WO2023155367A1 - 一种聚酯混纺面料的循环回收利用方法 - Google Patents

一种聚酯混纺面料的循环回收利用方法 Download PDF

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WO2023155367A1
WO2023155367A1 PCT/CN2022/104576 CN2022104576W WO2023155367A1 WO 2023155367 A1 WO2023155367 A1 WO 2023155367A1 CN 2022104576 W CN2022104576 W CN 2022104576W WO 2023155367 A1 WO2023155367 A1 WO 2023155367A1
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polyester
methanol
catalyst
recycling
reactor
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English (en)
French (fr)
Inventor
刘红港
郭青
郭彩红
毛德彬
胡文健
万晓波
穆有炳
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Qingdao Amino Material Technology Co Ltd
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Qingdao Amino Material Technology Co Ltd
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Priority to JP2024569664A priority Critical patent/JP7819979B2/ja
Priority to EP22926674.7A priority patent/EP4480942A4/en
Priority to US18/838,455 priority patent/US20250136781A1/en
Publication of WO2023155367A1 publication Critical patent/WO2023155367A1/zh
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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
    • C08J11/28—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 compounds containing nitrogen, sulfur or phosphorus
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0241—Imines or enamines
    • 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
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • 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
    • 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
    • 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 recovery and reuse of textiles, and further relates to a method for recycling and recycling polyester blended fabrics.
  • Polyester is one of the most popular fiber materials in the world. Since 2010, polyester fiber has been the most consumed fiber in the world. In 2020, the global annual polyester production will be as high as 57 million tons. As a textile fiber, polyester is often blended with other fibers in addition to being used alone. The blended polyester fabric not only has the excellent mechanical properties of polyester fabrics, but also obviously retains the excellent properties of other fiber fabrics. Therefore, various polyester blends are becoming more and more popular in the apparel industry. For example, a blend of polyester and cotton is one of the most common fabrics found in casual clothing. This fabric not only has the comfort of cotton but also has the cheapness of polyester fabric. In sportswear, polyester and spandex blend fabrics are the most important fabrics.
  • Such blended fabrics can not only retain the appearance and texture of polyester fibers, but also have excellent elasticity and wearing comfort. However, a large number of clothes made of blended fabrics are discarded after use. This is due to the lack of technology that can completely separate polyester and other fiber components in the existing technology. Millions of tons of polyester blend fabrics are therefore simply incinerated and landfilled each year. Such a treatment method not only wastes a lot of resources, but also has a serious negative impact on the environment in which we live. If polyester blended textile waste can be recycled into high value-added textile fibers in a sustainable process, it will not only reduce the negative impact on the environment caused by waste disposal, but also maximize the use of our limited resources.
  • Patent No. US 8,541,477 B2 discloses a method for depolymerizing polyester at a low temperature. This method can depolymerize polyester at a temperature of 120°C and above. The final spandex component loses its elasticity and is difficult to recycle.
  • Patent No. WO2021126661A1 discloses a method for depolymerizing polyester at a temperature of 100°C-180°C.
  • polyester cannot be 100% depolymerized under low temperature reaction conditions (100°C-140°C). This prevents the polyester from being completely separated from the blend, making it difficult to recycle other fabric components.
  • the method has a low yield of polyester monomer under low temperature conditions, which also makes the economic cost of the recycling process relatively high. Therefore, how to achieve 100% depolymerization of polyester components under low temperature conditions without damaging other components is the key to realizing the recyclability of polyester blended fabrics.
  • the purpose of the present invention is to provide a recycling method for polyester blended fabrics.
  • a recycling and utilization method for polyester blended fabrics After treating raw materials containing polyester, they are reacted at 40-120°C with a catalyst for 0.5-8 hours to degrade polyester to achieve complete depolymerization, and then separate and recycle. The final polyester component and other blended components can be reused.
  • the catalyst is an organic base main catalyst and an auxiliary catalyst, wherein the catalyst is added in an amount of 0.1-20 wt% of the mass of the blended fabric; the mass ratio of the organic base main catalyst to the auxiliary catalyst is 1:0.01-100.
  • the main catalyst of the organic base is one or more of nitrogen-containing amidine or guanidine compounds and derivatives; the auxiliary catalyst is a nitrile compound.
  • the organic base main catalyst is a) 1,8-diazabicycloundec-7-ene (DBU), polymer or compound-loaded DBU, and an organic salt formed of DBU, imidazole and its derivatives; b) 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), polymer or compound-loaded TBD, and organic salts of TBD with imidazole and its derivatives; c) 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), polymer or compound supported DBN, and organic salts of DBN and imidazole and its derivatives.
  • DBU 1,8-diazabicycloundec-7-ene
  • TBD 1,5,7-Triazabicyclo[4.4.0]dec-5-ene
  • DBN 1,5-diazabicyclo[4.3.0]non-5-ene
  • DBN 1,5-diazabicyclo[4.3.0]non-5-ene
  • polystyrene-supported DBU polystyrene-supported DBU
  • activated carbon-supported DBU polystyrene-supported DBU
  • the organic salt formed (taking the organic salt formed by DBU and imidazole and its derivatives as an example) is the organic salt ([HDBU][Im]) formed by DBU and imidazole (Imidazole), and the organic salt ([HDBU][Im]) formed by DBU and 2-ethylimidazole (2- Ethylimidazole) organic salt ([HDBU][2-EtIm]), DBU and benzimidazole (Benzimidazole) organic salt ([HDBU][BIm]), DBU and 2-methylimidazole (2-methylimidazole)
  • the auxiliary catalyst is one or more of acetonitrile, propionitrile, benzonitrile and adiponitrile.
  • the method add the polyester-containing raw material to the methanol solution after treatment, then add a catalyst at 60-110°C, react for 1-5 hours to degrade the polyester to achieve complete depolymerization, and then separate, recover and separate The polyester component is reused.
  • the method add the polyester-containing raw material to the methanol solution after treatment, then add a catalyst at 80-110°C, react for 1-2 hours to degrade the polyester to achieve complete depolymerization, and then separate and recover Separation of polyester components for reuse.
  • the polyester-containing raw material to be treated is a polyester blended fabric or a mixed fabric of polyester and other fabrics; wherein, the content of polyester in the mixed fabric is 5%-100%; the polyester blended fabric is spandex, cotton, The fabric obtained by blending one or more of viscose fiber, regenerated cellulose fiber, nylon, wool, cashmere, and silk with polyester.
  • the polyester content is at least 5%, or at least 25%, or at least 50%, or at least 75%, or at least 95%.
  • the polyester-containing raw material to be treated is to wash the raw material in alcohol or alcohol-containing mixed system at 40-130°C for 0.3-2 hours; wherein, the alcohol-containing mixed system is a mixture of alcohol and a basic compound, and the alkali One or more of the neutral compound soda ash (Na 2 CO 3 ), sodium acetate, sodium methoxide, sodium ethoxide, potassium carbonate, potassium acetate, potassium methoxide, calcium oxide, and calcium hydroxide.
  • the neutral compound soda ash Na 2 CO 3
  • sodium acetate, sodium methoxide, sodium ethoxide, potassium carbonate, potassium acetate, potassium methoxide, calcium oxide, and calcium hydroxide sodium acetate, sodium methoxide, sodium ethoxide, potassium carbonate, potassium acetate, potassium methoxide, calcium oxide, and calcium hydroxide.
  • the raw material is washed in alcohol or alcohol-containing mixed system at 50-110°C or 80-100°C or 90-100°C for 0.3-2 hours to remove the accompanying stains, oil stains and other impurities in the raw material.
  • the solid-liquid is separated, and the solid is collected and subjected to Soxhlet extraction to separate the polyester component and other fiber components; the liquid is subjected to atmospheric distillation to recover alcohol and auxiliary catalyst, and then vacuum distillation or extraction to recover polyester glycol and Dibasic acid monomers and organic base catalysts.
  • the recovered monomers such as dimethyl terephthalate (DMT) and ethylene glycol after depolymerization of the above polyesters can be purified by vacuum distillation and used as raw materials to synthesize new polyesters.
  • DMT dimethyl terephthalate
  • ethylene glycol after depolymerization of the above polyesters can be purified by vacuum distillation and used as raw materials to synthesize new polyesters.
  • the organic base main catalyst first activates methanol to make methanol generate methanol anions with strong nucleophilicity, as shown in the figure below
  • the formed methanol anion is more likely to attack the ester bond through a nucleophilic reaction, thereby achieving the cleavage of the ester bond.
  • the activation of methanol by the organic base catalyst is reversible.
  • a nitrile compound (R-C ⁇ N:) is added to the reaction system, the strong polarity of -C ⁇ N: and the lone pair of electrons on the nitrogen atom stabilize the organic base catalyst cation generated by the reaction in the system, making the reaction balance toward Generate more methanol anions to move in the direction, thereby improving the catalytic activity of the organic base main catalyst.
  • the method of the invention realizes 100% depolymerization of polyester under low temperature conditions.
  • the depolymerized polyester component can be easily separated from other components, thereby realizing the complete separation of polyester and other temperature-sensitive fiber components in blended fabrics.
  • the reaction separation process in the present invention is mild and efficient, other fibers can obtain 100% pure components and the fibers are hardly damaged, and can be directly re-spun into silk or used as raw materials to produce regenerated fibers.
  • the recovered polyester depolymerized monomers can also be used for the synthesis of new polyesters, thereby realizing the closed-loop recycling of different fiber components in polyester blended waste, which is of great significance to protecting the ecological environment and reducing the cost of recycled fibers. Significance.
  • an organic basic catalyst is used to catalyze the breaking of the polyester ester bond.
  • an auxiliary catalyst is added in the system process, and the organic base is realized under the cooperation of the auxiliary catalyst. 100% depolymerization reaction of polyester under low temperature condition, and, after adding auxiliary catalyst, the recovery rate of polyester monomer is significantly improved.
  • Fig. 1 is the infrared spectrogram (FTIR) of the polyester monomer dimethyl terephthalate (DMT) that reclaims after the depolymerization that the embodiment of the present invention provides
  • FTIR infrared spectrogram
  • Fig. 2 is the infrared spectrogram (FTIR) of the polyester monomer furan-2,5-dicarboxylate dimethyl ester recovered after depolymerization provided by the embodiment of the present invention
  • Fig. 3 is the separation and recovery polyester and cotton blended fabric that the embodiment of the present invention mentions; Wherein, A is the blended fabric before the separation reaction; B is the pure cotton fabric after the separation reaction
  • Fig. 4 is the separated and recovered polyester and spandex blended printed fabric that is mentioned in the embodiment of the present invention; wherein, A is the blended fabric before the separation reaction; B is the pure spandex fabric after the separation reaction; C is the spandex yarn that is not damaged under the optical microscope .
  • the method of the invention realizes 100% depolymerization of polyester fiber components under lower temperature conditions, and the recovery rate of polyester monomers is as high as 95%, so that the polyester can be recovered and regenerated more efficiently.
  • the lower reaction temperature makes the process more environmentally friendly, and the energy required for the reaction is reduced, so that the recovery process cost is lower.
  • the present invention aims to recycle and reuse the waste materials of temperature-sensitive fiber and polyester blending.
  • the regenerated cellulose fibers here can be modal fibers and lyocell fibers.
  • polyester depolymerization refers to the degradation of polyester into monomers and small molecular oligomers, such as dimers, trimers, tetramers, pentamers, hexamers, heptamers, etc.
  • the fabric is shed and separated, thereby realizing the separation and recycling of polyester components.
  • Polyester in this technology is a polymer containing ester chemical bonds, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT ), polyethylene 2,5-furandicarboxylate (PEF), polytrimethylene 2,5-furandicarboxylate (PTF), polybutylene 2,5-furandicarboxylate (PBF), polyemulsion Polyester (PLA), polyhydroxy fatty acid (PHA), polybutylene succinate (PBS), low melting point polyester copolymer.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • PEF polyethylene 2,5-furandicarboxylate
  • PPF polytrimethylene 2,5-furandicarboxylate
  • PBS polybutylene succinate
  • the depolymerization efficiency (E) can be calculated from the amount of solids remaining after the reaction.
  • the calculation formula is as follows:
  • Depolymerization efficiency (E) (polyester fiber content in textile fabric-undepolymerized polyester amount)/polyester fiber content in textile fabric.
  • the organic salt catalyst formed by DBU, imidazole and derivatives thereof is prepared by neutralizing DBU, imidazole and derivatives thereof in equal moles at room temperature.
  • the organic salt ([HDBU][2-EtIm]) formed by DBU and 2-Ethylimidazole (2-Ethylimidazole) as used in the examples is 0.025 mole of DBU and 0.025 mole of 2-Ethylimidazole at room temperature It was prepared after 5 hours of neutralization reaction.
  • the organic salt ([HDBU][BIm]) formed by DBU and benzimidazole (Benzimidazole), the catalyst ([HDBU][BIm]) formed by DBU and 2-methylimidazole (2-methylimidazole) can also be -MeIm]), DBU and 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole) formed catalyst ([HDBU][2-Et-4-MeIm]), and DBU and 2-benzene Catalyst ([HDBU][2-PhIm]) formed from 2-phenylimidazole.
  • the solid portion was extracted with methanol to obtain 8.94g of polyester depolymerized monomer dimethyl terephthalate (DMT) (see Figure 1), and no remaining solids were in the Soxhlet extractor, that is, the polyester fiber was completely Depolymerization.
  • the separated liquid fraction was recovered methanol and acetonitrile by distillation, and ethylene glycol and DBU were recovered by vacuum distillation (see Table 2).
  • the solid part and the liquid part in the reaction system were separated by filtration, and the solid part was subjected to Soxhlet extraction with methanol to obtain 9.35 g of polyester depolymerization monomer DMT, and no remaining solids were in the Soxhlet In the extractor, the polyester fiber is completely depolymerized.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation
  • the solid part was subjected to Soxhlet extraction with methanol, and 8.67 g of polyester depolymerization monomer DMT was isolated to obtain 8.67 g of polyester depolymerization monomer DMT.
  • the polyester fiber was completely depolymerized, and there was no remaining solid in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid part was recovered methanol by distillation, and then benzonitrile, ethylene glycol and DBU were recovered by vacuum distillation (see Table 2).
  • polyester fibers were washed with methanol at 50°C for 30 minutes. During the washing process, 0.1 g of soda ash was added for washing, and the washed fibers were dried at 75° C. for 1 hour. The dried fibers, 6.4g methanol, 1.6g acetonitrile and 0.14g [HDBU][2-EtIm] were added into the reactor, and then the reactor was heated to 90 °C. After reacting for 2 hours, the reactor was cooled to room temperature. The solid part and the liquid part in the reaction system were separated by filtration.
  • the solid part was Soxhlet extracted with methanol to obtain 1.74 g of polyester depolymerization monomer DMT, and no solid remained in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid fraction was recovered by distillation for methanol, acetonitrile, ethylene glycol and extraction for [HDBU][2-EtIm] (see Table 2).
  • the solid part was Soxhlet extracted with methanol to obtain 9.60 g of polyester depolymerization monomer DMT, and there was no remaining solid in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid fraction was recovered methanol and acetonitrile by distillation, and ethylene glycol and DBU were recovered by vacuum distillation (see Table 2).
  • the solid part was Soxhlet extracted with methanol to obtain 8.55 g of polyester depolymerization monomer DMT, and no solid remained in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid part was recovered methanol by distillation, and ethylene glycol, adiponitrile and DBU were recovered by vacuum distillation (see Table 2).
  • the solid part was subjected to Soxhlet extraction with methanol to obtain 8.61 g of polyester depolymerization monomer DMT, and no solid remained in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid fraction was recovered methanol and acetonitrile by distillation, and ethylene glycol and DBU were recovered by vacuum distillation (see Table 2).
  • the solid portion was Soxhlet extracted with methanol to obtain 7.79 g of polyester depolymerization monomer DMT, and no solid remained in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid fraction was recovered methanol and propionitrile by distillation, and ethylene glycol and DBU were recovered by vacuum distillation (see Table 2).
  • the solid part was subjected to Soxhlet extraction with methanol to obtain 8.36 g of polyester depolymerization monomer DMT, and no solid remained in the Soxhlet extractor, that is, the polyester fiber was completely depolymerized.
  • the separated liquid fraction was recovered methanol and acetonitrile by distillation, and ethylene glycol and TBD were recovered by vacuum distillation (see Table 2).
  • the solid portion was subjected to Soxhlet extraction with methanol to obtain 1.71 g of dimethyl furan-2,5-dicarboxylate, a polyester depolymerization monomer (see FIG. 2 ).
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • PHA polylactic acid
  • methanol methanol
  • soda ash 0.2 g
  • the fibers were dried at 75° C. for 1 hour.
  • the dried fibers are added to the reactor.
  • 36 g of methanol, 4 g of acetonitrile and 0.3 g of DBU were added to the reactor.
  • PLA fibers are completely depolymerized.
  • the reacted solution recovered methanol and acetonitrile by distillation, and then recovered 11.31 g of methyl lactate by vacuum distillation.
  • the solid part is subjected to Soxhlet extraction and separation with methanol to obtain cotton fibers.
  • the recoveries of cotton fibers were 98% (reaction temperature at 100°C) and 94% (reaction temperature at 115°C), respectively.
  • the physical properties of the recovered cotton fibers are shown in Table 4.
  • the solid part was subjected to Soxhlet extraction with methanol, and 98.6 g of cotton cloth component and 184.2 g of polyester depolymerization monomer DMT were obtained by separation.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • GB/T2912.3-2009 and GB/T7717.12-94 for the cotton cloth components, and no acetonitrile remains in the cotton fibers as detected by gas chromatography.
  • Cotton fibers are obtained after the recovered cotton cloth components (see Figure 3) are opened by an opener. These recycled cotton fibers are blended with virgin cotton fibers to create recycled yarn. The physical properties of some cotton regenerated yarns are shown in Table 5.
  • the solid part was separated by Soxhlet extraction to obtain 1.16 g of spandex (see Figure 4B and C) and 6.40 g of polyester depolymerized monomer DMT.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • the spandex recovered from the printed blended fabric is pure white, and the spandex filament has not been damaged, and can be directly used as a raw material to produce recycled spandex filament.
  • the solid part was separated by Soxhlet extraction to obtain 1.16 g of spandex and 6.36 g of polyester depolymerization monomer DMT.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • Recycled spandex from black printed blend fabric is ecru.
  • the spandex yarn has not been damaged and can be directly used as a raw material to produce recycled spandex yarn.
  • the solid part was separated by Soxhlet extraction to obtain 5.1 g of wool and 2.64 g of polyester depolymerization monomer DMT.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • the wool after reaction and separation can be recycled and used to produce recycled wool.
  • the separated liquid part recovers methanol and acetonitrile through distillation, and then recovers ethylene glycol and DBU through vacuum distillation.
  • the nylon separated by the reaction is analyzed by infrared spectroscopy and is 100% pure nylon, which can be recycled and used to produce regenerated nylon filaments.
  • polyester fibers 100 g were washed with methanol at 50°C for 30 minutes. During the washing process, 0.2 g of soda ash was added. After washing, the fibers were dried at 75° C. for 1 hour. The dried fibers, 360g of methanol, 40g of acetonitrile and 3g of DBU were added to the reactor, and then the reactor was heated to 95°C, and after 2 hours of reaction, the reactor was cooled to room temperature. The solid part and the liquid part in the reaction system were separated by filtration. The solid part was subjected to Soxhlet extraction with methanol to obtain DMT, a polyester depolymerization monomer.
  • the obtained polyester monomer is catalyzed by antimony trioxide, and is vacuum polymerized at 290°C for 3 hours to form a polyester, and the obtained polyester is repeatedly polymerized, depolymerized and polymerized.
  • the parameters of each depolymerization and polycondensation are as follows: Table 6.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
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Abstract

本发明涉及纺织品的回收再利用，进一步的说一种聚酯混纺面料的循环回收利用方法。将含聚酯的待处理原料处理后在催化剂于40℃-120℃，反应0.5-8小时进行聚酯降解，实现完全解聚，而后分离回收，分离后的聚酯组分和其他混纺组分实现重复利用。本发明方法实现聚酯在低温的条件下100％的解聚，解聚后的聚酯组分可以很容易从其他组分中分离，从而实现混纺面料中聚酯和其他温敏纤维组分完全分离。回收获得的聚酯解聚单体也可用于新的聚酯的合成，从而实现了聚酯混纺废料中不同纤维组分的闭环式循环再利用，这对保护生态环境和降低再生纤维的成本具有重要意义。

Description

一种聚酯混纺面料的循环回收利用方法 技术领域
本发明涉及纺织品的回收再利用，进一步的说一种聚酯混纺面料的循环回收利用方法。
背景技术
聚酯作为全球最流行的纤维材料之一，从2010年起，聚酯纤维一直是全球消耗量最多的纤维。在2020年，全球一年的聚酯产量高达5700万吨。作为纺织纤维，聚酯除了单独使用外，还经常与其他纤维混纺。混纺后的聚酯面料不但具有聚酯面料优良的机械性能，而且明显保留其他纤维面料优秀性能。因此，聚酯的各种混纺面料在服装行业里变得越来越流行。例如，聚酯和棉的混纺面料是休闲服装里最常见的面料之一。这种面料不但具有棉布的舒适性而且兼具了聚酯面料的廉价性。在运动服装里，聚酯与氨纶混纺的面料是最主要的面料。这样的混纺面料不但能保留聚酯纤维的外观和质感，而且有着优良的弹性和穿着舒适性。然而大量的混纺面料制作的衣物在使用后被丢弃。这是由于现有的技术中，缺乏能够将聚酯和其他纤维组分彻底分离的技术。因此每年数以百万吨的聚酯混纺织物被简单地焚烧和填埋。这样的处理方法不仅浪费了大量资源，而且已经对我们生存的环境造成严重的负面影响。如果能用可持续的工艺将聚酯混纺纺织废料回收成高附加值的纺织纤维，这样不仅能够减少因废物处理对环境造成的负面影响，而且能够最大化地利用我们有限的资源。
在现公开的关于聚酯混纺面料的循环回收技术中，化学解聚聚酯法是最主要的方法。然而，在聚酯纤维的解聚过程中，解聚温度通常高达200℃以上(CN106113319A,CN102250379B)，在这种温度下，对温度敏感的组分先于聚酯发生降解，难以实现混纺面料中其他组分的循环利用。专利号US 8,541,477 B2公开了一种低温解聚聚酯的方法，该方法可在120℃以及以上的温度解聚聚酯，然而对温度敏感的组分如氨纶，在120℃的反应条件下开始发粘，分离后的氨纶组分失去弹性，难以在循环利用。专利号WO2021126661A1公开一种在100℃-180℃温度条件下解聚聚酯的方法，然而在此公开的方法中，聚酯在低温的反应条件下(100℃-140℃)不能实100％解聚。这就使得聚酯不能从混纺面料中完全分离，因而导致其他面料组分难以循环利用。而且该方法在低温条件下聚酯单体收率低，也使得回收工艺经济成本较高。因此如何实现聚酯组分在低温条件下的100％解聚且不损害其他组分是实现聚酯混纺面料可循环再利用的关键。
发明内容
本发明的目的在于提供一种聚酯混纺面料的循环回收利用方法。
为实现上述目的，本发明采用技术方案为：
一种聚酯混纺面料的循环回收利用方法，将含聚酯的待处理原料处理后在催化剂于40-120℃，反应0.5-8小时进行聚酯降解，实现完全解聚，而后分离回收，分离后的聚酯组分和其他混纺组分实现重复利用。
所述催化剂为有机碱主催化剂和辅助催化剂，其中，催化剂的添加量为混纺面料质量的0.1-20wt％；有机碱主催化剂和辅助催化剂质量比为1:0.01-100。
所述有机碱主催化剂为含氮元素的脒或胍类的化合物、衍生物中的一种或几种；辅助催化剂为腈类化合物。
所述有机碱主催化剂为a)1,8-二氮杂二环十一碳-7-烯(DBU)，聚合物或化合物负载型DBU，以及DBU与咪唑及其衍生物形成的有机盐；b)1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)，聚合物或化合物负载型TBD，以及TBD与咪唑及其衍生物形成的有机盐；c)1,5-二氮杂二环[4.3.0]壬-5-烯(DBN)，聚合物或化合物负载型DBN，以及DBN与咪唑及其衍生物形成的有机盐。
上述中记载的聚合物或化合物负载型催化剂(以聚合物或化合物负载型DBU为例)为聚苯乙烯负载型DBU(PS-DBU)，活性炭负载型DBU。
形成的有机盐(以DBU与咪唑及其衍生物形成的有机盐为例)为DBU与咪唑(Imidazole)形成的有机盐([HDBU][Im]),DBU与2-乙基咪唑(2-Ethylimidazole)形成的有机盐([HDBU][2-EtIm]),DBU与苯并咪唑(Benzimidazole)形成的有机盐([HDBU][BIm]),DBU与2-甲基咪唑(2-methylimidazole)形成的有机盐([HDBU][2-MeIm]),DBU与2-乙基-4-甲基咪唑(2-Ethyl-4-Methylimidazole)形成的有机盐([HDBU][2-Et-4-MeIm]),以及DBU与2-苯基咪唑(2-Phenylimidazole)形成的有机盐([HDBU][2-PhIm])。
所述辅助催化剂为乙腈，丙腈，苯甲腈，己二腈一种或几种。
优选，所述方法：将含聚酯的待处理原料处理后加入至甲醇溶液中，而后添加催化剂于60-110℃，反应1-5小时进行聚酯降解，实现完全解聚，而后分离回收分离聚酯组分重复利用。
进一步优选，所述方法：将含聚酯的待处理原料处理后加入至甲醇溶液中，而后添加催化剂于80-110℃，反应1-2小时进行聚酯降解，实现完全解聚，而后分离回收分离聚酯组分重复利用。
所述含聚酯的待处理原料为聚酯混纺面料或聚酯和其他面料的混合面料；其中，混合面料中聚酯的含量5％-100％；所述聚酯混纺面料为氨纶、棉、粘胶纤维、再生纤维素纤维、尼龙、羊毛、羊绒、真丝中的一种或几种与聚酯混纺所得面料。
上述混纺面料中，聚酯的含量至少5％，或者至少25％，或者至少50％，或者至少75％，或者至少95％。
所述含聚酯的待处理原料为将原料于40-130℃下经醇或含醇的混合体系中洗涤0.3-2小时；其中，含醇的混合体系为醇和碱性化合物混合，所述碱性化合物纯碱(Na 2CO 3),醋酸钠，甲醇钠，乙醇钠，碳酸钾，醋酸钾，甲醇钾，氧化钙，氢氧化钙的一种或几种。
进一步的说，将原料于50-110℃或80-100℃或90-100℃下经醇或含醇的混合体系中洗涤0.3-2小时，去除原料中附带的污渍，油渍以及其他杂质。
所述聚酯降解后固液分离，收集固体经索式提取分离聚酯组分和其他纤维组分；液体经过常压蒸馏回收醇和辅助催化剂，再经过真空蒸馏或者萃取回收聚酯的二元醇和二元酸单体，以及有机碱催化剂上述聚酯解聚后回收的单体如对苯二甲酸二甲酯(DMT)和乙二醇可经真空蒸馏提纯后作为原料合成新聚酯。
本发明作用原理：
在有机碱主催化剂催化甲醇醇解聚酯过程中，有机碱主催化剂首先活化甲醇，使甲醇生成亲核性强的甲醇阴离子，如下图
Figure PCTCN2022104576-appb-000001
形成的甲醇阴离子更容易通过亲核反应攻击酯键，从而实现酯键的断裂。但是，有机碱主催化剂活化甲醇的反应是可逆的。当反应体系中加入腈化物(R-C≡N：)后，-C≡N：的强极性以及氮原子上的孤对电子使反应生成的有机碱主催化剂阳离子在体系中稳定，使反应平衡向产生更多甲醇阴离子方向移动，从而提高有机碱主催化剂的催化活性。
本发明所具有的优点：
本发明方法实现聚酯在低温的条件下100％的解聚。解聚后的聚酯组分可以很容易从其他组分中分离，从而实现混纺面料中聚酯和其他温敏纤维组分完全分离。而且，本发明中的反应分离过程温和且高效，其他纤维能够得到100％纯组分并且纤维几乎没有受到破坏，可以直接再纺成丝线或作为原料生产再生纤维。回收获得的聚酯解聚单体也可用于新的聚酯的合成，从而实现了聚酯混纺废料中不同纤维组分的闭环式循环再利用，这对保护生态环境和降低再生纤维的成本具有重要意义。
本发明分离过程中使用有机碱性催化剂来催化聚酯酯键断裂，为了提高有机碱在低温条件下的催化活性和效率，体系过程中加入辅助催化剂，有机碱在辅助催化剂的配合下，实现了聚酯在低温条件的100％解聚反应，并且，在加入辅助催化剂后，聚酯单体的回收率显著提高。
附图说明
图1为本发明实施例提供的解聚后回收的聚酯单体对苯二甲酸二甲酯(DMT)的红外光谱图(FTIR)
图2为本发明实施例提供的解聚后回收的聚酯单体呋喃-2,5-二甲酸二甲酯的红外光谱图(FTIR)
图3为本发明实施例提的分离回收聚酯和棉花混纺面料；其中，A为分离反应前混纺面料；B为分离反应后，纯棉面料
图4为本发明实施例提的分离回收聚酯和氨纶混纺印花面料；其中，A为分离反应前混纺面料；B为分离反应后，纯氨纶面料；C为光学显微镜下显示氨纶丝没有受到破坏。
具体实施方式
以下结合实例对本发明的具体实施方式做进一步说明，应当指出的是，此处所描述的具体实施方式只是为了说明和解释本发明，并不局限于本发明。
本发明方法在更低的温度条件下实现聚酯纤维组分的100％解聚，而且聚酯单体回收率高达95％，从而能更高效的回收和再生聚酯。更低反应温度使工艺过程更环境友好，而且降低的反应所需的能量，从而使回收的工艺成本更低。
本发明旨在回收再利用温度敏感纤维与聚酯混纺的废料。比如，氨纶与聚酯混纺面料，棉与聚酯混纺面料，粘胶纤维与聚酯的混纺面料，再生纤维素纤维与聚酯的混纺面料，尼龙与聚酯的混纺面料，羊毛与聚酯的混纺面料,羊绒与聚酯混纺面料，真丝与聚酯混纺面料，以及这些纤维的面料与聚酯面料的混合面料的回收利用。这里的再生纤维素纤维可以是莫代尔纤维和莱赛尔纤维。
上述聚酯解聚是指聚酯降解成为单体和小分子的低聚物，如二聚体，三聚体，四聚体，五聚体，六聚体，七聚体等，从而从混纺面料脱落分离，进而实现聚酯组分的分离和回收。该技术中的聚酯是含有酯化学键的聚合物，如聚对苯二甲酸乙二醇酯(PET)，聚对苯二甲酸丙二醇酯(PTT)，聚对苯二甲酸丁二醇酯(PBT)，聚2,5-呋喃二甲酸乙二醇酯(PEF)，聚2,5-呋喃二甲酸丙二醇酯(PTF)，聚2,5-呋喃二甲酸丁二醇酯(PBF)，聚乳酸酯(PLA)，聚羟基脂肪酸(PHA)，聚丁二醇丁二酸酯(PBS)，低熔点聚酯共聚物。
解聚效率(E)可以从反应后剩余的固体量计算。该计算式如下:
解聚效率(E)＝(纺织面料中聚酯纤维含量-未解聚的聚酯量)/纺织面料中聚酯纤维含量。
下述实施例中有机盐催化剂的制备：
制备DBU与咪唑及其衍生物形成的有机盐催化剂：
DBU与咪唑及其衍生物形成的有机盐催化剂是等摩尔数的DBU和咪唑及其衍生物在室温条件下进行中和反应制得。如实施例使用的DBU与2-乙 基咪唑(2-Ethylimidazole)形成的有机盐([HDBU][2-EtIm])是0.025摩尔的DBU和0.025摩尔的2-乙基咪唑在室温的条件下中和反应5小时后制得的。
同时，按照上述方式还可将DBU与苯并咪唑(Benzimidazole)形成的有机盐([HDBU][BIm])，DBU与2-甲基咪唑(2-methylimidazole)形成的催化剂([HDBU][2-MeIm]),DBU与2-乙基-4-甲基咪唑(2-ethyl-4-methylimidazole)形成的催化剂([HDBU][2-Et-4-MeIm]),以及DBU与2-苯基咪唑(2-phenylimidazole)形成的催化剂([HDBU][2-PhIm])。
实施例1
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与20g甲醇，20g乙腈和2g DBU加入到反应釜中,然后反应釜加热到65℃。反应8小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到8.94g聚酯解聚单体对苯二甲酸二甲酯(DMT)(参见图1)，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU(参见表2)。
实施例2
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与28g甲醇，12g不同辅助催化剂和0.54g DBU加入到反应釜中,然后反应釜加热到85℃。反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行经过索式提取，得到聚酯解聚单体DMT，而索式提取器中剩余固体即为未解聚聚酯纤维(参见表1)。
采用乙腈作为辅助催化剂解聚后，通过过滤将反应体系中的固体部分和液体部分分离，固体部分使用甲醇进行索式提取，得到9.35g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU
(参见表2)。
表1 在低温反应条件下不同辅助催化剂对DBU催化降解聚酯的活性比较
Figure PCTCN2022104576-appb-000002
Figure PCTCN2022104576-appb-000003
实施例3
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与28g甲醇，12g苯甲腈和0.54g DBU加入到反应釜中,然后反应釜加热到85℃。反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行经过索式提取，分离得到8.67g聚酯解聚单体DMT，聚酯纤维完全解聚，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇，再通过真空蒸馏回收苯甲腈，乙二醇和DBU(参见表2)。
实施例4
2g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与6.4g甲醇,1.6g乙腈和0.14g[HDBU][2-EtIm]加入到反应釜中,然后反应釜加热到90℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到1.74g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇，乙腈，乙二醇以及萃取回收[HDBU][2-EtIm](参见表2)。
实施例5
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与36g甲醇，4g乙腈和0.3g DBU加入到反应釜中,然后反应釜加热到95℃，反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到9.60g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU(参见表2)。
实施例6
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与36g甲醇，4g己二腈和0.3g DBU加入到反应釜中,然后反应釜加热到95℃，反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到8.55g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇，再通过真空蒸馏回收乙二醇，己二腈和DBU(参见表2)。
实施例7
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与28g甲醇，12g乙腈和0.18g DBU加入到反应釜中,然后反应釜加热到115℃，反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到8.61g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU(参见表2)。
实施例8
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与28g甲醇，12g丙腈和0.18g DBU加入到反应釜中,然后反应釜加热到115℃，反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到7.79g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和丙腈，再通过真空蒸馏回收乙二醇和DBU(参见表2)。
实施例9
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与28g甲醇，12g乙腈和0.18g TBD加入到反应釜中,然后反应釜加热到115℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到8.36g聚酯解聚单体DMT，无剩余固体物在索式提取器中，即聚酯纤维完全解聚。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和TBD(参见表2)。
对比实施例1
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与40g甲醇和2g DBU加入到反应釜中,然后反应釜加热到65℃。反应8小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到2.81g聚酯解聚单体DMT。同时索式提取器中还剩余4.55g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇和DBU(参见表2)。
对比实施例2
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与40g甲醇和0.54g DBU加入到反应釜中,然后反应釜加热到85℃。反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到3.99g聚酯解聚单体DMT。同时索式提取器中还剩余5.07g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇和DBU(参见表2)。
对比实施例3
2g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与8g甲醇和0.14g[HDBU][2-EtIm]加入到反应釜中,然后反应釜加热到90℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到0.91g聚酯解聚单体DMT。同时，索式提取器中还剩余0.75g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇以及萃取回收[HDBU][2-EtIm](参见表2)。
对比实施例4
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与40g甲醇和0.3g DBU加入到反应釜中,然后反应釜加热到95℃。反应2.5小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到5.41g聚酯解聚单体DMT。同时，索式提取器中还剩余3.48g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇和DBU(参见表2)。
对比实施例5
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与40g甲醇和0.18g DBU加入到反应釜中,然后反应釜加热到115℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到4.94g聚酯解聚单体DMT。同时，索式提取器中还剩余3.25g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇和DBU(参见表2)。
对比实施例6
10g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱洗涤，洗涤后纤维在75℃干燥1小时。干燥后的纤维与40g甲醇和0.18g TBD加入到反应釜中,然后反应釜加热到115℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，分离得到4.69聚酯解聚单体DMT。同时，索式提取器中还剩余3.61g未解聚的聚酯纤维。分离后的液体部分通过蒸馏回收甲醇，乙二醇和TBD(参见表2)。
表2 在辅助催化剂条件下的实施例与无辅助催化剂的对比实施例在解聚效率和DMT单体回收率的对比。
Figure PCTCN2022104576-appb-000004
Figure PCTCN2022104576-appb-000005
实施例10
2g聚酯纤维在60℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维与6.4g甲醇，1.6g乙腈和0.21g[HDBU][BIm]加入到反应釜中,然后反应釜加热到95℃。反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取分离1.82g聚酯解聚单体DMT，无剩余固体物在索式提取器中。分离后的液体部分通过蒸馏回收甲醇，乙二醇以及萃取回收[HDBU][BIm](参见表3)。
实施例11-13
具体实施步骤和反应条件与实施例7相同，只是反应主催化剂进行替换实施例8-9助催化剂依次分别是[HDBU][2-MeIm],[HDBU][2-Et-4-MeIm],[HDBU][2-PhIm],实验结果见表3。
表3 实施例11-13中聚酯解聚率和DMT单体回收率
Figure PCTCN2022104576-appb-000006
实施例14
2g聚2,5-呋喃二甲酸乙二醇酯(PEF)纤维在60℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维加入反应釜。同时在反应釜加入7.2g甲醇，0.8g乙腈和0.06g DBU。然后将反应釜加热到110℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到1.71g聚酯解聚单体呋喃-2,5-二甲酸二甲酯(参见图2)。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。
实施例15
10g聚乳酸(PLA)纤维在60℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维加入反应釜。同时在反应釜加入36g甲醇，4g乙腈和0.3gDBU。然后将反应釜加热到100℃，反应2小时后.反应结束后，将反应釜冷却至室温。PLA纤维完全解聚。反应后的溶液通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收到11.31g乳酸甲酯。
实施例16
2g聚酯纤维和2g棉花纤维在60℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维加入反应釜。同时在反应釜加入9.2g甲醇，0.8g乙腈和0.45g DBU。然后将反应釜加热到不同温度(100-115℃)，分别反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。聚酯纤维完全解聚。固体部分经过甲醇进行索式提取分离得到棉花纤维。棉花纤维的回收率分别是98％(反应温度在100℃)和94％(反应温度在115℃)。回收后的棉花纤维的物理性能见表4。
对比例7
2g聚酯纤维和2g棉花纤维在60℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.1g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维加入反应釜。同时在反应釜加入10甲醇和0.45g DBU。然后将反应釜加热到不同温度(190-240℃)，分别反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。聚酯纤维完全解聚。固体部分经过甲醇进行索式提取分离棉花纤维和聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。回收后的棉花纤维的物理性能见表4。
表4 不同反应温度下实施例与对比例回收棉花纤维的物理性能
Figure PCTCN2022104576-appb-000007
实施例17
200g聚酯和棉花混纺面料(棉含量为50％)在100℃下用甲醇洗涤45分钟。在洗涤过程中，加入4g Na 2CO 3.洗涤完的面料在75℃干燥1小时。燥后的混纺面料加入反应釜。同时在反应釜加入，752g甲醇，48g乙腈和5gDBU。然后将反应釜加热到110℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过甲醇进行索式提取，分离得到98.6g棉布组分和184.2g聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。棉布组分参见GB/T2912.3-2009和GB/T7717.12-94，由气相色谱法检测，无乙腈残留在棉纤维中。回收后的棉布组分(参见图3) 经过开松机开松后得到棉花纤维。这些回收的棉花纤维与新棉花纤维混纺后制成再生纱线。其中部分棉花再生纱线的物理性能见表5。
表5 反应分离聚酯组分后的回收棉组再生成纱线的力学性能
Figure PCTCN2022104576-appb-000008
实施例18
8g聚酯和氨纶混纺印花面料(氨纶含量为15％)在85℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.08g醋酸钠和0.08g氧化钙.洗涤完的面料在45℃真空干燥1小时。干燥后的混纺面料(参见图4A)加入反应釜。同时在反应釜加入，28.8g甲醇，3.2g乙腈和0.4g DBU。然后将反应釜加热到90℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取分离得到1.16g的氨纶(参见图4B和C)和6.40g聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。
由图4可见从印花混纺面料回收到的氨纶为纯白色的，而且氨纶丝没有受到破坏，可以作为原料直接用于生产再生氨纶丝。
对比例8
8g聚酯和氨纶混纺印花面料(氨纶含量为15％)在85℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.08g醋酸钠和0.08g氧化钙.洗涤完的面料在45℃真空干燥1小时。干燥后的混纺面料(参见图如14A)加入反应釜。同时在反应釜加入，32g甲醇和0.4g DBU。然后将反应釜加热到125℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取只得到6.67g聚酯解聚单体DMT，无氨纶组分。氨纶在此反应温度已经完全降解，无法循环再回收利用。
实施例19
8g聚酯和氨纶混纺染色面料(黑色，氨纶含量为15％)在85℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.08g醋酸钠和0.08g氧化钙.洗涤完的面料在45℃真空干燥1小时。燥后的混纺面料加入反应釜。同时在反应釜加入，28.8g甲醇，3.2g乙腈和0.4gDBU。然后将反应釜加热到90℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取分离得到1.16g的氨纶和6.36g聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。从黑色印花混纺面料 回收到的氨纶为淡褐色。氨纶丝没有受到破坏，可以作为原料直接用于生产再生氨纶丝。
实施例20
8g聚酯和羊毛混纺面料(羊毛含量为65％)在85℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.08g醋酸钠和0.08g氧化钙.洗涤完的面料在65℃真空干燥1小时。燥后的混纺面料加入反应釜。同时在反应釜加入，30g甲醇，2g乙腈和0.61g DBU。然后将反应釜加热到95℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取分离得到5.1g的羊毛和2.64g聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。反应分离后的羊毛，可循环再利用，用于生产再生羊毛。
实施例21
5g尼龙面料和5g聚酯面料在95℃下用甲醇洗涤45分钟。在洗涤过程中，加入0.08g碳酸钠和0.08g氧化钙.洗涤完的面料在95℃真空干燥1小时。燥后的混合面料加入反应釜。同时在反应釜加入，36g甲醇，4g乙腈和0.3g DBU。然后将反应釜加热到100℃，反应2小时后.反应结束后，将反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分经过索式提取分离得到4.91g的尼龙面料和4.71g聚酯解聚单体DMT。分离后的液体部分通过蒸馏回收甲醇和乙腈，再通过真空蒸馏回收乙二醇和DBU。反应分离后的尼龙经红外光谱分析，为100％纯尼龙，可循环再利用，用于生产再生尼龙丝。
实施例22
100g聚酯纤维在50℃下用甲醇洗涤30分钟。在洗涤过程中，加入0.2g纯碱.洗涤后纤维在75℃干燥1小时。干燥后的纤维与360g甲醇，40乙腈和3g DBU加入到反应釜中,然后反应釜加热到95℃，反应2小时后，反应釜冷却至室温。通过过滤将反应体系中的固体部分和液体部分分离。固体部分使用甲醇进行索式提取，得到聚酯解聚单体DMT。得到的聚酯单体用三氧化二锑为催化剂，在290℃的条件下真空聚合3小时，生成聚酯，得到聚酯重复多次聚解聚和聚合，每次解聚和缩聚的参数如表6。
表6 聚酯解聚单体多次重复聚合和解聚的参数
Figure PCTCN2022104576-appb-000009

Claims (8)

  1. 一种聚酯混纺面料的循环回收利用方法，其特征在于：将含聚酯的待处理原料处理后在催化剂于40℃-120℃，反应0.5-8小时进行聚酯降解，实现完全解聚，而后分离回收，分离后的聚酯组分和其他混纺组分实现重复利用。
  2. 按权利要求1所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述催化剂为有机碱主催化剂和辅助催化剂，其中，催化剂的添加量为混纺面料质量的0.1-20wt％；有机碱主催化剂和辅助催化剂质量比为1:0.01-100。
  3. 按权利要求2所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述有机碱主催化剂为含氮元素的脒或胍类的化合物、衍生物中的一种或几种；辅助催化剂为腈类化合物。
  4. 按权利要求3所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述有机碱主催化剂为a)1,8-二氮杂二环十一碳-7-烯(DBU)，聚合物或化合物负载型DBU，以及DBU与咪唑及其衍生物形成的有机盐；b)1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)，聚合物或化合物负载型TBD，以及TBD与咪唑及其衍生物形成的有机盐；c)1,5-二氮杂二环[4.3.0]壬-5-烯(DBN)，聚合物或化合物负载型DBN，以及DBN与咪唑及其衍生物形成的有机盐。
  5. 按权利要求3所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述辅助催化剂为乙腈，丙腈，苯甲腈，己二腈一种或几种。
  6. 按权利要求1所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述含聚酯的待处理原料为聚酯混纺面料或聚酯和其他面料的混合面料；其中，待处理原料中聚酯的含量5％-100％；所述聚酯混纺面料为氨纶、棉、粘胶纤维、再生纤维素纤维、尼龙、羊毛、羊绒、真丝中的一种或几种与聚酯混纺所得面料。
  7. 按权利要求1所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述含聚酯的待处理原料为将原料于40-130℃下经醇或含醇的混合体系中洗涤0.3-2小时；其中，含醇的混合体系为醇和碱性化合物混合，所述碱性化合物纯碱(Na 2CO 3),醋酸钠，甲醇钠，乙醇钠，碳酸钾，醋酸钾，甲醇钾，氧化钙，氢氧化钙的一种或几种。
  8. 按权利要求1所述的聚酯混纺面料的循环回收利用方法，其特征在于：所述聚酯降解后固液分离，收集固体经索式提取分离聚酯组分和其他纤维组分；液体经过常压蒸馏回收醇和辅助催化剂，再经过真空蒸馏或者萃取回收聚酯的二元醇和二元酸单体，以及有机碱催化剂。
PCT/CN2022/104576 2022-02-18 2022-07-08 一种聚酯混纺面料的循环回收利用方法 Ceased WO2023155367A1 (zh)

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