WO2023020293A1 - 一种光热降解聚酯的方法 - Google Patents

一种光热降解聚酯的方法 Download PDF

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WO2023020293A1
WO2023020293A1 PCT/CN2022/110348 CN2022110348W WO2023020293A1 WO 2023020293 A1 WO2023020293 A1 WO 2023020293A1 CN 2022110348 W CN2022110348 W CN 2022110348W WO 2023020293 A1 WO2023020293 A1 WO 2023020293A1
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polyester
photothermal
reaction
terephthalate
pet
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PCT/CN2022/110348
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English (en)
French (fr)
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刘钰
曹暮寒
陈金星
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苏州大学
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Publication of WO2023020293A1 publication Critical patent/WO2023020293A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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

Definitions

  • the invention belongs to polymer treatment technology, in particular to a method for photothermally degrading polyester.
  • Polyester is a conventional plastic product, among which polyethylene terephthalate (PET) is widely used.
  • PET is obtained by transesterification of dimethyl terephthalate and ethylene glycol, or esterification of terephthalic acid and ethylene glycol to bis(2-hydroxyethyl) terephthalate, and then polycondensation reaction. .
  • PET is widely used in high-strength fibers, packaging, films and plastic bottles.
  • PET is divided into fiber-grade polyester chips and non-fiber-grade polyester chips. 1Fiber-grade polyester is used to manufacture polyester staple fiber and polyester filament, and is a raw material for polyester fiber enterprises to process fibers and related products.
  • Polyester is the most productive variety among chemical fibers. 2 Non-fiber grade polyester is also used in bottles and films, and is widely used in packaging, electronic appliances, medical and health care, construction, automobiles and other fields. Among them, packaging is the largest non-fiber application market for polyester, and PET is the fastest growing market. fast field. At the same time, the huge consumption and production of PET produces a large amount of PET waste, which makes the degradation and recycling of PET waste a huge challenge. In addition, the raw materials for PET production come from limited and non-renewable petroleum resources. Therefore, the recycling of waste PET can not only reduce the damage to the environment, but also prolong the resource utilization cycle, bringing huge social and economic benefits.
  • PET recycling methods include mechanical recycling and chemical recycling.
  • the mechanical recycling method is to obtain new PET materials through physical treatment of PET waste through separation, crushing, washing, drying, melting and reforming.
  • the process of mechanical recovery method is simple, easy to control, and requires less investment in equipment. Therefore, it is currently the main PET recycling method.
  • Chemical recycling is the process of degrading PET waste into monomers or other chemical substances through various chemical means, and these monomers can be produced into PET through polycondensation reaction.
  • the method mainly includes hydrolysis, methanol alcoholysis, ethylene glycol alcoholysis, pyrolysis and ammonolysis, etc.
  • the advantage of the chemical recycling method is that it will not reduce the quality of PET, so PET recycling can be achieved permanent closed loop. Therefore, the chemical recycling method provides a more effective PET recycling method.
  • the ethylene glycol alcoholysis method and the methanol alcoholysis method are the two most mature chemical recycling methods. Among them, ethylene glycol alcoholysis method is the most potential method, because ethylene glycol has a high boiling point and is not easy to volatilize; but the existing technology is to carry out ethylene glycol alcoholysis under oil bath or microwave heating, resulting in ethylene glycol alcoholysis Recycling PET still consumes a lot of energy (heat). Therefore, new implementation methods need to be developed to achieve more efficient PET degradation.
  • the purpose of the present invention is to provide a method for chemical recycling of waste polyester by applying photothermal technology.
  • Sunlight is a clean and green energy source. It converts the absorbed photon energy into heat through the photothermal effect, and then releases the energy in the form of heat.
  • using photothermal technology to heat can reduce the degradation process of PET. The energy consumption greatly improves the PET degradation efficiency.
  • a method for photothermally degrading polyester comprising the steps of adding polyester, alcohol, catalyst and photothermal material into a photoreactor, and reacting with light for 30-90 minutes to complete the photothermally degrading polyester.
  • the invention discloses a method for preparing ester monomer by photothermally degrading polyester, which comprises the following steps: adding polyester, alcohol, catalyst and photothermal material into a photoreactor, reacting with light for 30-90 min, and then filtering the reaction liquid , to obtain a clear filtrate; the clear filtrate is cooled and filtered to obtain an ester monomer.
  • the reaction temperature generated by light is 80-190°C
  • the ester exchange reaction is carried out when the polyester is degraded to obtain the ester monomer, so as to realize the chemical recovery of the polyester, wherein the ester monomer includes bis(2-hydroxyethyl) terephthalate Esters, ethyl lactate, bisphenol A, etc.
  • the polyester can be waste polyester or non-waste polyester.
  • the waste polyester used in the present invention can be waste produced in the production process, or waste containing a large amount of impurities (oil, various inorganic fillers, pigments, and other polymers).
  • the photothermal materials used in the present invention are carbon nanomaterials (carbon nanotubes, graphene), sulfides (molybdenum sulfide, tungsten sulfide), plasmonic materials (gold nanorods, palladium nanosheets, Fe3O4 nanoclusters) , Cu 9 S 5 nanocrystals) or one or more of them; preferably one of carbon nanotubes, molybdenum sulfide, and palladium nanoclusters.
  • the dosage of the photothermal material is 0.1%-2% of the polyester mass, and the preferred dosage is 0.5%-1% of the polyester mass.
  • the catalyst used in the present invention is Zn(CH 3 COO) 2 , Mn(CH 3 COO) 2 , Mg(CH 3 COO) 2 , Pb(CH 3 COO) 2 , ZnO, Fe 2 O 3 , Co 3 O 4 , One or more of MnO 2 , SnO 2 , Ni 2 O 3 , ZnCl 2 , NaCl, MgCl 2 , Na 2 CO 3 ; preferably Zn(CH 3 COO) 2 , Fe 2 O 3 , MgCl 2 , Na 2 CO 3 2 One of CO 3 .
  • the dosage of the catalyst is 0.5% to 10% of the mass of the polyester, and the preferred dosage is 0.5% to 3% of the mass of the polyester.
  • Alcohols applicable to the present invention include ethylene glycol, glycerol, diethylene glycol, polyethylene glycol, triethylene glycol, butylene glycol, hexylene glycol, and the like.
  • the amount of alcohol used is 2 to 6 times the mass of the polyester, preferably ethylene glycol, butanediol, and hexanediol, and the amount used is 2 to 4 times the mass of the polyester.
  • the notable feature of the invention is that the photothermal technology is used for the first time to heat and catalyze the polyester degradation reaction system.
  • the photothermal reaction greatly improves the degradation efficiency, and the combination of the photothermal effect and the catalytic effect greatly shortens the reaction time, and the reaction can also be carried out under normal pressure.
  • Fig. 1 is the physical picture of the photoreactor of embodiment.
  • Figure 2 is the NMR spectrum of the ester monomer bis(2-hydroxyethyl) terephthalate, with deuterated-dimethyl sulfoxide as the solvent, using Bruker Avance DPX 600 MHz Instrument Test.
  • the raw materials of the present invention are all existing products, and the specific reaction operations and test methods are all conventional methods in the field, wherein the photothermal reaction is carried out under normal pressure, under conventional stirring, and in the air, using a 300W xenon lamp for illumination, and using an ATEST temperature detector Test the temperature of the reaction system; the size of the polyester fragments is similar to that of the nail cap, and the examples and comparative examples are similar; the waste polyester is purchased from Kunshan Shengdeli Chemical Materials Co., Ltd., wherein examples 1 to 17, comparative example 1 and comparative examples 2 is polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • Example 1 Take 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, and 20 g of ethylene glycol, add them to the photoreactor, and then place the reactor on the light source Under the light, the temperature of the system was 190 °C and the reaction was kept for 60 minutes; after the reaction was completed, the filter cake containing the photothermal material and catalyst was separated by filtration and dried, and no polyester fragments were observed; the clarified filtrate separated by filtration was naturally After cooling, white bis(2-hydroxyethyl)terephthalate crystals were precipitated; then, pure bis(2-hydroxyethyl)terephthalate monomer was obtained after filtration, washing and drying.
  • the degradation rate of PET is 100%, and the yield of bis(2-hydroxyethyl) terephthalate monomer is 95.39%.
  • the molar weight of the product ester monomer is compared to the molar weight of polyester, and the obtained Monomer yield, wherein the molecular weight of bis(2-hydroxyethyl) terephthalate is 254 g/mol, and the molecular weight of polyester is calculated as structural unit 192 g/mol;
  • Accompanying drawing 2 is the monomer bis(2-hydroxyethyl) terephthalate NMR spectrum of (2-hydroxyethyl) ester.
  • Embodiment 2 Take by weighing 5 g waste and old PET fragments, 0.025 g Zn(CH 3 COO) Catalyst , 0.05 g molybdenum sulfide photothermal material, measure 20 g ethylene glycol, join in the photoreactor, then the reactor Place it under the light source and keep the temperature of the system at 190°C for 60 minutes. After the reaction, the photothermal material was separated by filtration while it was hot and dried. No polyester fragments were observed. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 94.24%.
  • Embodiment 3 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) Catalyst , 0.05 g of palladium nanosheet photothermal material, weigh 20 g of ethylene glycol, add to the photoreactor, and then react The device was placed under the light source and the temperature of the system was 190 °C for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 93.77%.
  • Embodiment 4 Weigh 5 g waste PET fragments, 0.025 g Zn(CH 3 COO) Catalyst , 0.25 g carbon nanotube photothermal material, measure 20 g ethylene glycol, add to photoreactor, then reactor Place it under the light source, and keep the temperature of the system at 190 °C for 60 min. After the reaction is completed, filter and separate the photothermal material while it is hot and dry it. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET is 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate is 95.89%.
  • Example 5 Weigh 5 g waste PET fragments, 0.025 g Fe 2 O 3 catalyst, 0.05 g carbon nanotube photothermal material, weigh 20 g ethylene glycol, add them to the photoreactor, and place the reactor in Under the light source, the temperature of the system was 190 °C and the reaction was kept for 60 minutes; after the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 92.14%.
  • Example 6 Weigh 5 g of waste PET fragments, 0.025 g of MgCl catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of ethylene glycol, add them to the photoreactor, and then place the reactor under the light source Illuminated, and the temperature of the system was 190 °C, and the reaction was kept for 60 minutes; after the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET is 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate is 94.58%.
  • Example 7 Weigh 5 g waste PET fragments , 0.025 g Na2CO3 catalyst, 0.05 g carbon nanotube photothermal material, weigh 20 g ethylene glycol, add them to the photoreactor, and place the reactor in Under the light source, the temperature of the system was 190 °C and the reaction was kept for 60 minutes; after the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 85.03%.
  • Embodiment 8 Weigh 5 g waste PET fragments, 0.15 g Zn(CH 3 COO) 2 catalyst, 0.05 g carbon nanotube photothermal material, measure 20 g ethylene glycol, add in the photoreactor, and then react The device was placed under the light source and the temperature of the system was 190 °C for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET is 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate is 95.73%.
  • Embodiment 9 Weigh 5 g waste PET fragments, 0.025 g Zn(CH 3 COO) 2 catalyst, 0.05 g carbon nanotube photothermal material, measure 20 g butanediol, add in the photoreactor, and then react The device was placed under the light source and the temperature of the system was 190 °C for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxybutyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxybutyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxybutyl) terephthalate was 84.27%.
  • Example 10 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of hexanediol, add them to the photoreactor, and then react The device was placed under the light source and the temperature of the system was 190 °C for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyhexyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyhexyl) terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyhexyl) terephthalate was 66.37%.
  • Example 11 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 10 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source and the temperature of the system was 190 °C for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 90.27%.
  • Example 12 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source, and the temperature of the system was 160 °C, and the reaction was kept for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried, and a small amount of polyester fragments were observed. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the yield of monomeric bis(2-hydroxyethyl) terephthalate was 83.93%, and the degradation rate of PET was 94.30%, which was divided by the mass of a small amount of polyester fragments by 5g.
  • Example 13 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source, and the temperature of the system was 130 °C, and the reaction was kept for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried, and polyester fragments were observed. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 80.68%, and the yield of monomer bis(2-hydroxyethyl) terephthalate was 71.27%.
  • Example 14 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 30 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source, and the temperature of the system was 110 °C, and the reaction was kept for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried, and polyester fragments were observed. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 71.55%, and the yield of monomeric bis(2-hydroxyethyl) terephthalate was 59.82%.
  • Example 15 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 30 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source, and the temperature of the system was 80 °C, and the reaction was kept for 60 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried, and many polyester fragments were observed. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 65.39%, and the yield of bis(2-hydroxyethyl) terephthalate monomer was 51.65%.
  • Comparative example 1 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 30 g of ethylene glycol, add them to the reactor, and heat them in an oil bath. The temperature of the system was 80 °C and the reaction was kept for 60 minutes. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. A large number of polyester fragments were observed, which were still 5 g when taken out and weighed, and the size was similar to that of the original waste polyester fragments. No difference, indicating that waste polyester fragments are not degraded.
  • Example 16 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source and the temperature of the system was kept at 190 °C for 30 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and white bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET was 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate (BHET) was 90.39%.
  • BHET monomer bis(2-hydroxyethyl) terephthalate
  • Comparative example 2 Weigh 5 g of waste PET chips, 0.025 g of Zn(CH 3 COO) 2 catalyst, weigh 20 g of ethylene glycol, add them to the reactor, heat in an oil bath, and keep the temperature of the system at 190 °C for 30 min; after the reaction was completed, the solid was separated by filtration while it was hot and dried, and a little more polyester fragments were observed, which were taken out and weighed to calculate that the degradation rate of PET was 37.83%, and the monomer bis(2-hydroxyethyl) terephthalate The yield of ester was 20.39%.
  • Example 17 Weigh 5 g of waste PET fragments, 0.025 g of Zn(CH 3 COO) 2 catalyst, 0.05 g of carbon nanotube photothermal material, weigh 20 g of ethylene glycol, add them to the photoreactor, and then react The device was placed under the light source, and the temperature of the system was kept at 190 °C for 90 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was cooled, and the white monomer bis(2-hydroxyethyl)terephthalate crystals were precipitated. After filtering, washing and drying, pure bis(2-hydroxyethyl)terephthalate monomer was obtained. Under these conditions, the degradation rate of PET is 100%, and the yield of monomer bis(2-hydroxyethyl) terephthalate is 95.94%.
  • Example 18 Weigh 5 g waste polycarbonate (PC) fragments, 0.025 g Zn(CH 3 COO) 2 catalyst, 0.05 g carbon nanotube photothermal material, weigh 20 g ethylene glycol, and add them to the photoreactor , and then placed the reactor under the light source, and kept the temperature of the system at 100 °C for 30 min. After the reaction was completed, the photothermal material was separated by filtration while it was hot and dried. The filtrate was added to ethyl acetate for extraction, and the white monomer bisphenol A precipitated out. Then, pure bisphenol A monomer is obtained after filtering, washing with water and drying. Under these conditions, the degradation rate of PC is 100%, and the yield of monomeric bisphenol A monomer is 93.27%.
  • PC waste polycarbonate
  • the invention mainly uses photothermal technology to heat waste polyester and assist catalytic degradation.
  • Photothermal technology can convert a part of the absorbed photon energy into heat energy, and then the heat energy will be released into the reaction system to increase the temperature of the material.
  • the use of photothermal technology can reduce the polyester degradation process.
  • the energy consumption in the process has greatly improved the degradation efficiency of polyester.
  • the present invention can realize the degradation of polyester to prepare monomers under normal pressure and in the air, which is easy for industrial promotion.

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Abstract

本发明属于聚合物处理技术，具体涉及一种光热降解聚酯的方法。将聚酯、醇、催化剂和光热材料加入光反应器中，光照反应，完成光热降解聚酯，并进行酯交换反应得到酯单体，实现聚酯的化学回收。光热反应大幅提高了降解效率，光热效应与催化效应的结合，极大的缩短了反应时间，同时反应在常压下进行，利于工业应用。

Description

一种光热降解聚酯的方法 技术领域
本发明属于聚合物处理技术，具体涉及一种光热降解聚酯的方法。
 背景技术
聚酯为常规的塑料产品，其中聚对苯二甲酸乙二醇酯（PET）用量广泛。PET是由对苯二甲酸二甲酯与乙二醇酯交换或先以对苯二甲酸与乙二醇酯化合成对苯二甲酸双（2-羟乙基）酯，再进行缩聚反应制得。PET作为一种在较宽温度范围内具有优良物理机械性能和化学稳定性的热塑型塑料，广泛的应用于高强度纤维、包装、薄膜和塑料瓶中。PET分为纤维级聚酯切片和非纤维级聚酯切片。①纤维级聚酯用于制造涤纶短纤维和涤纶长丝，是供给涤纶纤维企业加工纤维及相关产品的原料。涤纶作为化纤中产量最大的品种。②非纤维级聚酯还有瓶类、薄膜等用途，广泛应用于包装业、电子电器、医疗卫生、建筑、汽车等领域，其中包装是聚酯最大的非纤应用市场，其中PET是增长最快的领域。同时，巨大的PET消耗量和生产量产生了大量的PET废料，这使得PET废料的降解回收面临着巨大的挑战，此外，PET的生产原料来自于有限的、不可再生的石油资源。因此，废弃PET的回收利用不仅可以减少对环境的破坏，还可以延长资源利用周期，带来巨大的社会效益和经济效益。
目前，PET回收法包括机械回收法和化学回收法。机械回收法是通过对PET废料进行物理处理，通过分离、粉碎、洗涤、干燥、熔化和重整，以获得新的PET材料。机械回收法过程简单，易于控制，设备投资少。因此，它是目前主要的PET回收方法。但是，由于断链会降低PET分子量，导致PET的性能退化，无法再次进行回收利用。化学回收法是通过各种化学手段将PET废料全部降解为单体或其他化学物质的过程，这些单体可以通过缩聚反应制取PET。该方法主要包括水解法、甲醇醇解法、乙二醇醇解法、热解法和氨解法等，与机械回收法相比，化学回收法的优势在于它不会降低PET的质量，因此可以实现PET回收的永久闭环循环。因此，化学回收法提供了一种更有效的PET回收方法，目前，乙二醇醇解法和甲醇醇解法是最为成熟的两种化学回收方法。其中，乙二醇醇解法是最具潜力的方法，因为乙二醇沸点高，不易挥发；但是现有技术都是在油浴或者微波加热下进行乙二醇醇解，导致乙二醇醇解回收PET仍然需要消耗大量的能量（热能）。因此，需要开发新的实施办法，从而实现更高效的PET降解。
 技术解决方案
本发明的目的是提供一种应用光热技术对废旧聚酯进行化学回收利用的方法。太阳光是一种清洁绿色能源，通过光热效应将吸收的光子能量转化成热，再以热的形式将能量释放出来，与传统的加热方式相比，利用光热技术加热既减少PET降解过程中的能量消耗又大幅度提高了PET降解效率。
一种光热降解聚酯的方法，包括以下步骤，将聚酯、醇、催化剂和光热材料加入光反应器中，光照反应30～90 min，完成光热降解聚酯。
本发明公开了一种光热降解聚酯制备酯单体的方法，包括以下步骤，将聚酯、醇、催化剂和光热材料加入光反应器中，光照反应30～90 min，然后过滤反应液，得到澄清滤液；所述澄清滤液经过冷却、过滤，得到酯单体。
本发明光照产生的反应温度在80～190 ℃，降解聚酯时进行酯交换反应得到酯单体，实现聚酯的化学回收，其中酯单体包括对苯二甲酸双（2-羟乙基）酯、乳酸乙酯、双酚A等。聚酯可以为废旧聚酯，也可为非废旧聚酯。本发明使用的废旧聚酯可以是生产过程中产生的废料，也可以是含有大量杂质（油、各种无机填料、颜料，以及其他聚合物）的废料。
本发明采用的光热材料是碳纳米材料（碳纳米管、石墨烯）、硫化物（硫化钼、硫化钨）、等离激元材料（金纳米棒、钯纳米片、Fe 3O 4纳米簇、Cu 9S 5纳米晶）中的一种或几种；优选为碳纳米管、硫化钼、钯纳米簇中的一种。光热材料的用量是聚酯质量的0.1%～2%，优选用量为聚酯质量的0.5%～1%。
本发明采用的催化剂是Zn(CH 3COO) 2、Mn(CH 3COO) 2、Mg(CH 3COO) 2、Pb(CH 3COO) 2、ZnO、Fe 2O 3、Co 3O 4、MnO 2、SnO 2、Ni 2O 3、ZnCl 2、NaCl、MgCl 2、Na 2CO 3中的一种或几种；优选为Zn(CH 3COO) 2、Fe 2O 3、MgCl 2、Na 2CO 3中的一种。催化剂用量是聚酯质量的0.5%～10%，优选用量为聚酯质量的0.5%～3%。
本发明适用的醇有乙二醇、丙三醇、一缩二乙二醇、聚乙二醇、三缩乙二醇、丁二醇、己二醇等。醇用量是聚酯质量的2～6倍，优选乙二醇、丁二醇、己二醇，用量为聚酯质量的2～4倍。
 有益效果
本发明的显著特点是首次采用光热技术对聚酯降解反应体系进行加热和催化。光热反应大幅提高了降解效率，光热效应与催化效应的结合，极大的缩短了反应时间，同时反应还可在常压下进行。
 附图说明
图1为实施例光反应器实物图。
图2为酯单体对苯二甲酸双（2-羟乙基）酯的核磁图谱，以氘代-二甲基亚砜作为溶剂，使用Bruker Avance DPX 600 MHz仪器测试。
 本发明的实施方式
本发明将通过以下实施例做进一步的说明，这些实施例仅用于举例说明本发明的主要技术特征和工艺优势，但本发明并不仅限于下述实施例，在不脱离前后所属宗旨的范围下，本发明还会有各种包含于本发明技术范围内的变化和改进。本发明的原料都是现有产品，具体反应操作以及测试方法都是本领域常规方法，其中光热反应在常压、常规搅拌下、空气中进行，利用300W氙灯进行光照，利用ATEST探温仪测试反应体系温度；聚酯碎片大小与指甲盖近似，实施例以及对比例近似；废旧聚酯购自昆山圣德力化工材料有限公司，其中实施例1至实施例17、对比例1以及对比例2为聚对苯二甲酸乙二醇酯（PET）。
实施例1：取5 g废旧PET碎片、0.025 g Zn(CH 3COO) 2催化剂、0.05 g碳纳米管光热材料、20 g乙二醇，加入光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出含有光热材料与催化剂的滤饼并进行干燥，未观察到聚酯碎片；将过滤分离出的澄清滤液自然冷却，有白色对苯二甲酸双（2-羟乙基）酯晶体析出；随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为95.39％，以产物酯单体的摩尔量比聚酯摩尔量，得到单体产率，其中对苯二甲酸双（2-羟乙基）酯的分子量为254 g/mol，聚酯分子量以结构单元192 g/mol计；附图2为单体对苯二甲酸双（2-羟乙基）酯的核磁图谱。
实施例2：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g硫化钼光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，未观察到聚酯碎片。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为94.24％。
实施例3：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g钯纳米片光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为93.77％。
实施例4：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.25 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为95.89％。
称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.1 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器，再将反应器放置于光源下光照，体系温度为190℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色BHET晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为94.93％。
称取5 g废旧聚酯碎片，0.025 g Zn(CH 3COO) 2催化剂，0.005 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为89.32％。
实施例5：称取5 g废旧PET碎片，0.025 g Fe 2O 3催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为92.14％。
实施例6：称取5 g废旧PET碎片，0.025 g MgCl 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为94.58％。
实施例7：称取5 g废旧PET碎片，0.025 g Na 2CO 3催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为85.03％。
实施例8：称取5 g废旧PET碎片，0.15 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为95.73％。
实施例9：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g丁二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟丁基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟丁基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟丁基）酯的产率为84.27％。
实施例10：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g己二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟己基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟己基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟己基）酯的产率为66.37％。
实施例11：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取10 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为90.27％。
称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取30 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为94.48％。
实施例12：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为160 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，观察到少量聚酯碎片。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，单体对苯二甲酸双（2-羟乙基）酯的产率为83.93％，PET的降解率为94.30％，以少量聚酯碎片质量除以5g。
实施例13：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为130 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，观察到聚酯碎片。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为80.68％，单体对苯二甲酸双（2-羟乙基）酯的产率为71.27％。
实施例14：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取30 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为110 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，观察到聚酯碎片。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为71.55％，单体对苯二甲酸双（2-羟乙基）酯的产率为59.82％。
实施例15：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取30 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为80 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，观察到较多聚酯碎片。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为65.39％，单体对苯二甲酸双（2-羟乙基）酯的产率为51.65％。
对比例1：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取30 g乙二醇，加入至反应器中，油浴加热，体系温度为80 ℃时保温反应60 min；反应完毕，趁热过滤分离出光热材料并进行干燥，观察到大量聚酯碎片，取出称量发现依然为5 g，且大小与原始废旧聚酯碎片无异，说明废旧聚酯碎片未降解。
称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，量取30 g乙二醇，加入至反应器中，油浴加热，体系温度为80℃时保温反应60 min；反应完毕，趁热过滤分离出固体并进行干燥，观察到大量聚酯碎片，取出称量发现依然为5 g，且大小与原始废旧聚酯碎片无异，说明废旧聚酯碎片未降解。
实施例16：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应30 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯(BHET)的产率为90.39％。
对比例2：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，量取20 g乙二醇，加入至反应器中，油浴加热，体系温度为190 ℃时保温反应30 min；反应完毕，趁热过滤分离出固体并进行干燥，观察到稍多聚酯碎片，取出称量计算，PET的降解率为37.83%，单体对苯二甲酸双（2-羟乙基）酯的产率为20.39％。
上述反应时间调整为90 min，PET的降解率为70.52%，单体对苯二甲酸双（2-羟乙基）酯的产率为60.18％。
实施例17：称取5 g废旧PET碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为190 ℃时保温反应90 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液冷却，白色单体对苯二甲酸双（2-羟乙基）酯晶体析出。随后经过过滤、水洗和干燥后得到纯对苯二甲酸双（2-羟乙基）酯单体。在此条件下，PET的降解率为100％，单体对苯二甲酸双（2-羟乙基）酯的产率为95.94％。
实施例18：称取5 g废旧聚碳酸酯（PC）碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 g乙二醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为100 ℃时保温反应30 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液加入乙酸乙酯萃取，白色单体双酚A沉淀析出。随后经过过滤、水洗和干燥后得到纯双酚A单体。在此条件下，PC的降解率为100％，单体双酚A单体的产率为93.27％。
称取5 g废旧聚乳酸（PLA）碎片，0.025 g Zn(CH 3COO) 2催化剂，0.05 g碳纳米管光热材料，量取20 乙醇，加入至光反应器中，再将反应器放置于光源下光照，体系温度为50 ℃时保温反应30 min；反应完毕，趁热过滤分离出光热材料并进行干燥。将滤液减压蒸馏得到乳酸乙酯。在此条件下，PLA的降解率为100％，单体乳酸乙酯的产率为89.11％。
本发明主要应用光热技术对废旧聚酯进行加热以及辅助催化降解。利用光热技术可以将吸收的一部分光子能量转化为热能，然后这些热能会释放到反应体系中，使物料温度升高，与传统的加热方式相比，利用光热技术加热既减少聚酯降解过程中的能量消耗又大幅度提高了聚酯的降解效率。尤其是，本发明在常压下、空气中即可实现聚酯降解制备单体，易于工业化推广。

Claims (10)

  1. 一种光热降解聚酯的方法，其特征在于，包括以下步骤，将聚酯、醇、催化剂和光热材料加入光反应器中，光照反应，完成光热降解聚酯。
  2. 一种光热降解聚酯制备酯单体的方法，其特征在于，包括以下步骤，将聚酯、醇、催化剂和光热材料加入光反应器中，光照反应，然后过滤反应液，得到澄清滤液；所述澄清滤液经过冷却、过滤，得到酯单体。
  3. 根据权利要求1或者2所述的方法，其特征在于，反应的温度为80～190℃，时间为30～90 min。
  4. 根据权利要求1或者2所述的方法，其特征在于，所述光热材料为碳纳米材料、硫化物、等离激元材料中的一种或几种。
  5. 根据权利要求1或者2所述的方法，其特征在于，光热材料的用量是聚酯质量的0.1%～2%。
  6. 根据权利要求1或者2所述的方法，其特征在于，所述催化剂是Zn(CH 3COO) 2、Mn(CH 3COO) 2、Mg(CH 3COO) 2、Pb(CH 3COO) 2、ZnO、Fe 2O 3、Co 3O 4、MnO 2、SnO 2、Ni 2O 3、ZnCl 2、NaCl、MgCl 2、Na 2CO 3中的一种或几种；所述醇为乙二醇、丙三醇、一缩二乙二醇、聚乙二醇、三缩乙二醇、丁二醇、己二醇中的一种或几种。
  7. 根据权利要求1或者2所述的方法，其特征在于，催化剂用量是聚酯质量的0.5%～10%；醇用量是聚酯质量的2～6倍。
  8. 根据权利要求2所述的方法，其特征在于，澄清滤液经过冷却得到晶体，再过滤，得到酯单体。
  9. 光热材料在光热降解聚酯中的应用。
  10. 根据权利要求9所述的应用，其特征在于，光热降解在常压下进行。
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