic acid (TPA) (PTA) and ethylene glycol (EG) esterification gained
Air-tightness well, the transparency, mechanical property, and it is odorless nontoxic, therefore it is widely used in the fields such as food packaging, fiber, film.
But PET is difficult to degrade in the natural environment, and huge consumption figure brings serious problem of environmental pollution while also resulting in money
The serious waste in source, waste PET recycle the problem of having become a global concern.Chemical recovery primarily now
Method such as Hydrolyze method, alcoholysis method, amine-decomposing method are widely had studied.Since reaction condition is relatively mild and reactant volatilization
The low advantage of property, glycolysis alcoholysis method is the method for being most hopeful to be mass produced.
For glycolysis alcoholysis method, at present researchers be directed generally to exploitation new catalyst accelerate alcoholysis reaction and
Improve reaction condition.Some new catalysts, it is difficult if heteropoly acid can accelerate reaction efficiency, but catalyst preparation process complexity
To meet the requirement of large-scale production.Ionic liquid is with steam forces down, liquid journey is wide, good conductivity, nonflammable and property is adjustable
The advantages of, there is more application during PET glycolysis alcoholysis.However, the ionic liquid synthesis process of functionalization is complicated, point
From needing to be unable to satisfy environmental-friendly demand in purification process using a large amount of organic solvents, and ionic liquid starting material price is high
High, these factors equally restrict its application.
Eutectic solvent is a kind of fusing point that is mixed to form by the two kinds of components composition lower than each component, usually by hydrogen
Key donor, as amine, alcohols, acids and hydrogen bond receptor, such as quaternary ammonium salt and metal inorganic salt are constituted.Eutectic solvent is in addition to tool
Have the advantages that with physicochemical properties similar in ionic liquid outside also have it is biodegradable, less toxic, be widely used in electrification
The fields such as, catalysis, extraction, biomass processes.And compare and ionic liquid, eutectic solvent price is cheaper, is easy to make
It is standby, it is more advantageous to industrially a large amount of uses.For the present invention using ureas and metal zinc salt or manganese salt as raw material, preparation eutectic is molten
Agent, by the concerted acid-base catalysis of two components, efficiently and rapidly alcoholysis waste PET in a mild condition, is waste PET
It recycles and a kind of new catalyst is provided.
Summary of the invention
The present invention provides a kind of preparation method of efficient eutectic solvent catalyst for PET alcoholysis reaction, it is intended to solve
The defect of certainly current existing PET alcoholysis low efficiency.
To achieve the goals above, the present invention by adjusting the type of urea-based compound in eutectic solvent and metal salt with
It matches to prepare the eutectic solvent catalyst of different coordination structures, and efficiently quickly catalytic alcohol depolymerization pair in a mild condition
Ethylene terephthalate prepares the process of monomers terephthalic acid glycol ester (BHET).
Reaction formula of the invention is (by taking ethylene glycol makees reactant and solvent as an example):
A kind of eutectic solvent catalyst for polyethylene terephthalate of degrading, it is characterised in that the catalyst is
One or more of 1,3- dimethyl urea, 1,1- dimethyl urea, trimethyl-urea and zinc acetate, zinc nitrate, zinc sulfate, chlorination
One or more of 1:2-10:1 in molar ratio of zinc, manganese acetate, manganese nitrate, manganese sulfate or manganese chloride are coordinated the composition to be formed.
The preparation method characteristic of eutectic solvent is will be in 1,3- dimethyl urea, 1,1- dimethyl urea, trimethyl-urea
It is one or more of with and zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, manganese acetate, manganese nitrate, one kind of manganese sulfate or manganese chloride
Or several 1:2-10:1 in molar ratio are directly mixed, and stir 1h-10h at 70 DEG C -120 DEG C, until obtaining solution.
The eutectic solvent catalyst is used for PET alcoholysis reaction, it is characterised in that the poly terephthalic acid second degraded
The raw material sources of diol ester are the one or two or more kinds of beverage bottle, pet film, fiber or particle,
Alcohols in the application is ethylene glycol, and the additional amount of catalyst is the 0.1%- of the additional amount of polyethylene terephthalate
10%, reaction temperature is 150 DEG C -197 DEG C, reaction time 10min-5h.
After reaction, the yield of the degradation rate of PET polyester and product presses formula (1) (2) calculating respectively:
Wherein, A indicates the initial mass for the PET being added, and B indicates undegradable PET mass.
Specific embodiment
The present invention is illustrated with following embodiment, but the present invention is not limited in following embodiments, is not departing from front and back
Under the range of affiliated objective, change is included in technical scope of the invention.
Embodiment 1
Implementation method: by 1g 1,4:1 is mixed 3- dimethyl urea in molar ratio with acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 82.01% of monomer BHET.
Embodiment 2
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and zinc nitrate hexahydrate, is heated at 90 DEG C
2h obtains supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is
190 DEG C, pressure 1atm, 0.25g urea groups eutectic ionic liquid catalyst is added, is cooled to room after being condensed back reaction 20min
Temperature.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition,
The degradation rate of PET polyester is 100%, the yield 81.41% of monomer BHET.
Embodiment 3
Implementation method: by 1g 1,10:1 is mixed in molar ratio for 3- dimethyl urea and Zinc vitriol, is heated at 70 DEG C
10h obtains supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is
190 DEG C, pressure 1atm, 0.25g urea groups eutectic ionic liquid catalyst is added, is cooled to room after being condensed back reaction 20min
Temperature.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition,
The degradation rate of PET polyester is 100%, the yield 78.69% of monomer BHET.
Embodiment 4
Implementation method: by 1g 1,4:1 is mixed 1- dimethyl urea in molar ratio with zinc chloride, is heated 2h at 90 DEG C, is obtained
Supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190 DEG C, pressure
Power is 1atm, and 0.25g urea groups eutectic ionic liquid catalyst is added, and is cooled to room temperature after being condensed back reaction 20min.Then it uses
Water separates BHET monomer and oligomer, and BHET solution condensing crystallizing is obtained BHET monomer, with this condition, PET polyester
Degradation rate is 100%, the yield 80.57% of monomer BHET.
Embodiment 5
Implementation method: by 0.5g trimethyl-urea, 1:1 is mixed in molar ratio with four hydration manganese acetates, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 79.68% of monomer BHET.
Embodiment 6
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and four nitric hydrate manganese, is heated at 90 DEG C
2h obtains supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is
190 DEG C, pressure 1atm, 0.25g urea groups eutectic ionic liquid catalyst is added, is cooled to room after being condensed back reaction 20min
Temperature.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition,
The degradation rate of PET polyester is 100%, the yield 78.36% of monomer BHET.
Embodiment 7
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and seven hydrated manganese sulfates, is heated at 90 DEG C
2h obtains supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is
190 DEG C, pressure 1atm, 0.25g urea groups eutectic ionic liquid catalyst is added, is cooled to room after being condensed back reaction 20min
Temperature.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition,
The degradation rate of PET polyester is 100%, the yield 75.45% of monomer BHET.
Embodiment 8
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and tetrahydrate manganese chloride, is heated at 120 DEG C
1h obtains supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is
190 DEG C, pressure 1atm, 0.25g urea groups eutectic ionic liquid catalyst is added, is cooled to room after being condensed back reaction 20min
Temperature.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition,
The degradation rate of PET polyester is 100%, the yield 76.88% of monomer BHET.
Embodiment 9
Implementation method: by 1g 1,2:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 97.44%, the yield 71.25% of monomer BHET.
Embodiment 10
Implementation method: by 1g 1,6:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 81.55% of monomer BHET.
Embodiment 11
Implementation method: by 1g 1,8:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 82.12% of monomer BHET.
Embodiment 12
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 1- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 81.71% of monomer BHET.
Embodiment 13
Implementation method: by 0.5g trimethyl-urea and acetic anhydride zinc, 4:1 is mixed in molar ratio, is heated 2h at 90 DEG C, is obtained
To supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190 DEG C,
Pressure is 1atm, and 0.25g urea groups eutectic ionic liquid catalyst is added, and is cooled to room temperature after being condensed back reaction 20min.Then
BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET polyester
Degradation rate be 100%, the yield 80.64% of monomer BHET.
Embodiment 14
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.05g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 23.36%, the yield 14.73% of monomer BHET.
Embodiment 15
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.15g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 70.92%, the yield 57.49% of monomer BHET.
Embodiment 16
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.35g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 82.24% of monomer BHET.
Embodiment 17
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 10min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 63.78%, the yield 51.18% of monomer BHET.
Embodiment 18
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 40min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 80.26% of monomer BHET.
Embodiment 19
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 190
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 60min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 100%, the yield 80.45% of monomer BHET.
Embodiment 20
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 150
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 2.3%, the yield 0.25% of monomer BHET.
Embodiment 21
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 160
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 10.12%, the yield 8.37% of monomer BHET.
Embodiment 22
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 170
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 46.45%, the yield 37.82% of monomer BHET.
Embodiment 23
Implementation method: by 1g 1,4:1 is mixed in molar ratio for 3- dimethyl urea and acetic anhydride zinc, heats 2h at 90 DEG C,
Obtain supernatant liquid.5.0gPET particle, 20g ethylene glycol are sequentially added in 50ml three-necked flask.Controlling reaction temperature is 180
DEG C, 0.25g urea groups eutectic ionic liquid catalyst is added in pressure 1atm, is cooled to room temperature after being condensed back reaction 20min.
Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET monomer, with this condition, PET
The degradation rate of polyester is 86.34%, the yield 67.99% of monomer BHET.
Embodiment 24
Implementation method: by 1g 1,3- dimethyl urea, acetic anhydride zinc and four water and manganese acetate 4:0.5:0.5 in molar ratio
Mixing, heats 2h at 90 DEG C, obtains supernatant liquid.5.0gPET particle, 20g second two are sequentially added in 50ml three-necked flask
Alcohol.Controlling reaction temperature is 180 DEG C, pressure 1atm, and 0.25g urea groups eutectic ionic liquid catalyst is added, and is condensed back
It is cooled to room temperature after reaction 20min.Then BHET monomer and oligomer are separated with water, BHET solution condensing crystallizing is obtained into BHET
Monomer, with this condition, the degradation rate of PET polyester are 87.52%, the yield 72.39% of monomer BHET.
Claims (4)
1. a kind of eutectic solvent catalyst for polyethylene terephthalate of degrading, it is characterised in that the catalyst is 1,
One or more of 3- dimethyl urea, 1,1- dimethyl urea, trimethyl-urea and zinc acetate, zinc nitrate, zinc sulfate, zinc chloride,
One or more of 1:2-10:1 in molar ratio of manganese acetate, manganese nitrate, manganese sulfate or manganese chloride are coordinated the composition to be formed.
2. a kind of preparation method of eutectic solvent as described in claim 1, it is characterised in that by 1,3- dimethyl urea, 1,1- bis-
One or more of methylurea, trimethyl-urea with zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, manganese acetate, manganese nitrate, sulphur
One or more of 1:2-10:1 in molar ratio of sour manganese or manganese chloride are directly mixed, and stir 1h-10h at 70 DEG C -120 DEG C, directly
To obtaining solution.
3. a kind of application of eutectic solvent catalyst as described in claim 1 in PET alcoholysis.
4. application according to claim 3, it is characterised in that the raw material for the polyethylene terephthalate degraded comes
Source is the one or two or more kinds of beverage bottle, pet film, fiber or particle, the alcohol in the application
Class is ethylene glycol, and the additional amount of catalyst is the 0.1%-10% of the additional amount of polyethylene terephthalate, reaction temperature
It is 150 DEG C -197 DEG C, reaction time 10min-5h.
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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 |
| 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 |
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| CN114524965B (en) * | 2022-02-20 | 2023-11-10 | 中国科学院山西煤炭化学研究所 | Method for preparing epoxy porous material or aromatic glyceryl ether compound by using anhydride cured epoxy resin |
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