CN114989400B - Preparation method of chemically regenerated PETG polyester - Google Patents
Preparation method of chemically regenerated PETG polyester Download PDFInfo
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- CN114989400B CN114989400B CN202210783158.5A CN202210783158A CN114989400B CN 114989400 B CN114989400 B CN 114989400B CN 202210783158 A CN202210783158 A CN 202210783158A CN 114989400 B CN114989400 B CN 114989400B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The invention provides a preparation method of chemically regenerated PETG polyester. The preparation method comprises the following steps: crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain PET polyester fragments, heating the PET polyester fragments to be molten, adding dihydric alcohol and a catalyst to perform primary alcoholysis, and filtering the products; carrying out secondary alcoholysis on the product under the action of dihydric alcohol and a catalyst, and carrying out post-treatment on the product; uniformly stirring the product and mixed slurry containing terephthalic acid and at least one diol in a nitrogen environment, carrying out esterification reaction at the temperature of 200-260 ℃, and distilling out excessive diol to obtain an esterification product; and (3) carrying out polycondensation on the esterification product at 260-280 ℃ under the action of a catalyst and within the pressure range of 0.1-10kPa, and carrying out post-treatment to obtain the PETG. The prepared PETG has obviously improved odor and emission characteristics, the TVOC value of the PETG is lower than 40ug C/g, has lower abrasion index, and presents excellent wear resistance and better mechanical property.
Description
Technical Field
The invention relates to a preparation method of amorphous copolyester, in particular to a preparation method of chemically regenerated PETG polyester.
Background
Polyethylene terephthalate (PET, polyester for short) is an important raw material, and is mainly used for producing fibers, polyester bottles, films, and the like. The polyester waste is mainly derived from waste materials, leftover materials, waste polyester bottles, polyester films and the like generated in the production process. The polyester plastic has chemical stability, corrosion resistance, electrical insulation and heat insulation, is not easy to naturally digest, can cause great damage to the environment after being retained in the environment for a long time, and is not beneficial to sustainable development; meanwhile, the cost of the polymer materials using crude oil or natural gas as raw materials is increasing, and the resources are decreasing. Moreover, with the rapid development of the polyester industry, the amount of polyester waste is increasing, and therefore the recycling of polyester waste has become a major issue in the development of the current polyester industry.
At present, the recycling of polyester waste materials mainly comprises a physical method and a chemical method. The physical method is mainly to make the waste polyester and the products thereof into regenerated chips for utilization through simple physical treatment methods such as direct doping, blending, granulation and the like, but the regenerated chips can only be used for producing conventional short fiber products due to large quality fluctuation. The chemical method mainly comprises a hydrolysis method, a methanol alcoholysis method, an ethylene glycol alcoholysis method and the like, and waste polyester is decomposed into raw materials or intermediates for producing the polyester through chemical treatment so as to achieve the aim of repeated use. But cannot be widely popularized due to the technical requirements, high recovery cost and the like. Conventional chemical recycling processes have been directed primarily to the complete degradation of polyesters to recover small molecule products such as terephthalic acid, dimethyl terephthalate, ethylene glycol, etc. which are then reused, such as in the production of short fibers for low add-on applications such as filling. Therefore, the traditional chemical recovery method not only has large raw material consumption and long time consumption, but also has more complex purification procedures of recovered products and the like.
The PETG is an amorphous or low-crystalline material generated by introducing monomer fragments for effectively controlling the crystallinity into the molecular structure of PET, has good optical performance, is particularly suitable for being made into a transparent thick-wall material or a transparent sheet, has environmental protection, degradability and good impact and toughness, can be applied to various packaging materials of sheet pipes, and replaces part of expensive PC and PVC which is not environment-friendly. PETG has excellent processing performance and short molding period, and is widely applied to various extrusion, injection molding, blow molding processes and the like.
Therefore, the production of PETG by using the recycled PET not only can reduce the dependence degree of the polyester industry on petroleum, but also can effectively reduce the energy consumption and the greenhouse gas emission in the PETG production process.
How to solve the above problems in the prior art is a problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The invention aims to: in order to overcome the problems in the prior art, the invention provides a preparation method of chemically regenerated PETG polyester, which uses PET polyester chips to prepare PETG, so that the prepared polyester has obviously improved odor and diffusion characteristics, the TVOC value of the prepared polyester is lower than 40ug C/g, the prepared polyester has lower abrasion index, and the prepared polyester has excellent wear resistance and better mechanical properties (higher tensile strength and stronger notch impact strength).
The technical scheme is as follows: the invention provides a preparation method of chemically regenerated PETG polyester, which comprises the following steps:
step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain PET polyester fragments, heating the PET polyester fragments to be molten, adding dihydric alcohol and a catalyst to carry out primary alcoholysis, and filtering primary alcoholysis products;
step 2, carrying out secondary alcoholysis on the product subjected to primary alcoholysis filtration under the action of dihydric alcohol and a catalyst, and carrying out aftertreatment on the product subjected to secondary alcoholysis;
step 3, adding the product after the secondary alcoholysis filtration into mixed slurry containing terephthalic acid and at least one diol in a nitrogen environment, uniformly stirring, carrying out esterification reaction at the temperature of 200-260 ℃, and distilling out excessive diol to obtain an esterified product;
and 4, carrying out polycondensation reaction on the esterification product at 260-280 ℃ under the action of a catalyst and within the pressure range of 0.1-10kPa, and carrying out post-treatment on the polycondensation product to obtain the PETG.
In the invention, by carrying out secondary alcoholysis on the PET polyester chips, the alcoholysis efficiency and the purity of alcoholysis products are fully improved, the subsequent esterification reaction is ensured to be carried out orderly, and solid impurities in the recovered PET polyester chips are not introduced into the reaction.
In some embodiments of the present invention, in step 1, the polyester chips are heated to be molten under the protection of nitrogen gas, so as to ensure the stability of the raw material melt.
In some embodiments of the invention, in step 1, the temperature of heating to melt is 200 to 270 ℃ (e.g., 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃, 270 ℃, or any point therein).
In some embodiments of the present invention, in step 1, the diol is selected from one of a straight chain aliphatic diol, a cyclized aliphatic diol, or a combination of at least two thereof.
In some embodiments of the invention, in step 1, the linear aliphatic diol is selected from one or a combination of at least two of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-tert-butyl-1, 3-propanediol, or 2, 4-trimethyl-1, 6-hexanediol.
In some embodiments of the invention, in step 1, the cycloaliphatic diol is selected from one or a combination of at least two of cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1-3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, or isosorbide.
In some embodiments of the present invention, in step 1, the diol is preferably a cyclic aliphatic diol, and is further preferably one or a combination of at least two of cyclopentanediol, 1, 2-cyclohexanedimethanol, 1-3-cyclohexanedimethanol, and 1, 4-cyclohexanedimethanol, and in order to obtain a better abrasion index and better mechanical properties, the diol is preferably cyclopentanediol.
In the invention, the weight ratio of PET polyester chips to dihydric alcohol has a certain influence on alcoholysis reaction, the use amount of the dihydric alcohol is too high, excessive dihydric alcohol can be mixed in an alcoholysis product, other byproducts can be generated in the alcoholysis product, the use amount of the dihydric alcohol is too low, alcoholysis is not thorough, the alcoholysis product also contains more long-chain waste polyester, and the two conditions can influence the quality stability of the alcoholysis product, thereby influencing the subsequent ester exchange reaction.
In some embodiments of the present invention, in step 1, the weight ratio of PET polyester chip to glycol is 1 to 4 (for example, can be 1.
In some embodiments of the invention, in step 1, the catalyst has the formula K 10 [M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 A heteropoly acid of O, wherein M isAny one of Zn, mn, co, ni or Cu, preferably, M is Co, in order to obtain a better wear index, better mechanical properties, and shorter reaction time.
In the invention, the dosage of the catalyst has great influence on the alcoholysis product, and the degradation efficiency of the polyester can be ensured only by controlling the dosage of the added catalyst within a proper range, and the catalyst is not wasted.
In some embodiments of the invention, in step 1, the catalyst molecules are added in an amount of 0.3 to 3wt% (e.g., may be 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3 wt%) based on the weight of the PET polyester chips.
In some embodiments of the invention, in step 1, the primary alcoholysis is carried out in a nitrogen environment in a microwave of 500-700W (e.g., 500W, 510W, 520W, 530W, 540W, 550W, 560W, 570W, 580W, 590W, 600W, 610W, 620W, 630W, 640W, 650W, 660W, 670W, 680W, 690W, 700W, or any point therein) for 2-20 min (e.g., 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20 min).
In the invention, the power of the microwave has an influence on the catalytic action of the catalyst, and only if the dosage of the added catalyst is matched with the power of the microwave, the degradation efficiency of the polyester can be ensured and the alcoholysis product can be ensured to have a proper molecular weight (1200-2000 g/mol, such as 1200g/mol, 1300g/mol, 1400g/mol, 1500g/mol, 1600g/mol, 1700g/mol, 1800g/mol, 1900g/mol and 2000 g/mol), so that the reaction time can be saved without wasting the catalyst.
In some embodiments of the invention, in step 1, the filtration can be divided into coarse filtration and filtered filtration, wherein the filtration precision of the coarse filtration is 1000 to 4000 μm (e.g., 1000 μm, 1100 μm, 1200 μm, 1300 μm, 1400 μm, 1500 μm, 1600 μm, 1700 μm, 1800 μm, 1900 μm, 2000 μm, 2100 μm, 2200 μm, 2300 μm, 2400 μm, 2500 μm, 2600 μm, 2700 μm, 2800 μm, 2900 μm, 3000 μm, 3100 μm, 3200 μm, 3300 μm, 3400 μm, 3500 μm, 3600 μm, 3700 μm, 3800 μm, 3900 μm, 4000 μm), the filtration precision of the fine filtration is 11 to 300 μm (e.g., can be 11 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 195 μm, 200 μm, 205 μm, 210 μm, 215 μm, 220 μm, 225 μm, 230 μm, 235 μm, 240 μm, 245 μm, 250 μm, 255 μm, 260 μm, 265 μm, 270 μm, 280 μm, 275 μm, 285 μm, 295 μm, 290 μm).
In some embodiments of the present invention, in step 2, the glycol is selected from one of a straight chain aliphatic glycol, a cyclized aliphatic glycol, or a combination of at least two thereof.
In some embodiments of the invention, in step 2, the linear aliphatic diol is selected from one or a combination of at least two of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-tert-butyl-1, 3-propanediol, or 2, 4-trimethyl-1, 6-hexanediol.
In some embodiments of the invention, in step 2, the cycloaliphatic diol is selected from one or a combination of at least two of cyclopentanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1-3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, or isosorbide.
In some embodiments of the present invention, in step 2, the diol is preferably a cyclic aliphatic diol, and is further preferably one or a combination of at least two of cyclopentanediol, 1, 2-cyclohexanedimethanol, 1-3-cyclohexanedimethanol, and 1, 4-cyclohexanedimethanol.
In some embodiments of the present invention, in step 2, the weight ratio of the product after primary alcoholysis filtration to glycol is 1.
In some embodiments of the invention, in step 2, the catalyst has the formula K 10 [M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 O or Na 10 [M 4 (H 2 O) 2 (ZnW 9 O 34 ) 2 ]·H 2 And the heteropolyacid of O, wherein M is any one of Zn, mn, co, ni or Cu, is preferably Co in order to obtain better abrasion index, better mechanical property and shorter reaction time.
In some embodiments of the invention, catalyst molecules are added in step 2 in an amount of 0.1 to 2wt% (e.g., can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.5wt%, 2 wt%) based on the weight of the product after the primary alcoholysis filtration.
In some embodiments of the invention, in step 2, the second alcoholysis is carried out in a nitrogen environment in a microwave of 400-600W (e.g., 400W, 410W, 420W, 430W, 440W, 450W, 460W, 470W, 480W, 490W, 500W, 510W, 520W, 530W, 540W, 550W, 560W, 570W, 580W, 590W, 600W, or any point thereof) for 1-10 min (e.g., 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10 min).
In some embodiments of the invention, in step 2, the post-treatment process is selective decolorization and/or filtration of the alcoholysis product as desired for production.
In some embodiments of the invention, in step 2, the product decolorization is activated carbon decolorization, the decolorization temperature is 150 to 200 ℃ (for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃), and the decolorization time is 15 to 40min (for example, 15min, 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40 min).
In some embodiments of the invention, in step 2, the filtration is a fine filtration, wherein the filtered filtration precision is 11 to 300 μm (e.g., can be 11 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 200 μm, 205 μm, 210 μm, 215 μm, 220 μm, 225 μm, 230 μm, 235 μm, 240 μm, 255 μm, 250 μm, 285 μm, 275 μm, 270 μm, 275 μm, 265 μm, 295 μm).
In some embodiments of the present invention, in step 3, the diol (e.g., which may be two, three, four) is selected from one or a combination of at least two of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-tert-butyl-1, 3-propanediol, or 2, 4-trimethyl-1, 6-hexanediol, preferably ethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-tert-butyl-1, 3-propanediol, and more preferably ethylene glycol or 1, 4-butanediol.
In some embodiments of the invention, in step 3, the glycol comprises at least one ethylene glycol and at least one 1, 4-butanediol, wherein the mass ratio of ethylene glycol and 1, 4-butanediol is 1-5.
In some embodiments of the present invention, in step 3, the weight ratio of the product after the secondary alcoholysis filtration to the mixed slurry comprising terephthalic acid and at least one glycol is 1.
In some embodiments of the present invention, in step 3, the weight ratio of terephthalic acid to glycol is 1.
In the invention, the product of PET polyester alcoholysis is directly mixed with the mixed slurry containing terephthalic acid and at least one diol, so that the proportion of the product of PET polyester alcoholysis in the prepared PETG can be easily regulated and controlled, and different production requirements can be met.
In some embodiments of the present invention, in step 3, the esterification reaction temperature may be 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, or any point value thereof.
In some embodiments of the present invention, in step 4, the polycondensation reaction temperature may be 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, or any value thereof.
In some embodiments of the invention, in step 4, the pressure is from 0.1 to 10kPa (which may be, for example, 0.1kPa, 0.5kPa, 1kPa, 2kPa, 3kPa, 4kPa, 5kPa, 6kPa, 7kPa, 8kPa, 9kPa, 10 kPa).
In some embodiments of the invention, in step 4, if the viscosity of the reaction mixture reaches the desired value, the pressure may be returned to atmospheric pressure by passing nitrogen gas through the reaction mixture, so that the polyester is rapidly cooled and pelletized, and a polyester having an intrinsic viscosity of 0.4 to 0.8DL/g is generally obtained.
In some embodiments of the invention, in step 4, the catalyst is antimony trioxide or germanium dioxide.
In some embodiments of the invention, catalyst molecules are added in step 4 in an amount of 0.3 to 3wt% (e.g., can be 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3 wt%) based on the weight of the esterification product.
In some embodiments of the invention, in step 4, the work-up process is selective filtration and/or partitioning of the polycondensation product as desired for production.
In some embodiments of the invention, in step 4, the filtration is a fine filtration, wherein the filtered filtration precision is 11 to 300 μm (e.g., can be 11 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 200 μm, 205 μm, 210 μm, 215 μm, 220 μm, 225 μm, 230 μm, 235 μm, 245 μm, 255 μm, 240 μm, 255 μm, 275 μm, 260 μm, 285 μm, 290 μm, 265 μm).
In some embodiments of the invention, in step 4, the partitioning may be by mechanical means to lump or granulate the product, a common technique being cutting.
In some embodiments of the present invention, a lubricant, stabilizer or antioxidant may also be included in the polycondensation reaction of step 4.
In some embodiments of the present invention, in step 4, the lubricant is added in an amount of 0.1 to 0.5wt% (e.g., may be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5 wt%) based on the weight of the esterification product.
In some embodiments of the invention, in step 4, the stabilizer is added in an amount of 0.1 to 0.5wt% (e.g., can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5 wt%) based on the weight of the esterification product.
In some embodiments of the invention, in step 4, the antioxidant is added in an amount of 0.1 to 0.5wt% (e.g., can be 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5 wt%) based on the weight of the esterification product.
In some embodiments of the invention, the lubricant is selected from one or a combination of at least two of silicone powder, white oil, silicone oil, paraffin, stearic acid, zinc stearate.
In some embodiments of the invention, the stabilizer is selected from one or a combination of at least two of phosphoric acid, sodium phosphate, potassium phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, phosphorous acid, sodium phosphite.
In some embodiments of the invention, the antioxidant is selected from one or a combination of at least two of pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1098) and tris- (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168).
Has the beneficial effects that: the polyester prepared by the preparation method has obviously improved odor and diffusion characteristics, the TVOC value of the polyester is lower than 40ug C/g, the polyester has a lower abrasion index, and the polyester presents excellent wear resistance and better mechanical properties (higher tensile strength and stronger notch impact strength). By carrying out secondary alcoholysis on the PET polyester chips, the alcoholysis efficiency and the purity of alcoholysis products are fully improved, the sequential esterification reaction is ensured, and solid impurities in the recovered PET polyester chips cannot be introduced into the reaction. The product after the alcoholysis of the PET polyester is directly mixed with the mixed slurry containing terephthalic acid and at least one diol, so that the proportion of the product after the alcoholysis of the PET polyester in the prepared PETG can be easily regulated and controlled, and different production requirements can be met.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
The solvents and starting materials used in the following examples are commercially available products.
Example 1
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at 260-270 ℃, and heating the PET polyester chips to be molten under the protection of nitrogenUnder gas protection, 160g of cyclopentanediol and 0.3g of K were added 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decolorizing the secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) into 40g of the product subjected to secondary alcoholysis filtration in a nitrogen environment, uniformly stirring, mixing into slurry in the nitrogen environment, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterified product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 2
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 120g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 260g of the product after the primary alcoholysis filtration are, under nitrogen, supplemented with 72g of cyclopentanediol and 0.18g of K 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) in a nitrogen environment, uniformly stirring, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 3
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 250g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 150g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) in a nitrogen environment, uniformly stirring, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 4
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 300g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, 60g of product after primary alcoholysis filtration is added with 180g of cyclopentane diol and 0.18g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen gas into the heteropolyacid catalyst of O under the stirring condition, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) in a nitrogen environment, uniformly stirring, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 5
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 160g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 micrometers) and fine filtration (the filtration precision is 300 micrometers) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 50g of mixed slurry containing terephthalic acid and ethylene glycol in a nitrogen environment, uniformly stirring (the weight ratio of the terephthalic acid to the ethylene glycol is 1.4), performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 6
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the conditions of 260-270 ℃ and nitrogen protection, and adding 160g of cyclopentanediol and 0.3g of K under the nitrogen protection 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 180g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 7
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 160g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Zn 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 8min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Zn 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen gas into the heteropolyacid catalyst of O under the stirring condition, carrying out alcoholysis reaction for 8min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) in a nitrogen environment, uniformly stirring, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 8
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the conditions of 260-270 ℃ and nitrogen protection, and adding 160g of cyclopentanediol and 0.3g of K under the nitrogen protection 10 [Cu 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 12min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Cu 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 10min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) in a nitrogen environment, uniformly stirring, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterification product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 9
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 160g of 1-3-cyclohexanedimethanol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of 1-3-cyclohexanedimethanol and 0.18g of K into 60g of a product obtained after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1.56) into 40g of the product subjected to secondary alcoholysis filtration under a nitrogen ring, uniformly stirring, performing an esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterified product;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 10
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 160g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 90g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 124g of mixed slurry containing terephthalic acid, ethylene glycol and 1, 4-butanediol (the weight ratio of the terephthalic acid to the dihydric alcohol (the weight ratio of the ethylene glycol to the 1, 4-butanediol is 2) is 1;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 11
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the conditions of 260-270 ℃ and nitrogen protection, and adding 250g of cyclopentanediol and 0.3g of K under the nitrogen protection 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 micrometers) and fine filtration (the filtration precision is 300 micrometers) on the product;
step 2, adding 150g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 114g of mixed slurry containing terephthalic acid, ethylene glycol and 1, 4-butanediol (the weight ratio of the terephthalic acid to the dihydric alcohol (the weight ratio of the ethylene glycol to the 1, 4-butanediol is 3) is 1;
and 4, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 12
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 160g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 micrometers) and fine filtration (the filtration precision is 300 micrometers) on the product;
step 2, 60g of the product after primary alcoholysis filtration is added under the protection of nitrogen90g of cyclopentanediol and 0.18g of K 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 3min under the action of 400W microwaves, decoloring a secondary alcoholysis product by using activated carbon, and filtering (the filtering precision is 300 mu m);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 121g of mixed slurry containing terephthalic acid, ethylene glycol and 1, 4-butanediol (the weight ratio of the terephthalic acid to the dihydric alcohol (the weight ratio of the ethylene glycol to the 1, 4-butanediol is 1: 1.56) in a nitrogen environment, uniformly stirring, carrying out esterification reaction at the temperature of 250-260 ℃, and distilling out excessive dihydric alcohol to obtain an esterification product;
and 4, adding 0.02g of silicone oil, 0.04g of sodium phosphate, 0.02g of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to be 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Example 13
Step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the protection of nitrogen at the temperature of between 260 and 270 ℃, and adding 250g of cyclopentanediol and 0.3g of K under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Continuously introducing nitrogen into the O heteropoly acid catalyst under stirring, carrying out alcoholysis reaction for 4min under the action of 500W microwaves, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the product;
step 2, adding 150g of cyclopentane diol and 0.18g of K into 60g of the product after primary alcoholysis filtration under the protection of nitrogen 10 [Co 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 Introducing nitrogen gas continuously under stirring for alcoholysis reaction for 3min under the action of 400W microwave, and reacting with activated carbonDecolorizing the decomposition product, and filtering (the filtering precision is 300 μm);
step 3, adding 40g of the product subjected to secondary alcoholysis filtration into 121g of mixed slurry containing terephthalic acid, ethylene glycol and 1, 4-butanediol (the weight ratio of the terephthalic acid to the dihydric alcohol is 1:1.56 (the weight ratio of the ethylene glycol to the 1, 4-butanediol is 1);
and 4, adding 0.02g of stearic acid, 0.04g of potassium phosphate, 0.02g of tris- (2, 4-di-tert-butylphenyl) phosphite and 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to be 260-280 ℃ and nitrogen atmosphere, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Comparative example 1
Step 1, crushing PET polyester waste products obtained by selection and sorting by using a crushing device to obtain 100g of PET polyester chips, heating the PET polyester chips to be molten under the condition of 260-270 ℃ and nitrogen protection, adding 160g of cyclopentanediol and 0.3g of zinc acetate under the condition of nitrogen protection, continuously introducing nitrogen while stirring, carrying out alcoholysis reaction for 40min at 260-270 ℃, and sequentially carrying out coarse filtration (the filtration precision is 3000 mu m) and fine filtration (the filtration precision is 300 mu m) on the products;
step 2, mixing 40g of the product subjected to primary alcoholysis filtration, 64g of terephthalic acid and 100g of ethylene glycol into slurry in a nitrogen environment, performing esterification reaction at the temperature of 250-260 ℃, and distilling out excessive ethylene glycol to obtain an esterified product;
and 3, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature at 260-280 ℃ and nitrogen environment, carrying out polycondensation reaction, filtering the polycondensation product (the filtering precision is 150 mu m), and pelletizing to obtain the PETG.
Comparative example 2
Step 1, adding 40g of PET into 124g of mixed slurry containing terephthalic acid and ethylene glycol (the weight ratio of the terephthalic acid to the ethylene glycol is 1;
and 2, adding 0.6g of antimony trioxide into 20g of the esterification product under the conditions of 1-10kPa, controlling the temperature to 260-280 ℃ and nitrogen atmosphere to perform polycondensation reaction, filtering the polycondensation product (the filtration precision is 150 mu m), and pelletizing to obtain the PETG.
The PETG prepared in examples 1 to 13 and comparative example 1 were each examined for mechanical properties (tensile strength, MPa, notched impact strength KJ/m) 2 ) Odor grade, TVOC (ugC/g) and abrasion resistance (750g, 1000r)). The mechanical properties are tested according to ASTM standard, the odor grade and TVOC are tested according to GAW standard, the wear resistance is tested according to GB/T5478-2008, and the physical property data are shown in Table 1 below.
TABLE 1 Performance test data for examples 1-13 and comparative example 1
| Tensile strength | Notched impact strength | Wear resistance | TVOC | Odor grade | |
| Example 1 | 145 | 28 | 0.11 | 37 | Stage 8 |
| Example 2 | 132 | 24 | 0.13 | 36 | Stage 8 |
| Example 3 | 147 | 29 | 0.09 | 36 | Stage 8 |
| Example 4 | 133 | 26 | 0.13 | 35 | Stage 8 |
| Example 5 | 138 | 26 | 0.10 | 33 | Stage 8 |
| Example 6 | 135 | 25 | 0.12 | 34 | Stage 8 |
| Example 7 | 128 | 27 | 0.12 | 36 | Stage 7 |
| Example 8 | 118 | 27 | 0.13 | 35 | Stage 7 |
| Example 9 | 131 | 26 | 0.11 | 36 | Stage 8 |
| Example 10 | 155 | 30 | 0.09 | 33 | Stage 8 |
| Example 11 | 157 | 29 | 0.08 | 35 | Stage 8 |
| Example 12 | 156 | 29 | 0.09 | 34 | Stage 8 |
| Example 13 | 158 | 30 | 0.08 | 35 | Stage 8 |
| Comparative example 1 | 80 | 5 | 0.51 | 163 | Grade 5 |
| Comparative example 2 | 160 | 29 | 0.08 | 34 | Stage 8 |
As can be seen from the data in Table 1, the PETG prepared by the method has obviously improved odor and diffusion characteristics, the prepared TVOC value is lower than 40ug C/g, the TVOC value has lower abrasion index, the excellent wear resistance is presented, the mechanical properties (larger tensile strength and stronger notch impact strength) are obviously improved, and the TVOC value is equivalent to the PETG property directly synthesized by using PET as a raw material, so that the resource recycling is effectively realized.
As can be seen from the comparison of examples 1 to 4, when the weight ratio of PET polyester chips to dihydric alcohol in step 1 is 1.6-1.
As can be seen from the comparison of examples 1 to 4, when the weight ratio of the product after the primary alcoholysis filtration in the step 2 to the glycol is 1.6 to 1.
As can be seen from the comparison between example 1 and examples 5-6, when the weight ratio of the product after the secondary alcoholysis filtration in step 3 to the mixed slurry containing terephthalic acid and at least one glycol is 1.
From a comparison of example 1 with examples 7 to 8, it can be seen that when K is 10 [M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 When M of the O heteropoly acid catalyst is Co, the PETG prepared by the method has better abrasion index and better mechanical property.
In conclusion, the PETG prepared by the method has obviously improved odor and diffusion characteristics, so that the prepared TVOC value is lower than 40ug C/g, the prepared TVOC value has a lower abrasion index, the prepared PETG has excellent wear resistance, and the mechanical properties (larger tensile strength and stronger notch impact strength) are obviously improved. Compared with PETG synthesized by a conventional method, the performance of the PETG is no different, and even better. And through two times of alcoholysis on the PET polyester chips, the alcoholysis purity of the polyester can be improved, the esterification reaction rate is easy to improve, and the PET polyester alcoholysis product is creatively mixed with the slurry containing terephthalic acid in the esterification stage, so that the proportion of the PET polyester alcoholysis product in the slurry is better controlled. Namely, the preparation method is more efficient and can meet the requirements of industrial production.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and equivalent changes and modifications made according to the spirit of the present invention should be covered thereby.
Claims (3)
1. The preparation method of the chemically regenerated PETG polyester is characterized by comprising the following steps of:
step 1, crushing the PET polyester waste products obtained by selection and sorting by using a crushing device to obtain PET polyester fragments, heating the PET polyester fragments to be molten, adding dihydric alcohol and a catalyst to carry out primary alcoholysis, and filtering primary alcoholysis products;
step 2, carrying out secondary alcoholysis on the product subjected to primary alcoholysis filtration under the action of dihydric alcohol and a catalyst, and carrying out aftertreatment on the product subjected to secondary alcoholysis;
step 3, adding the product subjected to secondary alcoholysis filtration into mixed slurry containing terephthalic acid and at least one diol in a nitrogen environment, uniformly stirring, carrying out esterification reaction at the temperature of 200-260 ℃, and distilling out excessive diol to obtain an esterification product;
step 4, carrying out polycondensation reaction on the esterification product at 260-280 ℃ under the action of a catalyst and within the pressure range of 0.1-10kPa, and carrying out post-treatment on the polycondensation product to obtain PETG;
in the step 1, the diol is cyclopentanediol; the mass ratio of the PET polyester chips to the dihydric alcohol is 1.6-1; the molecular formula of the catalyst is K 10 [M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 A heteropoly acid of O, wherein M is Co; based on the weight of the PET polyester chips, the addition amount of the catalyst molecules is 0.3-3 wt%; the primary alcoholysis is carried out for 2-20 min in 500-700W microwave under nitrogen environment;
in the step 2, the dihydric alcohol is one of cyclopentane diol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol and 1, 4-cyclohexanedimethanol or a combination of at least two of the two; the weight ratio of the product after the primary alcoholysis filtration to the dihydric alcohol is 1.6-1; the molecular formula of the catalyst is K 10 [M 4 (H 2 O) 2 (PW 9 O 34 ) 2 ]·H 2 O or Na 10 [M 4 (H 2 O) 2 (ZnW 9 O 34 ) 2 ]·H 2 A heteropoly acid of O, wherein M is Co;the weight of the product after the primary alcoholysis filtration is taken as a reference, and the addition amount of the catalyst molecules is 0.1-2 wt%; the secondary alcoholysis is carried out for 1-10 min in 400-600W microwave under nitrogen environment;
in the step 3, the dihydric alcohol is selected from one of ethylene glycol and 1, 4-butanediol or a combination of at least two of the ethylene glycol and the 1, 4-butanediol; the weight ratio of the product after the secondary alcoholysis filtration to the mixed slurry containing the terephthalic acid and at least one diol is 1.
2. The method according to claim 1, wherein the heating to the melting temperature in step 1 is 200 to 270 ℃.
3. The production method according to claim 1, wherein in the step 4, the catalyst is antimony trioxide or germanium dioxide; based on the weight of the esterification product, the addition amount of the catalyst molecules is 0.3-3 wt%.
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