WO2023060768A1 - 一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法 - Google Patents

一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法 Download PDF

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WO2023060768A1
WO2023060768A1 PCT/CN2021/141549 CN2021141549W WO2023060768A1 WO 2023060768 A1 WO2023060768 A1 WO 2023060768A1 CN 2021141549 W CN2021141549 W CN 2021141549W WO 2023060768 A1 WO2023060768 A1 WO 2023060768A1
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depolymerization
polyester
catalyst
waste
reaction
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PCT/CN2021/141549
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English (en)
French (fr)
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吴博
谢晓琼
李建军
陈平绪
宁红涛
叶南飚
庞承焕
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国高材高分子材料产业创新中心有限公司
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Priority to EP21957721.0A priority Critical patent/EP4215562A4/en
Priority to KR1020237014801A priority patent/KR102683118B1/ko
Priority to JP2023527370A priority patent/JP7453478B2/ja
Publication of WO2023060768A1 publication Critical patent/WO2023060768A1/zh

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    • 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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    • 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
    • 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
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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    • 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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    • 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
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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 relates to the technical field of chemical regeneration of polyester, and more specifically, relates to a method for preparing regenerated polyester by closed-loop recovery of waste polyester with typical green and low-carbon characteristics.
  • the recycling methods of waste polyester are mainly divided into two categories: physical recycling and chemical recycling.
  • Physical recycling mainly uses the thermoplasticity of polyester to remove impurities, wash, melt and re-granulate polyester and its products to obtain secondary plastic or fiber products.
  • the process is simple and the cost is low, it can only achieve the recycling of polyester. Downgrade recycling, and the number of recycling is limited, and the purpose of recycling cannot be achieved.
  • Chemical recovery refers to the reversibility of polyester polycondensation reaction and the nucleophilic reaction mechanism of transesterification reaction, through the attack of small molecule depolymerization agent on macromolecular chain, polyester is depolymerized into polymer monomer or intermediate, and then recycle after separation and purification. Polymerization achieves regeneration. Recycling waste polyester through chemical recycling can effectively utilize resources and reduce environmental load.
  • the residue that contains heavy metal depolymerization catalyst has adverse effect on the performance of regenerated polyester, as causing regenerated polyester to be easy to decompose , the viscosity is low, and the heavy metal content exceeds the standard;
  • the temperature is high during the depolymerization process of waste polyester, and the amount of depolymerization agent is high.
  • the energy consumption is relatively large, which does not meet the current green and low-carbon technical requirements.
  • Chinese patent application CN107266664A discloses a polyester waste recycling process, which uses zinc acetate as a catalyst to depolymerize PET waste, but the zinc ions remaining in the depolymerization product will cause regeneration due to its catalytic mechanism for carbonyl oxygen coordination.
  • side reactions such as thermal degradation are accelerated, so that the growth of molecular weight is limited, and the viscosity of recycled polyester is low and the quality is poor.
  • Chinese patent application CN102731310A discloses a method for catalyzing the alcoholysis of PET with a first transition metal ionic liquid, but the content of halogen group elements in the catalyst of this type of ionic liquid is very high, if the catalyst cannot be removed from the depolymerization product, then During the repolymerization process, the macromolecule will be decomposed due to the generation of hydrogen halide, which seriously affects the quality of the repolymerized product; and in this method, the amount of catalyst added needs to reach 10wt.% of PET, and the amount of alcoholysis solvent ethylene glycol is about PET 4 to 10 times of that, the amount of catalyst and diol is large.
  • Chinese patent application CN 104327260 A discloses a preparation method of biodegradable recycled polyester.
  • the depolymerization catalyst used is a dihydric alcohol titanium alkali metal coordination compound soluble in ethylene glycol to depolymerize waste PET. Further copolymerization to obtain recycled polyester.
  • this method can only recycle waste PET, and does not involve other types of waste polyester; on the other hand, the depolymerization temperature in the alcohol solution polymerization process of this method is 160-240 °C, and the depolymerization time is 0.5-5h , the temperature is too high and the time is too long, so that ethylene glycol is easily cyclodehydrated to form cyclized by-products, and the method uses a large amount of alcoholysis agent and the process is complicated.
  • the present invention provides a green method for closed-loop recovery of waste polyester to prepare regenerated polyester in order to overcome the defects of non-closed-loop recovery of waste polyester and high content of by-products described in the prior art.
  • a method for preparing regenerated polyester by closed-loop recovery of waste polyester with typical green and low-carbon characteristics comprising the following steps:
  • the depolymerization catalyst is one or more of titanate nanotubes, titanium phosphate, titanium dioxide, butyl titanate, titanium ethylene glycol or titanium butanedioxide;
  • the temperature of the depolymerization reaction is 150-170°C and the temperature fluctuation is ⁇ 2°C, and the depolymerization reaction time is 6-35min;
  • step S1 After the polyol solvent is removed from the depolymerized product obtained in step S1, the by-product is removed through purification to obtain the depolymerized monomer;
  • step S2 Mix the depolymerized monomer prepared in step S2 with dibasic acid, polyol, polymerization catalyst and chain extender, and carry out polymerization reaction under inert gas atmosphere and microwave conditions to obtain an esterification product;
  • step S3 The esterified product in step S3 is mixed with a catalyst and a stabilizer, and the polycondensation reaction is carried out under a vacuum condition to obtain the regenerated polyester.
  • the present invention utilizes waste polyester depolymerization to synthesize a series of aliphatic-aromatic copolyesters as regenerated polyesters, which not only effectively realizes the chemical recovery of polyesters, but also chemically depolymerizes and recycles the regenerated polyesters after use. Utilize to realize closed-loop recycling.
  • the present invention uses titanate nanotubes, phosphopeptides, titanium dioxide, butyl titanate, titanium ethylene glycol or titanium butanedioxide as the depolymerization catalyst, on the one hand its depolymerization effect is excellent, on the other hand,
  • the titanium-based catalyst does not need to be separated after the waste polyester is depolymerized, and can be directly used as a catalyst for the co-esterification of the regenerated polyester without adversely affecting the performance of the regenerated polyester.
  • the catalytic system of the present invention does not contain limiting elements of degradable polyester, and the raw materials are controlled during the synthesis of recycled polyester to provide a strong guarantee for subsequent recycling.
  • microwave can heat the inside and outside of the polyester raw material to be depolymerized at the same time, so that it can be heated evenly and depolymerize more thoroughly; on the other hand, microwave can The same depolymerization effect as the traditional heating method is achieved at an extremely low temperature, so that the depolymerization reaction can be carried out efficiently and quickly, which not only ensures the degree of depolymerization of waste polyester, but also greatly shortens the depolymerization time and lowers the reaction temperature , and reduce the generation of cyclization products caused by polyols in the depolymerization process, improve the yield, and reduce the environmental pollution caused by the treatment of by-products.
  • step S1 not only the temperature range of the depolymerization reaction is required to meet 150-170°C, but also the temperature of the depolymerization reaction is required to be constant, that is, the temperature fluctuation of a single depolymerization reaction does not exceed ⁇ 2°C.
  • Described waste polyester is polyadipate/butylene terephthalate (PBAT), poly(butylene sebacate-butylene terephthalate) copolyester (PBSeT), polyterephthalate Ethylene glycol formate-1,4-cyclohexanedimethanol (PETG), polyethylene terephthalate-1,4-cyclohexanedimethanol (PCTG), polybutylene terephthalate One or more of polyester (PBT) or polyethylene terephthalate (PET).
  • PBAT polyadipate/butylene terephthalate
  • PBSeT poly(butylene sebacate-butylene terephthalate) copolyester
  • PETG Ethylene glycol formate-1,4-cyclohexanedimethanol
  • PCTG polyethylene terephthalate-1,4-cyclohexanedimethanol
  • PBT polyethylene terephthalate
  • PET polyethylene terephthalate
  • the source of the waste polyester can be one or more of post-consumer recycled plastic (Post Consumer Recycled Plastic, PCR), industrial recycled plastic (Post Industry Recycle Plastic, PIR) or marine waste plastic.
  • Post-consumer recycled plastic Post Consumer Recycled Plastic, PCR
  • industrial recycled plastic Post Industry Recycle Plastic, PIR
  • marine waste plastic Marine waste plastic
  • the marine waste plastics may be Ocean Bound Plastics (OBP) and/or in-the-ocean plastics (IOP).
  • OBP Ocean Bound Plastics
  • IOP in-the-ocean plastics
  • the waste polyester can be directly used for depolymerization after removal of impurities, cleaning and crushing.
  • the depolymerization catalyst is one or more of titanate nanotubes, titanium phosphate or butyl titanate.
  • titanate nanotubes, titanium phosphate or butyl titanate as a depolymerization catalyst has better depolymerization efficiency and shorter depolymerization time, thereby further reducing the generation of cyclization products.
  • the depolymerization catalyst accounts for 0.05-0.15wt.% of the waste polyester.
  • the mass ratio of waste polyester to polyol in step S1 is 1: (0.6-3).
  • the microwave absorber is one or more of sodium carbonate, sodium chloride, activated carbon or sodium phosphate.
  • the microwave absorber is sodium carbonate.
  • the microwave absorber in step S1 accounts for 0.01-1 wt.% of the waste polyester.
  • the inventors have found that sodium carbonate not only has a microwave absorption effect, but also has a certain depolymerization catalytic effect.
  • the depolymerization efficiency of step S1 was further improved.
  • the microwave conditions in step S1 are microwave power 500-1000w, microwave wavelength 122mm.
  • the temperature of the depolymerization reaction in step S1 is 155-165° C., and the time is 10-30 min.
  • the temperature of the depolymerization reaction in step S1 is 160° C., and the time is 10 minutes.
  • the microwave power and the temperature of the depolymerization reaction are not directly corresponding.
  • the removal of the polyol solvent in step S2 is vacuum distillation and vacuum drying.
  • the purification in step S2 is dissolution, recrystallization and filtration.
  • the polymerization catalyst described in step S3 may be a commonly used polymerization catalyst for polyesters.
  • the polymerization catalyst in step S3 is one or more of butyl titanate, propyl titanate, titanium phosphorus compound, titanium silicon compound or ethyl titanate.
  • the polyol solvent in step S1 and the diol in step S3 are one or more of ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, and glycerin.
  • the dibasic acid in step S3 is an aliphatic dibasic acid with 2-36 carbon atoms.
  • the mass ratio of the polyol to the dibasic acid in step S3 is (0.2-1):1.
  • both the polyol solvent in step S1 and the diol in step S3 are 1,4-butanediol, and the dibasic acid in step S3 is sebacic acid and/or adipic acid.
  • the biomass content of the recycled polyester obtained is ⁇ 60%, which fully realizes the green and low-carbon cycle of biomass and chemical recovery. idea.
  • the microwave condition in step S3 is 500-1000w.
  • the temperature of the polymerization reaction in step S3 is 160-180° C., and the time is 30-90 minutes.
  • the polymerization catalyst in step S3 accounts for 0.03-2 wt.% of the sum of the mass of the depolymerization monomer, dibasic acid, diol and chain extender.
  • the chain extender in step S3 is one or more of polyol chain extenders, isocyanate chain extenders, acid anhydride chain extenders or epoxy compound chain extenders.
  • the polyol chain extender is one or more of ethylene glycol, glycerol, pentaerythritol, trimethylolpropane, xylitol or sorbitol.
  • the isocyanate chain extender is one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate kind.
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • isophorone diisocyanate kind isophorone diisocyanate kind.
  • the epoxy compound chain extender may be an ADR chain extender.
  • the catalyst in step S4 is the same as the polymerization catalyst in step S3.
  • the stabilizer in step S4 is one or more of organic phosphite stabilizers, phosphate stabilizers, and hindered phenol stabilizers.
  • the organic phosphite stabilizer may be one or more of trimethyl phosphite, triethyl phosphite or triphenyl phosphite.
  • the phosphate stabilizer may be one or more of triphenyl phosphate, trimethyl phosphate or triethyl phosphate.
  • the hindered phenolic stabilizer may be 3,5-di-tert-butyl-4-hydroxybenzyl diethylphosphonate (Antioxidant 1222) and/or Antioxidant 1010.
  • the temperature of the polycondensation reaction is 230-250° C.
  • the time is 3-5 hours
  • the pressure is 20-100 Pa.
  • the invention utilizes waste polyester to depolymerize and repolymerize, and the synthesized regenerated polyester is still a fully biodegradable polyester, which not only effectively realizes the chemical recovery of polyester, but also chemically depolymerizes and recycles the regenerated polyester after use Utilize to realize closed-loop recycling.
  • the present invention uses a specific titanium-based catalyst as a depolymerization catalyst to depolymerize waste polyester at a lower temperature and in a shorter time in the presence of a microwave absorber, and the amount of glycol solvent used Small, low catalyst addition.
  • a very high depolymerization efficiency is obtained, and at the same time, the yield of by-products is low, the depolymerization catalyst does not need to be separated, and the next step of esterification can be directly carried out, and the performance of the obtained recycled polyester will not be adversely affected. Effectively realize green chemical recycling.
  • the biomass content of the produced recycled polyester is ⁇ 60%, realizing the technical route of simultaneously developing biomass and chemical recovery.
  • life cycle assessment due to the introduction of biomass raw materials and waste polyester as raw materials, the carbon emission reduction rate compared with the existing chemical recycling route is more than 60%, which fully reflects the low carbon of the technical route and products feature.
  • the waste PET bottles from marine garbage are affected by many factors such as light, heat, seawater erosion, biological and microbial adhesion in the natural environment, and have obvious performance degradation, and their appearance is brittle, and the transparency is reduced. , the essence is that the molecular weight decreases after the polyester is degraded, and the intrinsic viscosity decreases. These degradation products become microplastics after entering the ocean. Since the performance of most marine waste PET has dropped significantly, conventional physical recycling after salvage and collection can only be downgraded or energy recovered, which cannot effectively reflect the principle of resource recycling and full utilization.
  • the invention can not only realize the purpose of protecting the environment and reducing microplastic pollution by recycling marine garbage, but also can chemically recycle the collected waste PET as a resource and convert it into a high-value secondary product for full utilization, realizing environmental protection and high-quality resources The double purpose of the loop.
  • Fig. 1 is the infrared spectrogram of the depolymerization reaction fraction and polymerization reaction fraction of Example 1, the depolymerization reaction fraction of Comparative Example 7, and tetrahydrofuran standard solution.
  • Fig. 2 is the infrared spectrogram of the depolymerization monomer that embodiment 1 makes.
  • Fig. 3 is the infrared spectrogram of the regenerated polyester that embodiment 1 makes.
  • Fig. 4 is the nuclear magnetic hydrogen spectrum of the regenerated polyester that embodiment 1 makes.
  • the raw material in embodiment and comparative example all can be obtained by commercially available;
  • PET particles from POLINDO PT; marine waste PET bottle flakes (intrinsic viscosity ⁇ 0.5dL/g, weight average molecular weight ⁇ 16000g/mol), from Blue Ribbon Marine Conservation Association; PCTG, PETG, from Guangzhou Ruisheng Plastic Co., Ltd.; PBAT, PBSeT, from Zhuhai Wantong Chemical Co., Ltd.
  • Titanate nanotubes were purchased from Xianfeng Nano; titanium phosphate was purchased from Weihai Tianchuang Fine Chemical Co., Ltd.; butyl titanate was purchased from Aladdin; zinc acetate was purchased from Aladdin.
  • Sodium carbonate and sodium chloride were purchased from McLean; activated carbon powder, commercially available, analytically pure, with an average particle size of 30 ⁇ m, and silicon carbide were purchased from McLean.
  • Trimethyl phosphite triphenyl phosphate was purchased from Aladdin.
  • 1,4-butanediol which is a bio-based BDO, was purchased from Shandong Landian Biotechnology Co., Ltd.;
  • sebacic acid purchased from Jinan Boao Chemical Co., Ltd.
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • Embodiments 1 to 5 respectively provide a method for preparing regenerated polyester by closed-loop recovery of waste polyester, including the following steps.
  • the specific raw materials and reaction conditions are shown in Table 1:
  • Dissolve waste polyester with an average particle size of ⁇ 2mm in a glycol solvent containing a depolymerization catalyst and a microwave absorber place it in a 500mL glass reactor, and transfer it to a microwave chemical synthesizer (model ANKS-SR8, Qingdao Enix Microwave Automation Equipment Co., Ltd.), in nitrogen atmosphere, under microwave conditions, carry out depolymerization reaction, obtain depolymerization product;
  • a microwave chemical synthesizer model ANKS-SR8, Qingdao Enix Microwave Automation Equipment Co., Ltd.
  • step S1 After the depolymerization product prepared in step S1 is subjected to vacuum distillation to remove solvents such as diols, the depolymerization monomer is obtained through purification;
  • step S2 Mix the depolymerized monomer prepared in step S2 with dibasic acid, diol, polymerization catalyst and chain extender, and carry out polymerization reaction under inert gas atmosphere and microwave conditions to obtain an esterification product;
  • step S3 The esterification product in step S3 is added with a stabilizer and a catalyst, and polycondensation is carried out under vacuum conditions to obtain the regenerated polyester.
  • Embodiments 6-10 provide a method for preparing biodegradable polyester by closed-loop recovery of waste polyester, except for the depolymerization conditions in step S1, other steps are the same as in embodiment 1;
  • step S1 of Example 6 the depolymerization condition is that the temperature is constant at 150 ⁇ 2°C and the time is 35 minutes;
  • step S1 of Example 7 the depolymerization condition is that the temperature is constant at 155 ⁇ 2°C and the time is 30 minutes;
  • step S1 of Example 8 the depolymerization condition is that the temperature is constant at 165 ⁇ 2°C and the time is 10 minutes;
  • step S1 of Example 9 the depolymerization condition is that the temperature is constant at 170 ⁇ 2° C. and the time is 8 minutes.
  • step S1 of Example 10 the depolymerization condition is that the temperature is constant at 160 ⁇ 1° C. and the time is 10 minutes.
  • Comparative Examples 1-6 provide a method for preparing biodegradable polyester by closed-loop recovery of waste PET and PETG blends. The steps are the same as in Example 1. The specific raw materials and reaction conditions are shown in Table 2.
  • Comparative Examples 4-6 provide a method for preparing biodegradable polyester by closed-loop recovery of waste PET and PETG blends. Except for the depolymerization conditions in step S1, other steps, raw materials and reaction conditions are the same as in Example 1;
  • step S1 of Comparative Example 4 the depolymerization condition is that the temperature is constant at 140 ⁇ 2°C and the time is 90 minutes;
  • step S1 of Example 5 the depolymerization condition is that the temperature is constant at 190 ⁇ 2°C and the time is 10 minutes;
  • the depolymerization conditions are a temperature of 160° C., a fluctuation range of ⁇ 5° C., and a time of 10 minutes.
  • Comparative Example 7 provides a method for preparing biodegradable polyester by closed-loop recovery of waste PET and PETG blends, the steps are similar to Example 1 of Chinese Patent Application CN 104327260 A, as follows:
  • reaction time is 3 hours, after the reaction is completed, at a temperature of 190 ° C and a pressure of the reaction system at 0.5 atm, the butanediol in the system is completely evaporated within 0.5 min, and the diol in the system is completely evaporated. Evaporate the alcohol completely to obtain a white solid, which is recrystallized three times with ethanol-chloroform to obtain a colorless crystal, which is to obtain lithium titanate butanediol;
  • step S7 Mix the products obtained in step S5 and step S6 at a mass ratio of 8:2, and add 100ppm butanediol lithium titanate as a polycondensation catalyst and 50ppm trimethyl phosphate heat stabilizer, and inert at 220°C, pressure 1atm Stir and mix under the condition of gas protection; then, raise the reaction temperature to 250°C, continue the reaction for 120min, and at the same time, reduce the pressure in the system to 1kPa at a uniform speed during this period of time; then, raise the reaction temperature to 265°C, make the system After the internal pressure was reduced to 20 Pa, the reaction was continued for 180 minutes to obtain recycled polyester.
  • Qualitative depolymerization monomer and regenerated polyester Depolymerization monomer and regenerated polyester are detected by infrared spectroscopy respectively, the test conditions are measurement method: transmission, reference sample: KBr, detector: DTGS, wave number range: 400 ⁇ 4000cm -1 , resolution: 4cm -1 , number of scans: 32.
  • Tetrahydrofuran (THF) yield Weigh the distilled fractions, use infrared for qualitative analysis, and use gas chromatography-hydrogen flame detector to analyze the amount of THF and other by-products; standard samples ethylene glycol, tetrahydrofuran, 1,4-butane Diol and isopropanol are analytically pure; the chromatographic column is a HP-FFAP gas-phase capillary column 30m*0.32mm*0.25 ⁇ m from Agilent Company of the United States, with isopropanol as the internal standard; the temperature of the injector is 250°C, and the temperature of the detector is 300°C , the carrier gas is N 2 , the flow rate is 30 mL/min, the flow rate of H 2 is 30 mL/min; the air flow rate is 300 mL/min, and the sample injection is 0.5 ⁇ L.
  • PET depolymerization rate (1-weight of unreacted waste polyester fine particles/feeding amount of waste polyester)*100%.
  • the depolymerization reaction fraction of Example 1, the polymerization reaction fraction and the depolymerization reaction fraction of Comparative Example 7 were collected by a double condensation system for infrared spectrum testing, and the spectrograms are shown in FIG. 1 . It can be seen that the depolymerization reaction cuts in Example 1 are mainly water and ethylene glycol, and the polymerization reaction cuts are mainly water and butanediol, while the depolymerization reaction cuts in Comparative Example 7 are compared with THF standard solution. The characteristic peaks are very obvious, which means that more THF by-products have been obtained in the reaction.
  • the depolymerized monomer obtained in embodiment 1 is carried out infrared spectrum test, can confirm according to the infrared spectrogram of Fig. 2, the depolymerized monomer obtained in embodiment 1 is polybutylene terephthalate oligomer (BHBT) .
  • BHBT polybutylene terephthalate oligomer
  • Example 1 The regenerated polyester obtained in Example 1 is tested by infrared spectrum.
  • the carbonyl group on the bond; 1120cm -1 and 1177cm -1 are the stretching vibration absorption peaks of the ether bond (COC).
  • the stretching vibration and out-of-plane bending vibration absorption peaks of the (-CH) group appearing at 3050 cm -1 belong to the (-CH) group on the benzene ring; the new absorption peak at 1578 cm -1 in the figure is the benzene
  • the stretching vibration peak of the ring skeleton, the strong absorption peak at 752cm -1 is the CH stretching vibration absorption peak close to the benzene ring, and the absorption peak at 1467cm -1 is the in-plane bending of -CH 2 -CH 2 - in PBSeT copolyester Vibration absorption peak; at 2931cm -1 and 1408cm -1 , 1360cm -1 are the stretching vibration absorption peak and in-plane bending vibration peak of methylene (-CH 2 -) on the molecular chain of PBSeT copolyester respectively; at 3400 ⁇ 3630cm -1 is the stretching vibration absorption peak of intermolecularly associated hydroxyl
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 depolymerized monomer BHBT BHBT BHBT BHBT BHBT BHBT BHBT BHBT BHBT Depolymerization rate of waste polyester 100% 100% 100% 100% 100% recycled polyester PBSeT PBAT PBSeT PBSeT PBSeT Recycled Polyester Yield 95% 88% 86% 87% 85% THF yield (%) 3.0 3.3 3.4 3.3 3.5 the Example 6
  • Example 7 Example 8
  • Example 10 Example 10
  • the method of the present invention can effectively close the loop to recycle waste polyester, the depolymerization temperature is low, the time is short, the depolymerization efficiency is high, and the depolymerization monomer yield is high and the by-product content is extremely high. Low.
  • Comparative Example 1 did not use microwaves in the depolymerization process, and the depolymerization efficiency was extremely low under the same depolymerization temperature and time, and almost no depolymerization occurred.
  • Comparative Example 2 microwave depolymerization was not used, but the reaction temperature was increased and the reaction time was prolonged. Although the depolymerization efficiency was improved to a certain extent, a large amount of cyclized by-products were produced during the depolymerization process, and the THF yield was 5%. .
  • Comparative Example 3 Although microwave conditions were used in the depolymerization process, since the depolymerization catalyst was zinc acetate, the depolymerization efficiency was poor, and the residual zinc in the reaction system affected the intrinsic viscosity of the regenerated polyester, and the final obtained The yield of recycled polyester was 84%, and the intrinsic viscosity was 1.251dL.g -1 . Although comparative example 4 adopts microwave conditions in the depolymerization process, because the temperature is too low, the depolymerization efficiency is low, and it is difficult to alcoholyze the waste polyester in a short time. In Comparative Example 5, the depolymerization temperature was 190 ⁇ 2° C., which was too high, so that the yield of THF reached 4.2%.
  • Comparative Example 6 the depolymerization temperature is not constant, and the fluctuation is as high as 5°C, which makes the depolymerization rate of waste polyester and the yield of recycled polyester lower.
  • Comparative Example 7 is to simulate the method of the prior art to prepare recycled polyester. It can be seen that the content of by-products obtained by using this method is relatively high, the THF yield reaches 7%, and the yield of recycled polyester is only 83%.

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Abstract

一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法，包括在微波条件下选用特定的解聚催化剂对废旧聚酯解聚；将解聚产物去除多元醇溶剂后，经过提纯去除副产物，得到解聚单体；将解聚单体与二元酸、多元醇、聚合催化剂和扩链剂混合，进行酯化反应，再加入稳定剂和催化剂进行缩聚得到再生聚酯。所述方法解聚温度低、效率高，多元醇溶剂用量少，副产物含量极低，同时解聚催化剂不需要进行分离，可直接进行再生聚酯的共酯化，也不会对制得的再生聚酯的性能造成不利影响。所述方法可以实现废旧聚酯的闭环回收。

Description

一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法 技术领域
本发明涉及聚酯的化学再生技术领域，更具体的，涉及一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法。
背景技术
聚酯行业飞速发展的同时，废旧聚酯制品的处理问题接踵而来，社会中废弃聚酯制品的巨大存量不仅给生态环境带来了巨大的压力，同时造成了石化资源的严重浪费。因此，有大量的废旧聚酯需要被回收利用、再生利用。
对废旧聚酯的回收再利用方法主要分为两类：物理回收和化学回收。物理回收主要是利用聚酯的热塑性，将聚酯及其制品经过除杂、清洗、熔融再造粒，得到二次塑料或者纤维制品，虽然工艺简便，成本较低，但仅能实现聚酯的降级回收，且回收次数有限，达不到循环使用的目的。化学回收是指基于聚酯缩聚反应的可逆性及酯交换反应的亲核反应机理，通过小分子解聚剂对大分子链的进攻使聚酯解聚成聚合单体或中间体，经分离提纯后进行再聚合实现再生。将废弃聚酯通过化学回收的方法再生利用，能够有效利用资源、降低环境负荷。
现有的化学法回收利用废旧聚酯的方法中，主要有以下几方面的缺陷：(1)含有重金属类解聚催化剂的残留对于再生聚酯的性能有不利影响，如导致再生聚酯易分解、粘度低，且造成重金属含量超标；(2)废旧聚酯的解聚过程中温度高、解聚剂用量高，大多需要加压反应，解聚时间较长，反应装置的安全性要求高，能耗比较大，不符合当下绿色低碳的技术要求，同时易产生成分较复杂的副产物，影响解聚效率同时导致副产物处理的能耗及一系列环境影响；(3)再生聚酯难以应用于回收前相同或相似场景，即难以实现闭环回收，且目前化学回收后以PET以制备塑料瓶，纤维和织物为主，而工业化制备可降解塑料的回收很少有涉及，且目前可降解塑料的堆肥条件苛刻，在自然环境下难以完成有效的充分的降解，实现可降解材料的闭环循环回收是大势所趋。
中国专利申请CN107266664A公开了一种聚酯废料回收工艺，使用醋酸锌作为催化剂对PET废料进行解聚，但残留在解聚产物中的锌离子会因为其对羰基氧配位的催化机理会导致再聚合过程中热降解等副反应加速，使得分子量增长受限，再生聚酯的粘度低，品质差。中国专利申请CN102731310A公开了一种第一 过渡系金属离子液体催化醇解PET的方法，但此类离子液体的催化剂中卤组元素含量很高，如果未能将催化剂从解聚产物中除去，则再聚合过程中会因为产生卤化氢而导致大分子的分解，严重影响再聚合制品的品质；并且该方法中催化剂添加量需要达到PET的10wt.％，醇解溶剂乙二醇的用量约为PET的4～10倍，催化剂和二元醇的用量大。
中国专利申请CN 104327260 A公开了一种生物可降解再生聚酯的制备方法，采用的解聚催化剂为可溶解于乙二醇的二元醇钛碱金属配位化合物，对废旧PET进行解聚，进而再共聚合得到再生聚酯。但一方面，该方法仅能回收废旧PET，而不涉及其他种类的废旧聚酯，另一方面，该方法的醇溶解聚过程中解聚温度为160～240℃，解聚时间为0.5～5h，温度过高、时间过长，使得乙二醇极易环化脱水形成环化副产物，并且该方法的醇解剂用量大，过程复杂。
现有技术(孟辉.聚丁二酸丁二醇酯合成中工艺条件对酯化过程副产物四氢呋喃的影响[D].华东理工大学,2011.)报道了对于环化副产物的解决方案，例如通过通入氮气、降低反应温度等方法降低酯化过程中环化产物四氢呋喃的生成速率和产量。但对于解聚反应，在过低的反应温度、过短的反应时间下聚酯无法解聚。
在绿色低碳循环的发展方针，以及国家碳达峰、碳中和的战略要求下，急需开发出一种典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法。
发明内容
本发明为克服上述现有技术所述的废旧聚酯未闭环回收、副产物含量高的缺陷，提供一种绿色的闭环回收废旧聚酯制备再生聚酯的方法。
为解决上述技术问题，本发明采用的技术方案是：
一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法，包括如下步骤：
S1.废旧聚酯解聚：
将废旧聚酯溶解于含有解聚催化剂和微波吸收剂的多元醇溶剂中，在常压、惰性气体氛围、微波条件下，进行解聚反应，得到解聚产物；
所述解聚催化剂为钛酸纳米管、磷酸钛、二氧化钛、钛酸丁酯、乙二醇钛或丁二醇钛中的一种或几种；
所述解聚反应的温度为150～170℃且温度波动≤2℃，解聚反应时间为 6～35min；
S2.解聚产物提纯：
将步骤S1制得的解聚产物去除多元醇溶剂后，经过提纯去除副产物，得到解聚单体；
S3.共酯化：
将步骤S2制得的解聚单体，与二元酸、多元醇、聚合催化剂和扩链剂混合，在惰性气体氛围、微波条件下，进行聚合反应，得到酯化产物；
S4.缩聚：
将步骤S3的酯化物与催化剂和稳定剂混合，在抽真空的条件下进行缩聚反应，得到所述再生聚酯。
本发明利用废旧聚酯解聚可合成一系列脂肪族-芳香族共聚酯作为再生聚酯，不仅有效实现了聚酯的化学回收，且该再生聚酯使用后可再次进行化学解聚、回收利用，实现闭环回收。
在解聚过程中，本发明以钛酸纳米管、磷酸肽、二氧化钛、钛酸丁酯、乙二醇钛或丁二醇钛作为解聚催化剂，一方面其解聚效果优异，另一方面，该钛系催化剂对废旧聚酯进行解聚后，不需要进行分离，可直接作为再生聚酯共酯化的催化剂，且不会对制得的再生聚酯的性能造成不利影响。并且，本发明的催化体系不含可降解聚酯的限制元素，在再生聚酯的合成过程中把控原料，为后续的循环回收提供有力保障。
发明人研究发现，废旧聚酯解聚反应在微波条件下进行，一方面微波能够使得待解聚的聚酯原料内外部同时受热，使得其受热均匀，解聚更彻底；另一方面，微波能够以极低的温度达到与传统加热方式同样的解聚效果，使得解聚反应可以高效、快速地进行，既保证了废旧聚酯的解聚程度，又极大地缩短了解聚时间、降低了反应温度，并减少了解聚过程中多元醇引起的环化产物的生成，提高了产率，减少了副产物处理对环境的污染。
在步骤S1的解聚反应过程中，不仅要求解聚反应的温度范围满足150～170℃，还要求解聚反应温度恒定，即单次解聚反应的温度波动不超过±2℃。
在温度恒定的情况下，能够减少副产物产生，同时保证极高的解聚率和反应效率。
所述废旧聚酯为聚己二酸/对苯二甲酸丁二酯(PBAT)、聚(癸二酸丁二醇- 对苯二甲酸丁二醇)共聚酯(PBSeT)、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯(PETG)、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯(PCTG)、聚对苯二甲酸丁二酯(PBT)中或聚对苯二甲酸乙二酯(PET)中的一种或几种。
所述废旧聚酯的来源可以为消费后回收塑料(Post Consumer Recycled Plastic，PCR)、工业回收塑料(Post Industry Recycle Plastic，PIR)或海洋废塑料中的一种或几种。
所述海洋废塑料可以为趋海塑料(OceanBoundPlastic，OBP)和/或海洋内塑料(in-the-ocean plastics，IOP)。
所述废旧聚酯经除杂、清洗、破碎后可直接用于解聚。
优选地，所述解聚催化剂为钛酸纳米管、磷酸钛或钛酸丁酯中的一种或几种。
对于同样的废旧聚酯，使用钛酸纳米管、磷酸钛或钛酸丁酯作为解聚催化剂，解聚效率更优，解聚时间更短，从而进一步减少了环化产物的生成。
优选地，所述解聚催化剂占废旧聚酯的0.05～0.15wt.％。
优选地，步骤S1中所述废旧聚酯与多元醇的质量比为1：(0.6～3)。
优选地，所述微波吸收剂为碳酸钠、氯化钠、活性炭或磷酸钠中一种或几种。
更优选地，所述微波吸收剂为碳酸钠。
优选地，步骤S1中所述微波吸收剂占废旧聚酯的0.01～1wt.％。
发明人研究发现，碳酸钠既具有微波吸收作用，又具有一定的解聚催化作用。在使用碳酸钠作为微波吸收剂时，步骤S1的解聚效率得到进一步提升。
优选地，步骤S1中所述微波条件为微波功率500～1000w，微波波长122mm。
优选地，步骤S1中所述解聚反应的温度为155～165℃，时间为10～30min。
更优选地，步骤S1中所述解聚反应的温度为160℃，时间为10min。
在本申请的技术方案中，在微波条件下进行解聚反应的过程中，微波功率与解聚反应的温度并非直接对应的关系。
优选地，步骤S2中所述去除多元醇溶剂为减压蒸馏和真空干燥。
优选地，步骤S2中所述提纯为溶解重结晶过滤。
步骤S3中所述聚合催化剂可以为聚酯类常用的聚合催化剂。
优选地，步骤S3中所述聚合催化剂为钛酸丁酯、钛酸丙酯、钛磷化合物、钛硅化合物或钛酸乙酯中的一种或几种。
优选地，步骤S1中所述多元醇溶剂和步骤S3中所述二元醇均为乙二醇、丙 二醇、1,4-丁二醇或戊二醇、丙三醇中一种或几种。
优选地，步骤S3中所述二元酸为碳原子数为2～36的脂肪族二元酸。
优选地，步骤S3中所述多元醇与二元酸的质量比为(0.2～1)：1。
优选地，步骤S1中所述多元醇溶剂和步骤S3中所述二元醇均为1,4丁二醇，步骤S3中所述二元酸为癸二酸和/或己二酸。
使用生物质的1,4丁二醇、癸二酸作为原料进行共酯化时，制得的再生聚酯的生物质含量≥60％，充分实现了生物质和化学回收并举的绿色低碳循环理念。
优选地，步骤S3中所述微波条件为500～1000w。
优选地，步骤S3中所述聚合反应的温度为160～180℃，时间为30～90min。
优选地，步骤S3中聚合催化剂占解聚单体、二元酸、二元醇和扩链剂质量之和的0.03～2wt.％。
优选地，步骤S3中所述扩链剂为多元醇类扩链剂、异氰酸酯类扩链剂、酸酐类扩链剂或环氧化合物扩链剂中一种或几种。
可选地，所述多元醇类扩链剂为乙二醇、丙三醇、季戊四醇、三羟甲基丙烷、木糖醇或山梨醇中的一种或几种。
可选地，所述异氰酸酯类扩链剂为甲苯二异氰酸酯(TDI)、二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)或异氟尔酮二异氰酸酯中一种或几种。
可选地，所述环氧化合物扩链剂可以为ADR扩链剂。
优选地，步骤S4中所述催化剂与步骤S3所述聚合催化剂一致。
优选地，步骤S4中所述稳定剂为有机亚磷酸酯类稳定剂、磷酸酯类稳定剂、受阻酚类稳定剂中的一种或几种。
可选地，所述有机亚磷酸酯类稳定剂可以为亚磷酸三甲酯、亚磷酸三乙酯或亚磷酸三苯酯中的一种或几种。
可选地，所述磷酸酯类稳定剂可以为磷酸三苯酯、磷酸三甲酯或磷酸三乙酯中的一种或几种。
可选地，所述受阻酚类稳定剂可以为3,5-二叔丁基-4-羟基苄基二乙基膦酸酯(抗氧剂1222)和/或抗氧剂1010。
优选地，所述缩聚反应的温度为230～250℃，时间为3～5h，压力为20～100Pa。
与现有技术相比，本发明的有益效果是：
本发明利用废旧聚酯解聚、再聚合，合成的再生聚酯仍是全生物降解聚酯，不仅有效实现了聚酯的化学回收，且该再生聚酯使用后可再次进行化学解聚、回收利用，实现闭环回收。
在解聚过程中，本发明以特定的钛系催化剂作为解聚催化剂，在微波吸收剂的存在下，以较低温度、较短的时间对废旧聚酯进行解聚，且二元醇溶剂用量小，催化剂添加量低。获得了极高的解聚效率，同时副产物产率低，解聚催化剂不需要进行分离，可直接进行下一步骤的酯化，也不会对制得的再生聚酯的性能造成不利影响，有效实现了绿色化学回收。
当使用生物质的1,4-丁二醇、癸二酸作为原料进行共酯化时，制得的再生聚酯的生物质含量≥60％，实现了生物质和化学回收并举的技术路线。根据生命周期评估(LCA)的测算结果，由于引入了生物质原料和废旧聚酯作为原料，相对现有化学回收路线的碳排放降低幅度超过60％以上，充分体现了技术路线和产品的低碳特征。
来自于海洋垃圾的废旧PET瓶由于在自然环境中受到光、热、海水冲刷，生物和微生物附着等多方面因素的影响，出现了明显了性能劣化，其外观呈现为脆化，透明度下降等特征，其实质是聚酯降解后导致分子量下降，特性粘数降低。这些降解产物进入海洋后成为微塑料，由于大部分海洋废旧PET性能下降明显，打捞收集后常规的物理回收只能降级回收或者能量回收，不能有效体现资源回收再充分利用的原则。本发明不但可以通过回收海洋垃圾实现保护环境和降低微塑料污染的目的，而且还能将收集的废旧PET作为资源进行化学回收转化为高值次级产物充分利用，实现了环境保护和资源高质循环的双重目的。
附图说明
图1为实施例1的解聚反应馏分和聚合反应馏分、对比例7的解聚反应馏分、四氢呋喃标准溶液的红外光谱图。
图2为实施例1制得的解聚单体的红外光谱图。
图3为实施例1制得的再生聚酯的红外光谱图。
图4为实施例1制得的再生聚酯的核磁氢谱。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例及对比例中的原料均可通过市售得到；
废旧聚酯：
PET粒子，来自POLINDO PT；海洋废旧PET瓶片(特性粘度<0.5dL/g，重均分子量<16000g/mol)，来自蓝丝带海洋保护协会；PCTG，PETG，来自广州市锐胜塑料有限公司；PBAT、PBSeT，来自珠海万通化工限公司。
解聚催化剂：
钛酸纳米管，购自先丰纳米；磷酸钛，购自威海天创精细化工有限公司；钛酸丁酯，购自阿拉丁；醋酸锌，购自阿拉丁。
微波吸收剂：
碳酸钠，氯化钠购自麦克林；活性碳粉，市售,分析纯,平均粒径30μm，碳化硅，购自麦克林。
稳定剂：
亚磷酸三甲酯，磷酸三苯酯，购自阿拉丁。
二元醇中：1，4-丁二醇(BDO)，为生物基BDO，购自山东兰典生物科技股份有限公司；
二元酸中：葵二酸，购自济南博奥化工有限公司。
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1～5
实施例1～5分别提供一种对废旧聚酯的闭环回收制备再生聚酯的方法，包括如下步骤，具体的原料及反应条件见表1：
S1.废旧聚酯解聚：
将平均粒径≤2mm的废旧聚酯溶解于含有解聚催化剂和微波吸收剂的二元醇溶剂中，放置于500mL的玻璃反应釜中，再转移到微波化学合成仪(型号ANKS-SR8，青岛艾尼克斯微波自动化设备有限公司)中，在氮气氛围中、微波条件下，进行解聚反应，得到解聚产物；
S2.解聚产物提纯：
将步骤S1制得的解聚产物经减压蒸馏去除二元醇等溶剂后，经过提纯得到解聚单体；
S3.共酯化：
将步骤S2制得的解聚单体，与二元酸、二元醇、聚合催化剂和扩链剂混合， 在惰性气体氛围、微波条件下，进行聚合反应，得到酯化产物；
S4.缩聚：
将步骤S3的酯化产物加入稳定剂和催化剂，在抽真空的条件下进行缩聚反应，得到所述再生聚酯。
表1实施例1～5的原料及反应条件
Figure PCTCN2021141549-appb-000001
Figure PCTCN2021141549-appb-000002
实施例6～10
实施例6～10提供一种对废旧聚酯的闭环回收制备可生物降解聚酯的方法，除了步骤S1中的解聚条件外，其他步骤同实施例1；
实施例6的步骤S1中，解聚条件为温度恒定为150±2℃，时间35min；
实施例7的步骤S1中，解聚条件为温度恒定为155±2℃，时间30min；
实施例8的步骤S1中，解聚条件为温度恒定为165±2℃，时间10min；
实施例9的步骤S1中，解聚条件为温度恒定为170±2℃，时间8min。
实施例10的步骤S1中，解聚条件为温度恒定为160±1℃，时间10min。
对比例1～6
对比例1～6提供一种对废旧PET和PETG共混物的闭环回收制备可生物降解聚酯的方法，步骤同实施例1，具体原料及反应条件如表2。
表2对比例1～3的原料及反应条件
Figure PCTCN2021141549-appb-000003
Figure PCTCN2021141549-appb-000004
对比例4～6
对比例4～6提供一种对废旧PET和PETG共混物的闭环回收制备可生物降解聚酯的方法，除了步骤S1中的解聚条件外，其他步骤、原料及反应条件同实施例1；
对比例4的步骤S1中，解聚条件为温度恒定为140±2℃，时间90min；
实施例5的步骤S1中，解聚条件为温度恒定为190±2℃，时间10min；
实施例6的步骤S1中，解聚条件为温度160℃，波动范围为±5℃，时间10min。
对比例7
对比例7提供一种对废旧PET和PETG共混物的闭环回收制备可生物降解聚酯的方法，步骤与中国专利申请CN 104327260 A实施例1相近，具体如下：
S1.制备醇解催化剂丁二醇钛酸锂，包括以下步骤：
a)将钛酸四乙酯在50℃和氮气保护条件下，与丁二醇均匀混合，钛酸四乙酯酯与丁二醇的摩尔比为1:100；b)加入氢氧化锂，氢氧化锂与钛酸四乙酯的摩尔比为2.05：1，持续搅拌至反应体系为均一透明的液体后，升高反应温度至180℃；c)反应过程中，回流丁二醇并排除反应生成的低沸点的乙醇和水，反应时间3小时，反应结束后在温度为190℃下，反应体系压力为0.5atm下，0.5min中内将体系内的丁二醇蒸发完全，将体系内的二元醇蒸发完全获得白色固体，对此固体利用乙醇-氯仿重结晶三次得到无色晶体，即制得丁二醇钛酸锂；
S2.将以上制得的醇解催化剂丁二醇钛酸锂溶解于解聚剂丁二醇中，丁二醇钛酸锂的用量为丁二醇质量的1％，形成解聚溶液；
S3.将解聚溶液与废旧PET粒子和PETG共混物混合，并进行在惰性气体保护下的解聚反应，同时搅拌，搅拌速率为1500转/min，解聚剂丁二醇用量与PET和PETG共混物的摩尔比为20:1，解聚反应温度为190℃，反应体系压力为1atm，反应时间为3h；
S4.所得溶液中加入含有活性炭质量分数为0.5％的丁二醇分散液，活性炭丁二醇分散液的加入量为解聚溶液质量的1.5倍，在温度为150℃下，常压回流搅拌脱色5h后，经过滤去除杂质及脱色用的活性炭，脱色及过滤过程反复进行2次；
S5.将除杂脱色后的解聚物的丁二醇溶液在温度为190℃且压力为0.5atm条件下，将溶液中的丁二醇蒸发完全，获得提纯及脱色后的解聚产物；
S6.己二酸一缩二丁二醇酯化物的制备：将1，6-己二酸，丁二醇，聚丁二醇4000三者以等物质量混合，并加入100ppm的丁二醇钛酸锂为催化剂，在反应温度为170℃，压力为1atm下进行酯化4h，同时及时馏出反应过程中生成的水，反应过程中以惰性气体进行保护，反应结束后获得己二酸一缩二丁二醇酯化物的制备；
S7.按质量比为8：2混合步骤S5和步骤S6获得的产物，并加入100ppm丁二醇钛酸锂作为缩聚催化剂和50ppm磷酸三甲酯热稳定剂，并在220℃，压力1atm，惰性气体保护条件下搅拌混合；然后，将反应温度升高至250℃，继续反应120min，同时在此段时间，使体系内压力匀速降低至1kPa；然后，将反应温度升高至265℃，使体系内压力降低至20Pa后，继续反应180min，即获得再生聚酯。
性能测试
对上述实施例及对比例制得的解聚产物和再生聚酯进行性能测试，具体方法如下：
解聚单体和再生聚酯的定性：对解聚单体和再生聚酯分别进行红外光谱检测，测试条件为测定方法：透射、参比样品：KBr、检测器：DTGS、波数范围：400～4000cm -1、分辨率：4cm -1、扫描次数：32。
四氢呋喃(THF)产率：蒸出的馏分称重,采用红外进行定性，用气相色谱- 氢火焰检测器分析其中四氢呋喃和其它副产物的量；标样乙二醇、四氢呋喃、1,4-丁二醇、异丙醇为分析纯；色谱柱为美国Agilent公司HP-FFAP气相毛细管柱30m*0.32mm*0.25μm，以异丙醇为内标；进样器温度250℃,检测器温度300℃,载气为N 2，流速30mL/min，H 2流速30mL/min:空气流速300mL/min，进样0.5μL。
PET解聚率＝(1-未反应的废旧聚酯细颗粒重量/废旧聚酯投料量)*100％。
再生聚酯的产率：再生聚酯产率＝产物的实际重量/理论重量*100％。
采用双冷凝系统收集对实施例1的解聚反应馏分、聚合反应馏分和对比例7的解聚反应馏分进行红外光谱测试，谱图见图1。可以看出，实施例1中解聚反应馏分主要是水和乙二醇、聚合反应馏分主要是水和丁二醇，而对比例7中的解聚反应馏分与四氢呋喃标准溶液相比，THF的特征峰非常明显，这表示其反应得到了较多THF副产物。
对实施例1制得的解聚单体进行红外光谱测试，根据图2的红外光谱图可以确认，实施例1得到的解聚单体为聚对苯二甲酸丁二醇低聚物(BHBT)。
对实施例1制得的再生聚酯进行红外光谱测试，根据图3的红外光谱图，在1730cm -1处出现的羰基(-C＝O)伸缩振动吸收峰，归属于PBSeT共聚酯中酯键上的羰基；1120cm -1、1177cm -1处为醚键(C-O-C)伸缩振动吸收峰。在3050cm -1处出现的(-C-H)基团的伸缩振动与面外弯曲振动吸收峰，归属于苯环上的(-C-H)基团；图中1578cm -1处新出现的吸收峰为苯环骨架的伸缩振动峰，752cm -1处的强吸收峰是靠近苯环的C-H伸缩振动吸收峰，1467cm -1处的吸收峰为PBSeT共聚酯中-CH 2-CH 2-的面内弯曲振动吸收峰；在2931cm -1和1408cm -1、1360cm -1处分别为PBSeT共聚酯分子链上亚甲基(-CH 2-)的伸缩振动吸收峰和面内弯曲振动峰；在3400～3630cm -1处为分子间缔合的羟基(-OH)的伸缩振动吸收峰，归属于PBSeT共聚酯中的端羟基。可以确认，实施例1制得的再生聚酯为PBSeT。
各实施例及对比例的测试结果见表3。
表3实施例1～10及对比例1～4的测试结果
  实施例1 实施例2 实施例3 实施例4 实施例5
解聚单体 BHBT BHBT BHBT BHBT BHBT
废旧聚酯解聚率 100％ 100％ 100％ 100％ 100％
再生聚酯 PBSeT PBAT PBSeT PBSeT PBSeT
再生聚酯产率 95％ 88％ 86％ 87％ 85％
THF产率(％) 3.0 3.3 3.4 3.3 3.5
  实施例6 实施例7 实施例8 实施例9 实施例10
解聚单体 BHBT BHBT BHBT BHBT BHBT
废旧聚酯解聚率 99％ 99.9％ 99.9％ 99.9％ 99.9％
再生聚酯 PBSeT PBSeT PBSeT PBSeT PBSeT
再生聚酯产率 89％ 91％ 94％ 92％ 96％
THF产率(％) 3.5 3.2 3.1 3.3 2.9
Figure PCTCN2021141549-appb-000005
根据上表的测试结果可以看出，采用本发明的方法可以有效闭环回收废旧聚酯，解聚温度低、时间短、解聚效率高，且获得解聚单体产率高、副产物含量极低。
而对比例1与实施例1相比，解聚过程中未使用微波，在相同的解聚温度和时间下解聚效率极低，几乎未解聚。对比例2仍未使用微波解聚，但提高了反应温度、延长了反应时间，虽然一定程度提高了解聚效率，但也使得解聚过程中产生了大量环化副产物，THF产率为5％。对比例3中，虽然在解聚过程中使用了微波条件，但由于解聚催化剂为醋酸锌，解聚效率差，且锌残留在反应体系内影响了再生聚酯的特性粘度，最终制得的再生聚酯产率为84％，特性粘度为1.251dL.g -1。对比例4虽然在解聚过程中采用了微波条件，由于温度太低，导致解聚效率低，难以在短时间是废旧聚酯醇解。对比例5中，解聚温度为190±2℃，温度过高，使得THF产率达到4.2％。对比例6中解聚温度不恒定，波动高达5℃，使得废旧聚酯解聚率和再生聚酯的产率都较低。对比例7为模拟现有技术的方法制备再生聚酯，可以看出，使用该方法得到的副产物含量较高，THF产率达到7％，且再生聚酯的产率仅为83％。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施 方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (10)

  1. 一种具有典型绿色低碳特点的闭环回收废旧聚酯制备再生聚酯的方法，其特征在于，包括如下步骤：
    S1.废旧聚酯解聚：
    将废旧聚酯溶解于含有解聚催化剂和微波吸收剂的多元醇溶剂中，在常压、惰性气体氛围、微波条件下，进行解聚反应，得到解聚产物；
    所述解聚催化剂为钛酸纳米管、磷酸钛、二氧化钛、钛酸丁酯、乙二醇钛或丁二醇钛中的一种或几种；
    所述解聚反应的温度为150～170℃且温度波动≤2℃，解聚反应时间为6～35min；
    S2.解聚产物提纯：
    将步骤S1制得的解聚产物去除多元醇溶剂后，经过提纯去除副产物，得到解聚单体；
    S3.共酯化：
    将步骤S2制得的解聚单体，与二元酸、多元醇、聚合催化剂和扩链剂混合，在惰性气体氛围、微波条件下，进行反应，得到酯化产物；
    S4.缩聚：
    将步骤S3的酯化产物与催化剂和稳定剂混合，在抽真空的条件下进行缩聚反应，得到所述再生聚酯。
  2. 根据权利要求1所述方法，其特征在于，步骤S1中所述解聚反应的温度为155～165℃，时间为10～30min。
  3. 根据权利要求1所述方法，其特征在于，所述解聚催化剂占废旧聚酯的0.05～0.15wt.％。
  4. 根据权利要求1所述方法，其特征在于，步骤S1中所述废旧聚酯与多元醇的质量比为1：(0.6～3)。
  5. 根据权利要求1所述方法，其特征在于，步骤S1中所述微波条件为微波功率500～1000w，微波波长122mm。
  6. 根据权利要求1所述方法，其特征在于，所述废旧聚酯为聚己二酸/对苯二甲酸丁二酯、聚(癸二酸丁二醇-对苯二甲酸丁二醇)共聚酯、聚对苯二甲酸乙二醇酯-1,4-环己烷二甲醇酯、聚对苯二甲酸乙二醇-1,4-环己烷二甲醇酯、聚对苯 二甲酸丁二酯或聚对苯二甲酸乙二酯中的一种或几种组合。
  7. 根据权利要求1所述方法，其特征在于，所述微波吸收剂为碳酸钠、氯化钠、活性炭或磷酸钠中一种或几种。
  8. 根据权利要求1所述方法，其特征在于，所述聚合催化剂为钛酸丁酯、钛酸丙酯、钛磷化合物、钛硅化合物或钛酸乙酯中的一种或几种。
  9. 根据权利要求1所述方法，其特征在于，步骤S4中所述稳定剂为有机亚磷酸酯类稳定剂、磷酸三甲酯类稳定剂、受阻酚类稳定剂中的一种或几种。
  10. 根据权利要求1所述方法，其特征在于，步骤S3中所述微波条件为500～1000w，所述聚合反应的温度为160～180℃，时间为30～90min。
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