WO2025007970A1 - 可降解高分子材料的再生处理方法及应用 - Google Patents

可降解高分子材料的再生处理方法及应用 Download PDF

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WO2025007970A1
WO2025007970A1 PCT/CN2024/103994 CN2024103994W WO2025007970A1 WO 2025007970 A1 WO2025007970 A1 WO 2025007970A1 CN 2024103994 W CN2024103994 W CN 2024103994W WO 2025007970 A1 WO2025007970 A1 WO 2025007970A1
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degradation
degradable polymer
polymer material
molecular weight
phosphate
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French (fr)
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俞麟
吴婉华
吴凯婷
丁建东
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Fudan University
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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
    • 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
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0257—Phosphorus acids or phosphorus acid esters
    • B01J31/0258—Phosphoric acid mono-, di- or triesters ((RO)(R'O)2P=O), i.e. R= C, R'= C, H
    • 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
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0264—Phosphorus acid amides
    • B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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 present application relates to the technical field of polymer material recycling, and in particular to a method for regenerating and treating degradable polymer materials and its application.
  • Degradable polymer materials have received widespread attention due to their inherent characteristics of being degradable under specific conditions, especially polylactic acid, polycaprolactone, polybutylene adipate/terephthalate, etc.
  • environmentally friendly materials they have replaced some traditional polymer materials (polyethylene terephthalate, polyvinyl chloride, polypropylene, etc.) in the market and are widely used in packaging and medicine, etc., in order to reduce the pollution caused by polymer materials to the environment.
  • the natural degradation rate of degradable polymer materials is slow. It takes two to three years to degrade to a low molecular state in the ocean and soil. Even under industrial composting conditions, it takes about half a year to completely degrade. The uneven natural degradation rate of degradable polymer materials will form broken plastic particles rather than oligomers. The microplastic problem caused is even more serious than that of petroleum-based plastics. Not only can the recycling of resources not be achieved, but it will also cause secondary pollution to the environment. At the same time, traditional recycling methods such as thermal cracking, alcoholysis and hydrolysis have harsh processing conditions, small single processing volume and slow processing speed. The degradation products need to undergo cumbersome purification steps before they can be effectively reused.
  • the purpose of the present application includes providing a regeneration method for degradable polymer materials, using a specific catalyst with low cost to achieve efficient degradation of degradable polymer materials, the method not only has a fast degradation rate, but also a high conversion rate and a high reaction yield.
  • the present application also provides an application using the regeneration method.
  • a method for regenerating a degradable polymer material is provided.
  • a method for regenerating a degradable polymer material comprising the following steps: degrading the degradable polymer material in a system in which an organic non-metallic catalyst and an aqueous solvent exist to obtain a degradation product;
  • the degradable polymer material includes one or more of polyester material and polycarbonate material
  • the organic non-metal catalyst is selected from one or more of diphenyl phosphate, binaphthol phosphate and organic bases, and the organic base is selected from one or more of nitrogen-containing heterobicyclic bases, 4-dimethylaminopyridine and phosphazene base compounds.
  • the diphenyl phosphate has a structure shown in formula (I):
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently selected from any one of -H, halogen, -NO 2 , -CN, C 1 ⁇ C 4 alkoxy, C 1 ⁇ C 6 alkyl, halogen-substituted C 1 ⁇ C 6 alkyl, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of -NO 2 , -CN, halogen and C 1 ⁇ C 4 alkyl;
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently selected from any one of -H, halogen, -NO 2 , C 1 ⁇ C 4 alkoxy, C 1 ⁇ C 6 alkyl, halogen-substituted C 1 ⁇ C 6 alkyl, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of halogen and C 1 ⁇ C 4 alkyl;
  • the binaphthol phosphate has a structure shown in formula (II):
  • R 3 and R 3 ' can be independently selected from -H, -SiPh 3 or Wherein, “*” indicates the attachment site of a covalent single bond;
  • R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from any one of -H, halogen, -NO 2 , -CN, C 1 ⁇ C 6 alkyl, halogen-substituted C 1 ⁇ C 6 alkyl, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , -CN, phenyl and C 1 ⁇ C 4 alkyl; or at least two of R 41 , R 42 , R 43 , R 44 and R 45 form a ring and participate in forming a condensed ring, and the non-annular groups in R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from -H, halogen, -NO 2 , -CN, C 1 ⁇ C 6 alkyl, halogen-substit
  • R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from any one of -H, halogen, -NO 2 , C 1 to C 6 alkyl, halogen-substituted C 1 to C 6 alkyl, phenyl, and substituted phenyl, and the phenyl ring in the substituted phenyl is substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , phenyl and C 1 to C 4 alkyl; or at least two of R 41 , R 42 , R 43 , R 44 and R 45 form a ring and participate in forming a condensed ring, and the non-annular groups in R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from -H, halogen, -NO 2 , C 1 to C 6 alkyl, halogen-substituted C 1 to C 6 alkyl, 6 alkyl
  • the nitrogen-containing heterobicyclic base is selected from the group consisting of:
  • Y is -CH 2 -, -NH- or -N(CH 3 )-; n is 1 or 2;
  • the phosphazene base compound has a structure shown in formula (IV):
  • R is halogen, C 1 ⁇ C 4 alkyl or C 1 ⁇ C 4 alkoxy.
  • the regeneration method satisfies one or more of the following characteristics:
  • the number average molecular weight of the degradable polymer material is 10 kDa to 250 kDa;
  • the mass ratio of water to the degradable polymer material in the system is (0.01-10):1;
  • the mass ratio of the organic non-metallic catalyst to the degradable polymer material is (0.001-0.1):1;
  • the average degree of polymerization of the degradation product is ⁇ 20.
  • the regeneration method satisfies one or more of the following characteristics:
  • the degradable polymer material is selected from polylactic acid, polyglycolic acid, poly ⁇ -caprolactone, polylactic acid-glycolic acid copolymer, polyglycolic acid- ⁇ -caprolactone copolymer, polylactic acid- ⁇ -caprolactone copolymer, poly ⁇ -valerolactone, polybutyrolactone, polybutylene succinate, One or more of polybutylene adipate/terephthalate, polybutylene succinate/adipate, polyhydroxyalkanoate and polytrimethylene carbonate;
  • the degradable polymer material is selected from one or more of polylactic acid, polyglycolic acid, poly ⁇ -caprolactone, polylactic acid-glycolic acid copolymer, polyglycolic acid- ⁇ -caprolactone copolymer, polylactic acid- ⁇ -caprolactone copolymer, poly ⁇ -valerolactone, polybutyrolactone, polybutylene succinate, polybutylene adipate/terephthalate, polyhydroxyalkanoate and polytrimethylene carbonate;
  • the diphenyl phosphate catalyst is selected from one or more of diphenyl phosphate, bis(4-nitrophenyl) phosphate, bis(4-fluorophenyl) phosphate, bis(4-trifluoromethylphenyl) phosphate, bis(4-chlorophenyl) phosphate, bis(4-methoxyphenyl) phosphate and bis(4-methylphenyl) phosphate;
  • the diphenyl phosphate catalyst is selected from one or more of diphenyl phosphate, bis(4-nitrophenyl)phosphate and bis(2,6-dimethylphenyl)phosphate;
  • the binaphthol phosphate catalyst is selected from one or more of binaphthol phosphate, R-binaphthol phosphate, R-3,3'-bis(triphenylsilyl)binaphthol phosphonate and R-3,3'-bis(2,4,6-triisopropylphenyl)binaphthol phosphonate;
  • the organic base catalyst is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 4-dimethylaminopyridine, tert-butylimino-tris(dimethylamino)phosphorane, 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2 ⁇ 5,4 ⁇ 5-bis(phosphorus nitrogen-based compound) and cyclotriphosphazene base and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2 ⁇ 5,4 ⁇ 5-bis(phosphorus nitrogen-based compound) One or more.
  • the regeneration method comprises the following steps: performing a first degradation treatment on the first degradable polymer material in a system in which the organic non-metallic catalyst and the aqueous solvent exist to obtain a first degradation product;
  • the regeneration method satisfies one or more of the following characteristics:
  • the temperature of any degradation treatment is independently 125°C to 200°C;
  • the time of any degradation treatment is independently 0.1h to 5h, and can be optionally 0.25h to 5h;
  • the pressure of any degradation treatment is independently 1 atm-100 atm.
  • the pressure of any degradation treatment is independently 100 ⁇ 5 kPa.
  • the regeneration method further includes the following steps: washing the degradation product with an organic solvent; wherein the organic solvent is selected from one or more of chloroform, petroleum ether, carbon disulfide, ether, dichloromethane, benzene, toluene and ethyl acetate.
  • organic solvent is selected from one or more of chloroform, petroleum ether, carbon disulfide, ether, dichloromethane, benzene, toluene and ethyl acetate.
  • the second aspect of the present application provides a low molecular weight composition, which is a degradation product of a degradable polymer material, and the low molecular weight composition is prepared according to the regeneration method described in the first aspect, wherein the average degree of polymerization of the low molecular weight composition is ⁇ 20.
  • the third aspect of the present application provides a method for recycling degradable polymer materials, comprising the following steps: conducting a polymerization reaction using a low molecular weight composition as an initial raw material; wherein the low molecular weight composition is a degradation product prepared by the regeneration method described in the first aspect or the low molecular weight composition described in the second aspect.
  • organic non-metallic catalyst and the degradable polymer material are as defined in the first aspect.
  • FIG. 1 is a 1 H NMR spectrum of the sample product in Example 1 of the present application after being washed with chloroform and before being washed.
  • Figure 2 is an optical photograph of the residues of the polylactic acid film disc of Experiment A1 of the present application at the 8th hour (8h), 16th hour (16h), 24th hour (24h), 32nd hour (32h), 48th hour (48h) and 72nd hour (72h) after the start of the reaction.
  • DPP diphenyl phosphate
  • FIG4 shows the change of the peak molecular weight (M peak ) of the reaction system over time in some examples of the present application; wherein, the reaction system of test A6 is polylactic acid pellets (pre-crushed to a diameter ⁇ 1 mm), diphenyl phosphate DPP (the mass ratio of DPP to polylactic acid pellets is 5%), the reaction temperature is 160° C. oil bath, 2 drops of deionized water are added every 5 minutes, and the reaction is carried out for 0.5 hours; the difference between test A7 and test A6 is that no diphenyl phosphate DPP is added.
  • the reaction system of test A6 is polylactic acid pellets (pre-crushed to a diameter ⁇ 1 mm), diphenyl phosphate DPP (the mass ratio of DPP to polylactic acid pellets is 5%), the reaction temperature is 160° C. oil bath, 2 drops of deionized water are added every 5 minutes, and the reaction is carried out for 0.5 hours; the difference between test A7 and test A6 is that no
  • Figure 5 is a degradation test conducted with different polymer materials as substrates; wherein, Figure A is a photograph of the plastic before the reaction with a mixed plastic (polyethylene terephthalate PET + polypropylene PP + polyethylene PE + polylactic acid PLA) as the substrate; Figures B and C are photographs of the degradation product (B in the figure) and the undegraded plastic (C in the figure) obtained after the aforementioned mixed plastic is reacted as a substrate; Figures D, E and F are the DSC curves of polyethylene terephthalate PET, polypropylene PP and polyethylene PE in the reaction substrate (mixed plastic) before and after treatment, respectively, and Tm is the melting point.
  • a mixed plastic polyethylene terephthalate PET + polypropylene PP + polyethylene PE + polylactic acid PLA
  • Figures B and C are photographs of the degradation product (B in the figure) and the undegraded plastic (C in the figure) obtained after the aforementioned mixed plastic is reacted as a substrate
  • Alkyl refers to the part of a hydrocarbon with single bonds between carbon atoms and between carbon atoms and between carbon atoms and hydrogen atoms removed. Phrases containing this term, for example, "C 1 -C 6 alkyl” refers to an alkyl group containing 1 to 6 carbon atoms, and each occurrence can be independently C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl or C 6 alkyl.
  • Suitable examples include, but are not limited to, ethyl (Et, —CH 2 CH 3 ), 1-propyl (n-Pr, n-propyl, —CH 2 CH 2 CH 3 ), 1-methylethyl (i-Pr, i-propyl, —CH(CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, —CH 2 CH 2 CH 2 CH 3 ), 1-methylpropyl (s-Bu, s-butyl, —CH(CH 3 )CH 2 CH 3 ), 2-methylpropyl (i-Bu, i-butyl, —CH 2 CH(CH 3 ) 2 ), 1,1-dimethylethyl (t-Bu, t-butyl, —C(CH 3 ) 3 ), 1-pentyl (n-pentyl, —CH 2 CH 2 CH 2 CH 3 ), 1-methylbutyl (—CH(CH 3 )CH 2 CH 2 CH 3 ), 1-
  • Alkoxy refers to a group having an -O-alkyl group, i.e., an alkyl group as defined above connected to the main chain structure via an oxygen atom.
  • C 1 -C 4 alkoxy means that the alkyl portion contains 1 to 4 carbon atoms, and each occurrence can be independently C 1 alkoxy, C 2 alkoxy, C 3 alkoxy or C 4 alkoxy. Suitable examples include, but are not limited to, methoxy (-O-CH 3 or -OMe), ethoxy (-O-CH 2 CH 3 or -OEt) and tert-butoxy (-OC(CH 3 ) 3 or -Ot-Bu).
  • Halogen or "halo” refers to -F, -Cl, -Br or -I.
  • Phenyl refers to -C 6 H 5 ; an alkyl-substituted phenyl group includes a phenyl group substituted by an alkyl group at least at one site.
  • the distribution of the optional numerical values in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints.
  • the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer.
  • the numerical range disclosed herein should be understood to include any and all sub-ranges included therein.
  • the "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc.
  • “Numerical interval” allows for broadly including quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.
  • substantially and “approximately” used herein are used to describe the allowable small fluctuations in numerical values. It should be understood that as long as the numerical range is within the allowed fluctuation range, it is within the semantic scope of "substantially” or “approximately”. For example, “substantially” and “approximately” cover the situation of no fluctuation. For example, they can refer to less than or equal to ⁇ 5%, such as less than or equal to ⁇ 2%, such as less than or equal to ⁇ 1%, such as less than or equal to ⁇ 0.5%, such as less than or equal to ⁇ 0.2%, such as less than or equal to ⁇ 0.1%, such as less than or equal to ⁇ 0.05%.
  • the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions of the listed features.
  • the temperature parameters in this application are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ⁇ 5°C, ⁇ 4°C, ⁇ 3°C, ⁇ 2°C, and ⁇ 1°C are allowed.
  • biodegradable polyester and polycarbonate materials represented by polylactic acid.
  • these biodegradable materials can be degraded under certain conditions, they usually require professional industrial composting conditions, and the materials currently in use far exceed the processing capacity of existing industrial composting plants.
  • the material degradation cycle is usually 3 to 6 months, and the materials and degradation products are directly discharged into the natural environment, making it impossible to recycle and reuse resources.
  • biodegradable polymer materials such as polylactic acid, polycaprolactone, polybutylene succinate, polybutylene adipate/terephthalate, etc., degrade very slowly under natural conditions and will not undergo significant changes in morphology even if left in the air for a year. Effective degradation of biodegradable polymer materials requires human intervention.
  • thermal cracking In order to better realize the treatment and recycling of degradable polymer materials, chemical recovery can be selected, and methods such as thermal cracking, alcoholysis and hydrolysis can be generally selected.
  • the thermal cracking method has high reaction temperature, low yield of target product, more side reactions and easy racemization of product, and it is difficult to obtain high-purity products.
  • Alcoholysis method is usually to treat waste materials with low alkyl alcohol or ethylene glycol under the action of catalyst to recycle hydroxy acids or esters therein, for example, patent documents (US5264614A, US5264617A) report alcoholysis recovery of polyhydroxyalkanoic acid ester (PHA) with low alkyl alcohol such as n-butanol as solvent, but it is necessary to add a large amount of strong acid catalyst (such as sulfuric acid), which is easy to corrode equipment, and the process is complicated, and it is difficult to expand to industrial scale, and neutralization and washing will also produce a large amount of waste water.
  • PHA polyhydroxyalkanoic acid ester
  • the hydrolysis rule has the problem of slow hydrolysis speed, and it is difficult to recycle valuable products within a limited time. It usually requires high temperature and high pressure conditions and the catalysis of strong acids or strong bases, and the single processing volume is small, which cannot meet actual needs. In general, the degradation rate of degradable polymer materials in traditional chemical recycling methods is slow, the conversion rate of polymer substrates is low, and the complex reaction system makes it difficult to separate the products after the reaction, resulting in low yields and easy environmental pollution.
  • the present application at least provides a regeneration method and application of a degradable polymer material.
  • the regeneration method of the degradable polymer material comprises the following steps: in a system where an organic non-metallic catalyst and an aqueous solvent exist, the degradable polymer material is degraded to obtain a degradation product; wherein the degradable polymer material comprises one or more of a polyester material and a polycarbonate material; the organic non-metallic catalyst is selected from diphenyl phosphate, binaphthol phosphate and an organic non-metallic catalyst; One or more of organic alkalis.
  • the method uses a specific organic non-metallic catalyst to achieve efficient degradation of degradable polymer materials, with fast degradation, high conversion rate, high reaction yield and low cost; the degradation products can be effectively reused as valuable chemicals.
  • a specific organic non-metallic catalyst is used to regenerate and recycle degradable polymer materials.
  • the specific organic non-metallic catalyst used has been screened through a large number of experiments and found to be able to efficiently catalyze the hydrolysis of degradable polymer materials such as polyester and polycarbonate.
  • the conversion rate of degradable polymer materials is high, the degree of polymerization of degradation products is low (for example, monomers or close to monomer levels can be obtained), and the low molecular weight composition in the system after the degradation reaction can achieve a high proportion (for example, more than 95%).
  • the post-processing operation is simple, the recovery efficiency is high, the process is green and environmentally friendly, and the cost is low.
  • the catalytic degradation process of the degradable polymer material can be carried out at normal pressure and relatively low temperature, without involving organic solvents, and without the need for strong acid or strong alkali environment, not only does not generate a large amount of waste water, but also has a small degree of corrosion to the reaction vessel and low requirements for the treatment equipment, and does not require a series of cumbersome steps such as concentration and multiple purification, which is convenient for industrial expansion of production.
  • Most of the organic non-metallic catalysts used have been commercialized, cheap and easy to obtain. At the same time, these catalysts are stable in nature, have no strict requirements on the temperature and humidity of the storage environment, and can also be recycled many times, which helps to further reduce costs.
  • the low molecular weight composition obtained by the regeneration treatment method can be directly used as a reaction raw material to prepare polymer materials or composite materials, etc., thereby realizing the recycling of plastic waste.
  • the first aspect of the present application provides a method for regenerating a degradable polymer material, which uses an organic non-metallic catalyst with a specific structure to regenerate and recover the degradable polymer material.
  • the specific organic non-metallic catalyst used has been screened through a large number of experiments and it has been found that the catalyst can efficiently catalyze the hydrolysis of degradable polymer materials such as polyester and polycarbonate.
  • a method for regenerating a degradable polymer material comprising the following steps: degrading the degradable polymer material in a system in which an organic non-metallic catalyst and an aqueous solvent exist to obtain a degradation product;
  • the degradable polymer material includes one or more of polyester material and polycarbonate material
  • the organic non-metal catalyst is selected from one or more of diphenyl phosphate, binaphthol phosphate and organic bases. Further, the organic base is selected from one or more of nitrogen-containing heterobicyclic bases, 4-dimethylaminopyridine and phosphazene base compounds.
  • Ar 1 and Ar 2 are each independently an aromatic group
  • the number of ring atoms of the aromatic ring can be 12 to 60
  • the number of ring atoms of the aromatic ring can be 12 to 56
  • Ar1 and Ar2 are each independently an unsubstituted naphthyl group or a substituted naphthyl group, in which case a binaphthyl structure is formed between Ar1 and Ar2
  • the diphenyl phosphate-based organic non-metallic catalyst refers to a catalyst having A class of compounds with a skeleton
  • the two benzene rings can be independently unsubstituted or substituted
  • the two benzene rings can be independently substituted by 0, one or more Q 1
  • any Q 1 can be independently a substituent selected from the following group: halogen, -NO 2 , -CN, C 1 ⁇ C 4 alkoxy, C 1 ⁇ C 6 alkyl, halogen-substituted C 1 ⁇ C 6 alkyl, phenyl and one or more Q a- substituted phenyl
  • any Q a can be independently a plurality of substituents selected from the following group: -NO 2 , -CN, halogen and C 1 ⁇ C 4 alkyl.
  • the diphenyl phosphate-based organic non-metallic catalyst is a catalyst having The two benzene rings can be independently unsubstituted or substituted, and further, the two benzene rings can be independently 0
  • the invention relates to a phenyl group comprising one or more Q 1 groups, any Q 1 group being independently selected from the group consisting of halogen, -NO 2 , C 1 ⁇ C 4 alkoxy, C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 alkyl substituted with halogen, phenyl and phenyl substituted with one or more Q a groups , and any Q a group being independently selected from the group consisting of halogen and C 1 ⁇ C 4 alkyl groups.
  • the organic non-metallic catalyst of the binaphthol phosphate class refers to a catalyst having A class of compounds having a skeleton, wherein the two naphthalene rings may be independently unsubstituted or substituted, further, the two naphthalene rings may be independently substituted by 0, one or more Q 2 , any one Q 2 may be independently a substituent selected from the group consisting of triphenylsilyl (-SiPh 3 , wherein Ph represents a phenyl group), a phenyl group and a substituted phenyl group, further, the phenyl ring in the substituted phenyl group may be substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , -CN, C 1 ⁇ C 6 alkyl, a halogen-substituted C 1 ⁇ C 6 alkyl group, a phenyl group, and one or more Q
  • the organic non-metallic catalyst of the binaphthol phosphate class is A class of compounds with a skeleton, wherein the two naphthalene rings can be independently unsubstituted or substituted, further, the two naphthalene rings can be independently substituted by 0, one or more Q 2 , any Q 2 can be independently a substituent selected from the group consisting of triphenylsilyl (-SiPh 3 , wherein Ph represents a phenyl group), a phenyl group and a substituted phenyl group, further, the phenyl ring in the substituted phenyl group can be substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , C 1 to C 6 alkyl, a halogen-substituted C 1 to C 6 alkyl group, a phenyl group, and one or more Q b -substituted phenyl groups, any Q
  • the diphenyl phosphate has a structure shown in formula (I):
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently selected from any one of -H, halogen, -NO 2 , -CN, C 1 ⁇ C 4 alkoxy, C 1 ⁇ C 6 alkyl, halogen-substituted C 1 ⁇ C 6 alkyl, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of -NO 2 , -CN, halogen and C 1 ⁇ C 4 alkyl.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 are each independently selected from any one of -H, halogen, -NO 2 , C 1 -C 4 alkoxy, C 1 -C 6 alkyl, halogen-substituted C 1 -C 6 alkyl, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of halogen and C 1 -C 4 alkyl.
  • the binaphthol phosphate has a structure shown in formula (II):
  • R 3 and R 3 ' can be independently selected from -H, -SiPh 3 or Wherein, “*” indicates the attachment site of a covalent single bond;
  • R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from any one of -H, halogen, -NO 2 , -CN, C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 alkyl substituted with halogen, phenyl, and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of halogen, -NO 2 , -CN, phenyl and C 1 ⁇ C 4 alkyl; or at least two of R 41 , R 42 , R 43 , R 44 and R 45 form a ring and participate in forming a condensed ring, and the ring-forming groups of R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from -H, halogen, -NO 2 , -CN, C 1 ⁇ C 6 alkyl, C 1 ⁇ C 6 alkyl substituted
  • R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from -H, halogen, -NO 2 , C 1 to C 6 alkyl, halogen-substituted C 1 to C 6 alkyl, phenyl, and substituted phenyl, and the phenyl ring in the substituted phenyl is substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , phenyl and C 1 to C 4 alkyl; or at least two of R 41 , R 42 , R 43 , R 44 and R 45 form a ring and participate in forming a fused ring, and the ring-forming groups in R 41 , R 42 , R 43 , R 44 and R 45 are each independently selected from -H, halogen, -NO 2 , C 1 to C 6 alkyl, halogen-substituted C 1 to C 6 alkyl, Any
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 in the structure of formula (I) are each independently -H, -F, -Cl, -Br, -I, -NO 2 or -CN.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 in formula (I) are each independently selected from -H, -F, -Cl, -Br , -I, -NO 2 .
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 in the structure of formula ( I) are each independently selected from C 1 to C 4 alkoxy groups; and can further be each independently selected from -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH(CH 3 ) 2 , -OCH 2 CH 2 CH 2 CH 3 , -OCH 2 CH(CH 3 ) 2 , -OCH(CH 3 ) CH 2 CH 3 , -OC(CH 3 ) 3 .
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 in the structure of formula (I) are each independently selected from C 1 to C 6 alkyl, i.e., C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl or C 6 alkyl; and can further be independently selected from: ethyl (Et, -CH 2 CH 3 ), 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ), 1-methylethyl (i-Pr, i-propyl, -CH(CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ), 1-methylpropyl (s-Bu, s-butyl, -CH(CH 3 )CH 2 CH 3 ), 2-methylpropyl (i-
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 21 , R 22 , R 23 , R 24 and R 25 in the structure of formula (I) are each independently selected from any one of phenyl and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted with one or more substituents selected from the group consisting of halogen and C 1 -C 4 alkyl.
  • R 12 , R 13 , R 14 , R 15 , R 22 , R 23 , R 24 and R 25 in the structure of formula (I) are H.
  • R 11 and R 21 in the structure of formula (I) are selected from the same group.
  • the diphenyl phosphate has a structure shown in formula (I-1):
  • R 11 , R 13 , R 14 , R 15 , R 21 , R 23 , R 24 and R 25 in the structure of formula (I) are H.
  • R 12 and R 22 in the structure of formula (I) are selected from the same group.
  • the diphenyl phosphate has a structure shown in formula (I-2):
  • R 11 , R 12 , R 14 , R 15 , R 21 , R 22 , R 24 and R 25 in the structure of formula (I) are H.
  • R 13 and R 23 in the structure of formula (I) are selected from the same group.
  • the diphenyl phosphate has a structure shown in formula (I-3):
  • R 12 , R 13 , R 14 , R 22 , R 23 and R 24 in the structure of formula (I) are H.
  • R 11 , R 15 , R 21 and R 25 in the structure of formula (I) are selected from the same group.
  • the diphenyl phosphate has a structure shown in formula (I-4):
  • R 12 , R 14 , R 22 and R 24 in the structure of formula (I) are H.
  • R 11 , R 13 , R 15 , R 21 , R 23 and R 25 in the structure of formula (I) are selected from the same group.
  • the diphenyl phosphate has a structure shown in formula (I-5):
  • R 3 and R 3 ' in the structure of formula (II) are independently selected from -H, -SiPh 3 “*” represents the attachment site.
  • R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) are each independently -H, -F, -Cl, -Br, -I, -NO 2 or -CN.
  • R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) are each independently selected from -H, -F, -Cl, -Br, -I, -NO 2 .
  • R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) are each independently selected from C 1 to C 6 alkyl, i.e., C 1 alkyl, C 2 alkyl, C 3 alkyl, C 4 alkyl, C 5 alkyl or C 6 alkyl; and can further be independently selected from: ethyl (Et, -CH 2 CH 3 ), 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH 3 ), 1-methylethyl (i-Pr, i-propyl, -CH(CH 3 ) 2 ), 1-butyl (n-Bu, n-butyl, -CH 2 CH 2 CH 2 CH 3 ), 1-methylpropyl (s-Bu, s-butyl, -CH(CH 3 )CH 2 CH 3 ), 2-methylpropyl (i-Bu, i-butyl, -CH 2 CH(CH 3 )
  • R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) are each independently selected from any one of phenyl and substituted phenyl, and the phenyl ring in the substituted phenyl is substituted by one or more substituents selected from the following group: halogen, -NO 2 , -CN, phenyl and C 1 to C 4 alkyl substituted phenyl; for example, 4-ClC 6 H 4 , 4-NO 2 C 6 H 4 , 4-CH 3 C 6 H 4 , 4-CF 3 C 6 H 4 , 4-t-BuC 6 H 4 , 4-PhC 6 H 4 , 4-(2,4,6-(CH 3 ) 3 C 6 H 2 )C 6 H 4 , 3,5-(CF 3 ) 2 C 6 H 3 , 3,5-t-Bu 2 C 6 H 3 , 3,5-Ph 2 C 6 H 3 , 2,4,6-CH 3 C 6 H 2 , 2,4,6-(i-
  • the alkyl-substituted phenyl group includes alkyl groups substituting at least one position of the phenyl group.
  • R 42 and R 44 are both selected from phenyl groups substituted with multiple methyl groups, such as 2,4,6-(CH 3 ) 3 C 6 H 2
  • R 3 and R 3 ' can each be independently selected from -5'-2,2",4,4",6,6"-hexamethyl-1,1':3",1"-terphenyl
  • R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) are each independently selected from any one of phenyl and substituted phenyl, wherein the phenyl ring in the substituted phenyl is substituted by one or more substituents selected from the group consisting of halogen, -NO 2 , phenyl and C 1 to C 4 alkyl substituted phenyl; for example, 4-ClC 6 H 4 , 4-NO 2 C 6 H 4 , 4-CH 3 C 6 H 4 , 4-CF 3 C 6 H 4 , 4-t-BuC 6 H 4 , 4-PhC 6 H 4 , 4-(2,4,6-(CH 3 ) 3 C 6 H 2 )C 6 H 4 , 3,5-(CF 3 ) 2 C 6 H 3 , 3,5-t-Bu 2 C 6 H 3 , 3,5-Ph 2 C 6 H 4 , 6 H 3 , 2,4,6-CH 3 C 6 H 2 , 2,4,6-CH 3 C 6
  • the alkyl-substituted phenyl group includes alkyl groups substituting at least one position of the phenyl group.
  • R 42 and R 44 are both selected from phenyl groups substituted with multiple methyl groups, such as 2,4,6-(CH 3 ) 3 C 6 H 2
  • R 3 and R 3 ' can be independently selected from -5'-2,2",4,4",6,6"-hexamethyl-1,1':3",1"-terphenyl.
  • two or more substituents among R 41 , R 42 , R 43 , R 44 and R 45 in the structure of formula (II) form a fused further, the fused ring formed by R 41 , R 42 , R 43 , R 44 and R 45 is 1-naphthyl 2-Naphthyl 4- ⁇ -Naphthyl-phenyl 9-Anthracene 9-Fiki
  • the structural formula shown in formula (II) can also be in its R configuration Or S configuration
  • the organic base is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene 1,5,7-Triazidobicyclo[4.4.0]dec-5-ene 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene
  • One or more of 4-dimethylaminopyridine and phosphazene base compounds are selected from 1,8-diazabicyclo[5.4.0]undec-7-ene 1,5,7-Triazidobicyclo[4.4.0]dec-5-ene 7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene.
  • the organic base is selected from one or more of nitrogen-containing heterobicyclic bases, 4-dimethylaminopyridine and phosphazene base compounds.
  • the nitrogen-containing heterobicyclic base is selected from the group consisting of:
  • Y is -CH 2 - , -NH- or -N(CH 3 )-; and n is 1 or 2.
  • the phosphazene base compound has a structure shown in formula (IV):
  • R is halogen, C 1 ⁇ C 4 alkyl or C 1 ⁇ C 4 alkoxy.
  • the phosphazene base compound refers to a monomer or a polymer thereof, for example tert-Butylimino-tris(dimethylamino)phosphorane 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2 ⁇ 5,4 ⁇ 5-di(phosphorus nitrogen compound) Cyclotriphosphazene base (such as ) and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2 ⁇ 5,4 ⁇ 5-linked di(phosphorus nitrogen compound)
  • the diphenyl phosphate catalyst is selected from one or more of diphenyl phosphate, bis(4-nitrophenyl)phosphate, bis(4-fluorophenyl)phosphate, bis(4-trifluoromethylphenyl)phosphate, bis(4-chlorophenyl)phosphate, bis(4-methoxyphenyl)phosphate and bis(4-methylphenyl)phosphate.
  • the diphenyl phosphate catalyst is selected from one or more of diphenyl phosphate, bis(4-nitrophenyl)phosphate and bis(2,6-dimethylphenyl)phosphate.
  • the binaphthol phosphate catalyst is selected from one or more of binaphthol phosphate, R-binaphthol phosphate, R-3,3'-bis(triphenylsilyl)binaphthol phosphonate and R-3,3'-bis(2,4,6-triisopropylphenyl)binaphthol phosphonate.
  • the organic base catalyst is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 4-dimethylaminopyridine, tert-butylimino-tris(dimethylamino)phosphorane, 1-tert-butyl-2,2,4,4,4-penta(dimethylamino)-2 ⁇ 5,4 ⁇ 5-bis(phosphorus nitrogen-based compound) and cyclotriphosphazene base and 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)-phosphoranylideneamino]-2 ⁇ 5,4 ⁇ 5-bis(phosphorus nitrogen-based compound) One or more.
  • the diphenyl phosphate is selected from diphenyl phosphate (diphenylphosphate, referred to as DPP), bis(4-nitrophenyl) phosphate (bis(4-nitrophenyl) phosphate, referred to as BNPP), bis(4-fluorophenyl) phosphate (bis(4-fluorophenyl) phosphate, referred to as BFPP), bis(4-trifluoromethylphenyl) phosphate (bis(4-trifluoromethylphenyl) phosphate, referred to as BTFPP), bis(4-methylphenyl) phosphate (bis(4-methylphenyl) phosphate, referred to as bis(4-methoxyphenyl)phosphate (BMOPP), bis(2,6-dimethylphenyl)phosphate (DXP), wherein the binaphthol phosphates are selected from binaphthol phosphate (1,1'-bin
  • R-TiPSY naphthol phosphonate
  • R-TRIP 1,8-diazabicyclo[5.4.0]undec-7-ene (1,8-diazabicyclo[5.4 .0]undec-7-ene
  • DBU 1,8-diazabicyclo[4.4.0]dec-5-ene
  • TBD 7-methyl-1,5,7-triazabicyclo[4.4.0]dec
  • the diphenyl phosphate is selected from diphenyl phosphate, bis(4-nitro).
  • the invention relates to a novel organic base comprising: a first ester of 1,4-dihydro-2-nitro-1-yl-2-nitro-2-ol; a second ester of 1,4-dihydro-2-nitro-2-ol; a third ester of 1,4-dihydro-2-nitro-2-ol; a fourth ester of 1,4-dihydro-2-nitro-2-ol; a fifth ester of 1,4-dihydro-2-nitro-2-ol; a fifth ester of 1,4-dihydro-2-nitro-2-ol; a sixth ...
  • the organic non-metal catalyst may be selected from diphenyl phosphates, binaphthol phosphates, and organic bases.
  • diphenyl phosphate bis(4-nitrophenyl) phosphate, bis(4-fluorophenyl) phosphate, bis(4-trifluoromethylphenyl) phosphate, bis(4-methylphenyl) phosphate, bis(4-methoxyphenyl) phosphate, bis(2,6-dimethylphenyl) phosphate, binaphthol phosphate, R-binaphthol phosphate, R-3,3'-bis(triphenylsilyl)binaphthol phosphonate, R-3,3'-bis(2,4,6-triisopropylphenyl)binaphthol phosphonate, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazid
  • organic non-metallic catalysts selected above are mature commercial products, which are not only cheap and easy to obtain, but also can catalyze the efficient hydrolysis of degradable polymer materials to obtain degradation products with low degree of polymerization (for example, close to monomers, or oligomers with a degree of polymerization below 10).
  • the low molecular weight degradation products obtained by the method provided in the present application can be reused as raw materials, for example, can be used in the preparation of polymers, and realize efficient closed-loop recycling of degradable polymer waste.
  • the organic non-metal catalyst may be selected from diphenyl phosphate, binaphthol phosphate and organic bases.
  • the conversion rate of degradable polymer materials is high, the polymerization degree of degradation products is low (for example, close to the monomer level), and the low molecular weight composition in the system after the degradation reaction can achieve a high proportion (for example, more than 95%).
  • the treatment method has low equipment requirements, simple post-treatment operation, green process and low cost.
  • the regeneration treatment method can efficiently degrade the degradable polymer material into monomers and/or oligomers. It is also possible to control the degree of degradation within a certain range by adjusting the reaction raw materials, process parameters (such as the content of water in the reaction system, the content of the catalyst, the reaction time, the reaction temperature and the reaction pressure, etc.), i.e., obtain degradation products with a certain molecular weight and distribution and/or a certain conversion rate.
  • the degradation products with a certain molecular weight and distribution and/or a certain conversion rate can be directly or conveniently used as the raw material of the polymerization reaction under the condition of not carrying out the treatment such as purification, or under the condition of simple separation treatment, to prepare the degradable polymer material through polymerization and other reactions.
  • the degradable polymer material is degraded into a product with reduced molecular weight.
  • the degradation products are substantially low molecular weight products.
  • low molecular weight products mainly refer to degradation products with a molecular weight of ⁇ 1500 Da.
  • oligomer and “oligomer” in this application have the same meaning and can be used interchangeably.
  • degradation products may include monomers and/or oligomers at near monomer levels.
  • the oligomer or oligomer in this application mainly refers to a polymer with a molecular weight of ⁇ 1500Da and containing fewer repeating units.
  • Some molecules in the degradation products may be water-soluble when the molecular weight is low (e.g., PLA oligomer molecular weight ⁇ 500 Da, corresponding to degree of polymerization ⁇ 6.9). Therefore, the water-soluble molecules in the degradation products are recorded as "water-soluble small molecules”.
  • the "near monomer level oligomer” in this application mainly refers to an oligomer with a degree of polymerization ⁇ 10, which may also be recorded as a "quasi-monomer oligomer” or a “quasi-monomer oligomer”.
  • polylactic acid in polyester materials as an example, polylactic acid can be continuously degraded in the presence of organic non-metallic catalysts and water to form low molecular weight degradation products basically composed of monomers and/or oligomers (such as monomers and/or oligomers close to the monomer level).
  • the low molecular weight degradation product can be directly used as a raw material for efficient polymerization reaction, and can be used to prepare a polymerization product with a certain molecular weight (such as a number average molecular weight ⁇ 50kDa).
  • the degree of polymerization of the degradation product in the reaction system can be controlled at a certain level (for example, ⁇ 8) by appropriately adjusting the raw material ratio, process parameters, etc., and then the degradation product in the degradation product system is first used to prepare lactide, and then a high molecular weight polymerization product (such as a number average molecular weight ⁇ 150kDa) is prepared using lactide as a raw material.
  • a high molecular weight polymerization product such as a number average molecular weight ⁇ 150kDa
  • the number average molecular weight of the degradable polymer material is 10kDa to 250kDa, and can further be 10kDa to 150kDa, and further can be 10kDa to 130kDa, and can also be selected from any one of the following number average molecular weight values or an interval consisting of any two number average molecular weight values: 10kDa, 20kDa, 30kDa, 40kDa, 50kDa, 60kDa, 70kDa, 80kDa, 90kDa, 100kDa, 110kDa, 120kDa, 130kDa, 140kDa, 150kDa, 160kDa, 170kDa, 180kDa, 190kDa, 200kDa, 210kDa, 220kDa, 230kDa, 240kDa, 250kDa, etc.
  • the weight average molecular weight of the degradable polymer material is 10kDa to 500kDa, further 10kDa to 250kDa, further 30kDa to 230kDa, and can also be selected from any one of the following weight average molecular weight values or an interval consisting of any two weight average molecular weight values: 10kDa, 20kDa, 30kDa, 40kDa, 50kDa, 60kDa, 70kDa, 80kDa, 90kDa, 100kDa, 110kDa, 120kDa, 130kDa, 140kDa, 150kDa, 160kDa, 170kDa, 180kDa, 190kDa, 200kDa, 210kDa, 220kDa, 230kDa, 240kDa, 250kDa, 260kDa, 270kDa, 280kDa, 290kDa, 300kDa, 310
  • the mass ratio of water in the system to the degradable polymer material is (0.01-10):1, further can be (0.1-1):1, further can be (0.08-0.33):1:, and can also be selected from any one of the following mass ratios or an interval consisting of any two mass ratios: (0.01:1), (0.02:1), (0.03:1), (0.04:1), (0.05:1), (0.06:1), (0.07:1), (0.08:1), (0.083:1), (0.1:1), (0.15:1), (0.156:1) (0.2:1), (0.25:1), (0.3:1), (0.31:1) , (0.32:1), (0.33:1), (0.34:1), (0.35:1), (0.36:1), (0.37:1), (0.38:1), ( 0.39:1), (0.4:1), (0.5:1), (0.6:1), (0.7:1), (0.8:1), (0.9:1), (1:1)
  • a more appropriate water amount relative to the mass ratio of the degradable polymer material is more conducive to improving the degradation rate of the degradable polymer material. If the water amount in the system is higher than the mass ratio of the degradable polymer material, the internal temperature of the system is difficult to exceed the boiling point of the solvent (taking water as an example, 100°C) under normal pressure, which slows down the reaction process, and the water as a raw material will boil violently and evaporate in large quantities, which poses certain operational risks; if the water amount in the system is lower than the mass ratio of the degradable polymer material, it may cause insufficient amount of raw materials to participate in the reaction, reduce the probability of contact between reactants, and slow down the reaction rate, which may lead to a higher degree of polymerization of the final product.
  • the mass ratio of the organic non-metallic catalyst to the degradable polymer material is (0.001-0.1):1, further can be (0.01-0.05:1), further can be (0.035-0.05:1), and can also be selected from any one of the following mass ratios or any two mass ratios: (0.001:1), (0.002:1), (0.003:1), (0.004:1), (0.005:1), (0.006:1), (0.007:1), (0.008:1), (0.0088:1) , (0.009:1), (0.01:1), (0.015:1), (0.02:1), (0.025:1), (0.03:1), (0.031:1), (0.032:1), (0.033:1), (0.034:1), (0.035:1), (0.036:1), (0.037:1), (0.038:1), (0.039:1), (0.04:1), (0.045:1), (0.05:1), (0.06:1), (0.07:1), (0
  • a more appropriate catalyst amount relative to the mass ratio of the degradable polymer material is more conducive to reducing the economic cost of the recycling scheme. If the mass ratio of the catalyst to the degradable polymer material is too high, the use of a large amount of catalyst increases the raw material cost of the regeneration process; if the mass ratio of the catalyst to the degradable polymer material is too low, it may cause the degradation rate to be too slow, increasing time cost and energy consumption.
  • the degradation treatment of degradable polymer materials can be carried out under the condition of small amount of catalyst, with high catalytic efficiency and low cost.
  • the average degree of polymerization of the degradation product is ⁇ 20, further ⁇ 15, further ⁇ 10, and can also be selected from any one of the following average degree of polymerization values or an interval consisting of any two average degree of polymerization values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.
  • the average degree of polymerization of the degradation product can also be selected from any one of the following ranges, such as 1-20, 1-15, 1-10, 2-20, 2-15, 2-12, 2-10, 2.3-9.6, etc.
  • the molar percentage of the monomer in the degradation product is ⁇ 30%, further ⁇ 50%, further ⁇ 80%, and can also be selected from the following molar percentage values of any one monomer or the interval composed of the molar percentage values of any two monomers: 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 80%, 90%, etc.
  • the molar percentage of the monomer in the degradation product can also be selected from any of the following ranges, such as 30% to 60%, 30% to 70%, 30% to 80%, 30% to 90%, 30% to 100%, etc.
  • the above-mentioned regeneration treatment method is used to degrade the degradable polymer material, and as the degradation treatment time is extended, the molar percentage of the monomer in the degradation product can be higher.
  • the molar percentage of the monomer in the degradation product refers to: the percentage of the molar number of the monomer to the total molar number of the degradation product.
  • I 1.23 is the integral value of the characteristic peak corresponding to the methyl group (HOOCCH(CH 3 )OH) of the lactic acid monomer at 1.23 ppm
  • I 1.27 is the integral value of the characteristic peak corresponding to the terminal methyl group (-COCH(CH 3 )OH) of the lactic acid oligomer at 1.27 ppm. It is understood that when different batches are tested, the chemical shifts of the above characteristic peaks at 1.23 ppm and 1.27 ppm may shift. However, those skilled in the art can The characteristic peak positions corresponding to 1.23 ppm and 1.27 ppm in the measured 1 H NMR spectrum were determined according to the characteristic peak attribution method.
  • the mass proportion of low molecular weight products relative to the degradation products is ⁇ 80%, further ⁇ 90%, and further ⁇ 95%.
  • the mass proportion of low molecular weight products in the system refers to: the weight percentage of low molecular weight products in the degradation products.
  • the standard for low molecular weight products in the reaction system is to detect the degradation products by gel permeation chromatography (Gel Permeation Chromatography, GPC) and Fourier transform nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) spectrometer, and no polymer characteristic peaks appear.
  • GPC Gel Permeation Chromatography
  • NMR Nuclear Magnetic Resonance
  • the mass percentage of the low molecular weight products relative to the total mass of the degradation products is ⁇ 80%, further ⁇ 90%, and further ⁇ 95%.
  • the water-soluble small molecule conversion rate is ⁇ 20%, and can further be ⁇ 23%, and can also be selected from any of the following water-soluble small molecule conversion rate values or any two water-soluble small molecule conversion rate values: 20%, 23.7%, 25%, 30%, 32.6%, 35%, 40%, 45%, 50%, 53%, 55%, 60%, 61.6%, 65%, 70%, 72.1%, 74.1%, 75%, 80%, 85%, 86%, 88.3%, 90%, 90.4%, 91%, 92.8%, 95%, 99.2%, etc. It can be understood that when the degradable polymer material is degraded by the above-mentioned regeneration method, the value of the water-soluble small molecule conversion rate in the degradation product can be higher as the degradation treatment time is prolonged.
  • the conversion rate of polymer raw materials into water-soluble small molecules refers to the ratio of the amount of the initial raw material that has been degraded and dissolved in water after the degradation reaction to the initial raw material when the system continues to react to the preset stop or termination conditions.
  • the mass ratio can be used as a standard for calculation and judgment.
  • the “conversion rate of water-soluble small molecules” can be calculated based on the mass percentage of water-soluble products (corresponding to water-soluble small molecules) in the degradation products relative to the degraded raw materials (i.e., polymer raw materials).
  • minput is the mass of the polymer before the reaction
  • mresidue is the mass of the remaining insoluble matter after the reaction.
  • the polydispersity index (PDI) of the degradable polymer material is ⁇ 3.3, further can be 1 to 3.3, and further can be 1 to 3.27.
  • the polydispersity index (PDI) is used to describe the molecular weight distribution of a polymer.
  • the polydispersity index (PDI) is calculated as the ratio of Mw divided by Mn ; the larger the value, the wider the molecular weight distribution.
  • PDI can also be equal to molar-mass dispersity ( DM ).
  • the degradable polymer material is selected from polylactic acid (PLA), polyglycolic acid (PGA), poly ⁇ -caprolactone (PCL), polylactic acid-glycolic acid copolymer (PLGA), polyglycolic acid- ⁇ -caprolactone copolymer (PCGA), polylactic acid- ⁇ -caprolactone copolymer (e), PCLA), poly( ⁇ -valerolactone), PVL), poly( ⁇ -butyrolactone), PBS), PBAT), poly(butylene adipate terephthalate), PHA), and PTMC.
  • PLA polylactic acid
  • PGA polyglycolic acid
  • PCL poly ⁇ -caprolactone
  • PCLA polylactic acid-glycolic acid copolymer
  • PCGA polyglycolic acid- ⁇ -caprolactone copolymer
  • PCGA polylactic acid- ⁇ -caprolactone copolymer
  • e polylactic acid- ⁇ -caprolactone copolymer
  • PCLA poly
  • degradable polymer material and water are continuously added to the degradation product, the content of the catalyst in the reaction system is reduced, and a secondary degradation reaction is carried out, and oligomers and/or monomers corresponding to the degradable polymer material can still be obtained, that is, the regeneration treatment of the degradable polymer material can be carried out continuously, which is conducive to industrial continuous production.
  • the regeneration method comprises the following steps:
  • the average degree of polymerization of the second degradation product can refer to the above definition, for example, ⁇ 20, and further for example, ⁇ 10.
  • the first degradable polymer material is subjected to a first degradation treatment to obtain a first degradation product
  • the third degradation product and the fourth degradable polymer material are mixed and subjected to a fourth degradation treatment to obtain a fourth degradation product;
  • the average degree of polymerization of the fourth degradation product can refer to the above definition, for example ⁇ 20, further for example ⁇ 10, etc.
  • the regeneration method comprises the following steps:
  • the average degree of polymerization of the 10th degradation product can refer to the above definition, for example ⁇ 20, further for example ⁇ 10, etc.
  • the temperature of any degradation treatment is independently 25°C to 200°C, further 50°C to 200°C, and further 125°C to 200°C.
  • the temperature of any degradation treatment is independently 125°C to 200°C, further 130°C to 200°C, further 140°C to 180°C, and can also be selected from any one of the following temperatures or any two of the following temperatures: 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C, etc.
  • a more suitable reaction temperature is conducive to improving the degradation efficiency of the degradable polymer material.
  • reaction temperature If the reaction temperature is too high, it may cause the water in the system to evaporate violently, which on the one hand loses the reaction raw materials, and on the other hand makes the operation dangerous, and puts forward higher requirements on the reaction equipment; if the reaction temperature is too low, it may cause a slow reaction speed, and the degradation of the degradable polymer material into oligomers and/or monomers takes a long time, increasing time cost and energy consumption.
  • the temperature of the degradation treatment can be the actual temperature of the reaction system, or can be the ambient temperature of the reaction system, such as the water bath temperature, oil bath temperature, etc.
  • the time of any degradation treatment is independently 0.1h to 5h, optionally 0.25h to 5h, further 0.5h to 4h, further 1h to 4h, further 1.5h to 4h, and can also be selected from any one of the following time intervals or any two of the following time intervals: 0.1h, 0.25h, 0.5h, 0.75h, 1h, 1.2h, 1.4h, 1.6h, 1.8h, h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h; it can also be selected from any one of the following time or any two time intervals: 0.25h, 0.5h, 0.75h, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h.
  • a more appropriate reaction time is independently 0.25h to 5
  • the temperature of any degradation treatment is independently 125°C to 200°C, and the time of any degradation treatment is independently 0.1h to 5h, and can be optionally 0.25h to 5h.
  • the temperature of any degradation treatment is independently 130° C. to 200° C.
  • the time of any degradation treatment is independently 1 h to 4 h.
  • the temperature of any degradation treatment is independently 140° C. to 180° C.
  • the time of any degradation treatment is independently 1.5 h to 4 h.
  • the pressure of any degradation treatment can be independently 1 atm-100 atm. It can also be selected from the following pressures or any two pressure intervals: 1 atm, 10 atm, 20 atm, 30 atm, 40 atm, 50 atm, 60 atm, 70 atm, 80 atm, 90 atm, 100 atm, etc.
  • the pressure of any degradation treatment is independently 100 ⁇ 5 kPa. It can also be selected from any one of the following pressures or an interval consisting of any two pressures: 95 kPa, 96 kPa, 97 kPa, 98 kPa, 100 kPa, 101 kPa, 102 kPa, 103 kPa, 104 kPa, 105 kPa, etc.
  • the regeneration process can be carried out in a non-sealed environment and non-high temperature and high pressure conditions, the efficiency of catalytic degradation is high, and the degradable polymer material can be quickly converted into reusable oligomers and/or monomer raw materials.
  • the boiling point of the solvent can be affected and the internal temperature of the system can be affected. In addition, it can also affect the intensity of molecular motion, which will affect the reaction rate. If the reaction pressure is high, the internal temperature of the system rises and the molecular collision is more intense, the reaction becomes faster, but higher requirements are placed on the equipment; if the reaction pressure is low, it may cause the internal temperature of the system to be low and the probability of molecular collision is reduced, and the probability of reaction is reduced, so that the reaction slows down.
  • the degradation treatment of degradable polymer materials can be carried out under the conditions without strong acid, strong alkali and organic solvent, which is helpful Used to improve equipment corrosion and wastewater discharge problems in industrial applications.
  • the regeneration method further comprises the following steps:
  • the degradation product is washed with an organic solvent, wherein the organic solvent is selected from one or more of chloroform, petroleum ether, carbon disulfide, ether, dichloromethane, benzene, toluene and ethyl acetate. It can be understood that the process of washing the degradation product with an organic solvent is also called extraction treatment.
  • the degradation products after degradation treatment can be effectively separated from the organic non-metallic catalyst by simple washing (such as extraction).
  • the separated degradation products can be directly used as raw materials for the polymerization process without concentration or re-purification, which is convenient for industrial production.
  • the regeneration treatment method comprises the following steps: adding a degradable polymer material, an organic non-metallic catalyst and water into a reaction vessel, and carrying out a degradation reaction at 125°C to 200°C under dispersed conditions (such as under stirring conditions) (optionally, the degradation time can be as defined above, for example, it can be 0.1h to 5h, and further can be 0.25h to 5h); further, the mass ratio of organic non-metallic catalyst: water: degradable polymer material can be (0.001 to 0.1): (0.08 to 10): 1.
  • the degradation reaction can be carried out in an atmospheric environment of 100 ⁇ 5kP. In some embodiments, the degradation reaction can be carried out in a pressure environment of 1atm-100atm.
  • the regeneration treatment method comprises the following steps: adding a degradable polymer material, an organic non-metallic catalyst and water to a reaction vessel, performing a degradation reaction at 125°C to 200°C under dispersed conditions (such as under stirring conditions) (optionally, the degradation time can be as defined above, for example, it can be 0.1h to 5h, and further can be 0.25h to 5h), and washing with an organic solvent after cooling; further, the mass ratio of organic non-metallic catalyst: water: degradable polymer material can be (0.001 to 0.1): (0.08 to 10): 1; further, the organic solvent can be any one of chloroform, petroleum ether, and dichloromethane or any combination thereof, and further, the organic solvent can be any one of chloroform, petroleum ether, and dichloromethane.
  • the degradation reaction can be carried out in an atmospheric environment of 100 ⁇ 5kP. In some embodiments, the degradation reaction can be carried out in a pressure environment of 1atm-100atm
  • the regeneration treatment method comprises the following steps: adding a degradable polymer material, an organic non-metallic catalyst and water into a reaction vessel, carrying out a degradation reaction at 160 ⁇ 20°C under dispersed conditions (such as under stirring conditions) (optionally, the degradation time can be as defined above, for example, 1.5 ⁇ 1h), and washing with an organic solvent after cooling; further, the mass ratio of organic non-metallic catalyst: water: degradable polymer material can be (0.035 ⁇ 0.02): (0.3 ⁇ 0.1): 1; further, the organic solvent can be any one of chloroform, petroleum ether, and dichloromethane.
  • the degradation reaction can be carried out in an atmospheric environment of 100 ⁇ 5kP. In some embodiments, the degradation reaction can be carried out in a pressure environment of 1atm-100atm.
  • the regeneration treatment method comprises the following steps: adding a degradable polymer material, an organic non-metallic catalyst and water into a reaction vessel, carrying out a degradation reaction at 160 ⁇ 10°C under dispersed conditions (such as under stirring conditions) (optionally, the degradation time can be as defined above, for example, 1.5 ⁇ 0.5h), and washing with an organic solvent after cooling; further, the mass ratio of organic non-metallic catalyst: water: degradable polymer material can be (0.035 ⁇ 0.005): (0.3 ⁇ 0.05): 1; further, the organic solvent can be any one of chloroform, petroleum ether, and dichloromethane.
  • the degradation reaction can be carried out in an atmospheric environment of 100 ⁇ 5kP. In some embodiments, the degradation reaction can be carried out in a pressure environment of 1atm-100atm.
  • the regeneration treatment method comprises the following steps: adding a degradable polymer material, an organic non-metallic catalyst and water into a reaction vessel, carrying out a degradation reaction at 160 ⁇ 10°C under dispersed conditions (such as under stirring conditions) (optionally, the degradation time can be as defined above, for example, 1.5 ⁇ 0.5h), and washing with an organic solvent after cooling; further, the mass ratio of organic non-metallic catalyst: water: degradable polymer material can be (0.0035 ⁇ 0.001): (0.15 ⁇ 0.05): 1; further, the organic solvent can be any one of chloroform, petroleum ether, and dichloromethane.
  • the degradation reaction can be carried out in an atmospheric environment of 100 ⁇ 5kP. In some embodiments, the degradation reaction can be carried out in a pressure environment of 1atm-100atm.
  • the second aspect of the present application provides a low molecular weight composition, wherein the low molecular weight composition is a degradation product of a degradable polymer material, and the low molecular weight composition can be prepared according to the regeneration method described in the first aspect.
  • the low molecular weight composition is the low molecular weight product of the first aspect.
  • the average degree of polymerization of the low molecular weight composition is ⁇ 20, further ⁇ 15, and further ⁇ 10.
  • the average degree of polymerization of the low molecular weight composition can also be selected from any one of the following average degree of polymerization values or an interval consisting of any two average degree of polymerization values: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc.
  • the average degree of polymerization of the degradation product can also be selected from any one of the following ranges, such as 1-20, 1-15, 1-10, 2-20, 2-15, 2-12, 2-10, etc.
  • the low molecular weight composition can be obtained by hydrolyzing a degradable polymer material (abandoned degradable polymer material can be used) with a catalyst.
  • the product purification method is simple, the process is economical, and has a good cost advantage.
  • the third aspect of the present application provides a method for recycling degradable polymer materials.
  • the recycling method comprises the following steps: performing a polymerization reaction using a low molecular weight composition as an initial raw material; wherein the low molecular weight composition is a degradation product prepared by the regeneration method described in the first aspect or the low molecular weight composition described in the second aspect.
  • a polymerization reaction can be carried out under the catalysis of a traditional catalyst to obtain the polymer material again, thereby realizing the secondary use of the degraded polymer material, that is, recycling.
  • This recycling method is not only cost-effective but also environmentally friendly.
  • the method for recycling degradable polymer materials comprises the following steps: S100: degrading the degradable polymer materials in a system in which an organic non-metallic catalyst and an aqueous solvent exist, and obtaining a degradation product system containing degradation products after the reaction is completed;
  • step S100 please refer to the first aspect of the present application.
  • the synthesis reaction in step S200 is not particularly limited as long as the degradation product in step S100 participates in the reaction.
  • the degradation product system is directly used as a raw material for synthesizing lactide.
  • the molecular weight or degree of polymerization of the degradation products in the degradation product system can refer to the above.
  • the average degree of polymerization of the degradation products in the degradation product system is ⁇ 8, and further the average degree of polymerization can be ⁇ 5, etc.
  • the weight ratio or molar ratio of the monomer-like oligomers in the degradation products can be increased, for example, the weight ratio or molar ratio of the monomer-like oligomers in the degradation products is controlled to be greater than or equal to a certain value, such as ⁇ 50%, ⁇ 80%, ⁇ 90%, etc.
  • the degradation product system in step S200, is directly used as a raw material in a polymerization reaction, and can be used to prepare a homopolymer or a copolymer.
  • the organic non-metal catalyst used in the present application can be separated from the degradation product by a simple separation step.
  • the degradation product may not be separated from the organic non-metal catalyst, and the reaction system obtained by the degradation treatment may be directly used for the next step.
  • the degradation of polylactic acid PLA is catalyzed by the organic non-metal catalyst diphenyl phosphate DPP. If the degradation product system obtained by the degradation treatment is used to prepare lactide monomer, since the preparation process of lactide is usually subjected to a reduced pressure distillation operation, the degradation product in the degradation product system can be separated from the organic non-metal catalyst diphenyl phosphate DPP while preparing lactide.
  • the catalyst for synthesizing lactide can be directly added to the system.
  • the generated lactide can enter the container for receiving the lactide product or enter the next step of the reaction process, so as to achieve separation from the components of the degradation product system and the catalyst for synthesizing lactide.
  • organic non-metallic catalyst and the degradable polymer material are as defined in the first aspect of the present application.
  • polyester/polycarbonate materials such as discarded polyester/polycarbonate materials
  • polyester/polycarbonate materials can be converted into products with high added value under mild conditions.
  • the obtained products can be simply removed from the impurities to obtain oligomers and/or monomers corresponding to the degradable polyester/polycarbonate materials, which can be used again in the polymerization process, thus realizing the recycling of plastics.
  • the obtained monomer aqueous solution is of comparable quality to commercially available products and can be used for conventional purposes after extraction to remove the catalyst.
  • the technical solution in this application can be used to degrade polyester/polycarbonate materials (such as discarded polyester/polycarbonate materials) into low molecular weight degradation products (such as oligomers and/or monomers), and the degradation products can also be used for the next synthesis process or utilization.
  • polyester/polycarbonate materials such as discarded polyester/polycarbonate materials
  • low molecular weight degradation products such as oligomers and/or monomers
  • the degradation products can also be used for the next synthesis process or utilization.
  • polylactic acid as a polymer material (raw material)
  • the degradation product such as lactic acid monomer aqueous solution
  • Lactic acid as a widely used platform molecule, can be used in chemical, food, cosmetics, pharmaceutical and other industries in addition to preparing polylactic acid.
  • lactic acid can be used to prepare a variety of commodities and intermediate chemicals, such as lactic acid esters, 1,2-propylene glycol, acrylic acid, pyruvic acid, acetaldehyde, 2,3-pentanedione, etc.
  • lactic acid can be used as an antifreeze agent, a fixing agent for wool fabric printing, and can also be used for softening leather, descaling, cleaning, adjusting pH, etc. It is also a green organic solvent.
  • Number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) test method Gel permeation chromatography (1260, Agilent) was used to test. The sample was dissolved in tetrahydrofuran (THF) at a concentration of 10 mg/mL and tested at 35°C. The mobile phase was tetrahydrofuran, the flow rate was 1.0 mL/min, and the standard sample was narrow distribution polystyrene (PS). Gel permeation chromatography The lower limit of the test is 550Da-600Da. According to the 1 H NMR spectrum of the sample, the number average molecular weight (M n ) and average degree of polymerization of the sample can be calculated.
  • THF tetrahydrofuran
  • PS narrow distribution polystyrene
  • the detailed test method is as follows: lactic acid and/or its oligomers were dissolved in DMSO-d 6 at a concentration of 100 mg/mL and tested at 25°C by Fourier transform nuclear magnetic resonance spectrometer (400 MHz, AVANCE III HD, Bruker), and a small amount of D 2 O was added to the test sample. Other compounds were dissolved in CDCl 3 at a concentration of 10 mg/mL for testing.
  • the polylactic acid model used in Example 1 is LX175 (TotalEnergies Corbion).
  • the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the PLA used were measured by gel permeation chromatography to be 121.0 kDa, 199.7 kDa and 1.65, respectively.
  • the catalyst used was diphenyl phosphate DPP.
  • the molecular weight of the degradation product was tested by the above method and was lower than the detection limit of GPC, indicating that its molecular weight was lower than 600Da.
  • the average molecular weight of the degradation product was measured by nuclear magnetic resonance and was 191Da, with an average degree of polymerization of
  • the 1H NMR spectrum of the product after chloroform extraction is shown in Figure 1. The methyl peak shifts are different in different chemical environments.
  • 1.23ppm is the methyl (OHCOCH(CH 3 )OH) peak in the lactic acid monomer (the position marked as a in Figure 1)
  • 1.27ppm is the methyl (-COCH(CH 3 )OH) peak near the hydroxyl end in the lactic acid oligomer (the position marked as c in Figure 1)
  • 1.38-1.50ppm is the other methyl (-COCH(CH 3 )O-) peak in the lactic acid oligomer (the position marked as f in Figure 1).
  • 4.03-5.50ppm is the peak corresponding to the secondary methyl in the lactic acid monomer and its oligomer (the position marked as b, d, and e in Figure 1), which overlaps with the water peak.
  • 7.0-7.4ppm corresponds to the characteristic peak of the benzene ring of DPP (the position marked as i, h, and g in Figure 1). Except for the characteristic peak corresponding to the solvent DMSO-d 6 at 2.5ppm, there are no other obvious signals.
  • the calculation method of the molar percentage of monomers in the degradation product and the conversion rate of polymers into water-soluble small molecules is as described above. Taking Example 1 as an example, the calculation method is as follows: the characteristic peak integral value corresponding to the terminal methyl group of lactic acid oligomer at 1.27ppm is set to 1, the characteristic peak integral value at 1.23ppm is 1.15, and the characteristic peak integral value at 1.38-1.50ppm is 3.01.
  • the number average molecular weight of the degradation product is (90+72*3.01/(1+1.15) ⁇ 191)
  • the molar percentage of lactic acid monomers in the degradation product is 1.15/(1+1.15) ⁇ 0.535
  • the remaining water-insoluble solid residue is 0.2406g
  • the conversion rate of polymers into water-soluble small molecules is (1-0.2406/2.5 ⁇ 0.904).
  • the degradation product obtained by regenerating the degradable polymer material (in the presence of an organic non-metallic catalyst and water) using a gel permeation chromatography is tested, and the measured molecular weight is lower than the GPC detection limit, which means that the molecular weight of the polymer material contained in the obtained degradation product is lower than 600Da.
  • Example 2 The raw materials and degradation process of Example 2 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.025 g, and the organic solvent used to wash the degradation product is petroleum ether. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.01:0.3:1.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 387 Da, the average degree of polymerization was 5.1, and the conversion rate was 40.0%.
  • Example 3 The raw materials and degradation process of Example 3 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.05 g, and the organic solvent used to wash the degradation product is dichloromethane. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.02:0.3:1.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 289 Da, the average degree of polymerization was 3.8, and the conversion rate was 61.6%.
  • Example 4 The raw materials and degradation process of Example 4 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.125 g, and the organic solvent used to wash the degradation product is ether. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.05:0.3:1.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 185 Da, the average degree of polymerization was 2.3, and the conversion rate was 99.2%.
  • the raw materials and degradation process of Examples 5 to 9 are basically the same as those of Example 1, except that the environmental temperature of the degradation process is Different, they are 120°C, 140°C, 150°C, 170°C and 180°C respectively.
  • the washed degradation products were tested in the same manner as in Example 1.
  • the molecular weight of the degradation products was lower than the GPC detection limit.
  • the conversion rate of the degradation products and the average molecular weight and average degree of polymerization calculated by the measured H NMR spectrum are shown in Table 1.
  • Example 10 The raw materials and degradation processes of Examples 10 to 13 are substantially the same as those of Example 1, except that the degradation treatment time is different, namely 0.5 h, 1 h, 2 h and 2.5 h, respectively.
  • the washed degradation products were tested in the same manner as in Example 1.
  • the molecular weight of the degradation products was lower than the detection limit of GPC.
  • the conversion rate of the degradation products and the average molecular weight, average degree of polymerization and conversion rate calculated by the measured hydrogen nuclear magnetic resonance spectrum are shown in Table 2.
  • the average molecular weight of the degradation product (equivalent to the second degradation product) was calculated based on the measured nuclear magnetic resonance hydrogen spectrum to be 181 Da.
  • the PLA raw material was added repeatedly for 8 degradation steps (equivalent to the 3rd to 10th degradation treatments), and the average molecular weight of the final degradation product (equivalent to the 10th degradation product) was calculated based on the measured nuclear magnetic resonance hydrogen spectrum to be 193Da.
  • a total of 25g of PLA was added (equivalent to the sum of the masses of the 1st to 10th degradable polymer materials), and water was also added in the 3rd to 10th degradation treatments, and the mass ratio of the added water to the degradable polymer material remained the same as that of the second time.
  • the average molecular weight of the obtained degradation product (equivalent to the second degradation product) was calculated based on the measured nuclear magnetic resonance hydrogen spectrum to be 284 Da.
  • the average molecular weight of the final product (equivalent to the 4th degradation product) was calculated based on the measured nuclear magnetic resonance hydrogen spectrum to be 287Da Among them, a total of 4000g of PLA was added (equivalent to the sum of the masses of the 1st to 4th degradable polymer materials), and water was also added in the 3rd and 4th degradation treatments.
  • the mass ratio of the added water to the degradable polymer material remained the same as that of the 1st and 2nd times.
  • Example 16 The raw materials and degradation process of Example 16 are basically the same as those of Example 1, except that the catalyst used is di(4- BNPP is a nitrophenyl phosphate.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 182 Da, the average degree of polymerization was 2.3, and the conversion rate was 84.6%.
  • Example 17 The raw materials and degradation process of Example 17 are basically the same as those of Example 1, except that the catalyst used is bis(4-fluorophenyl) phosphate (BFPP for short), and the degradation treatment time is 0.5 h.
  • the catalyst used is bis(4-fluorophenyl) phosphate (BFPP for short)
  • the degradation treatment time is 0.5 h.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 354 Da, the average degree of polymerization was 4.7, and the conversion rate was 67.4%.
  • Example 18 The raw materials and degradation process of Example 18 are basically the same as those of Example 1, except that the catalyst used is bis(4-trifluoromethylphenyl)phosphate (BTFPP for short), and the degradation treatment time is 0.5 h.
  • BTFPP bis(4-trifluoromethylphenyl)phosphate
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 343 Da, the average degree of polymerization was 4.5, and the conversion rate was 69.2%.
  • Example 19 The raw materials and degradation process of Example 19 are basically the same as those of Example 1, except that the catalyst used is binaphthol phosphate (BNDHP for short), and the degradation treatment time is 4 hours.
  • BNDHP binaphthol phosphate
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 243 Da, the average degree of polymerization was 3.1, and the conversion rate was 73.8%.
  • Example 20 The raw materials and degradation process of Example 20 are basically the same as those of Example 1, except that the catalyst used is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU for short), the degradation treatment time is 3 h, and the organic solvent used to wash the degradation product is petroleum ether.
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 333 Da, the average degree of polymerization was 4.4, and the conversion rate was 68.0%.
  • Example 21 The raw materials and degradation process of Example 21 are basically the same as those of Example 1, except that the catalyst used is 1,5,7-triazidebicyclo[4.4.0]dec-5-ene (TBD for short), and the degradation treatment time is 4 hours.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 249 Da, the average degree of polymerization was 3.2, and the conversion rate was 73.0%.
  • Example 22 The raw materials and degradation process of Example 22 are basically the same as those of Example 1, except that the degradable polymer material used is polycaprolactone (PCL for short), the degradation treatment time is 3 hours, and the organic solvent used to wash the degradation product is dichloromethane.
  • PCL polycaprolactone
  • Polycaprolactone model 6800 (Perstorp Company), the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the PCL used were measured by gel permeation chromatography and were 65.2 kDa, 213.1 kDa and 3.27, respectively.
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 23 The raw materials and degradation process of Example 23 are basically the same as those of Example 1, except that the degradable polymer material used is polylactic acid-glycolic acid copolymer (PLGA for short), and the degradation treatment time is 2.5 h.
  • the degradable polymer material used is polylactic acid-glycolic acid copolymer (PLGA for short)
  • PLGA polylactic acid-glycolic acid copolymer
  • the poly(lactic acid-co-glycolic acid) was prepared in the laboratory.
  • the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the PLGA were measured by gel permeation chromatography and were 9.97 kDa, 15.0 kDa and 1.50, respectively.
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 24 The raw materials and degradation process of Example 24 are basically the same as those of Example 1, except that the degradable polymer material used is polybutylene adipate/terephthalate (PBAT for short), and the degradation treatment time is 2.5 h.
  • PBAT polybutylene adipate/terephthalate
  • Polybutylene adipate/terephthalate model is F Blend C1200 (BASF SE), the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the PBAT used were measured by gel permeation chromatography and were 17.3 kDa, 31.0 kDa and 1.79, respectively.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • PDI polydispersity index
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 25 The raw materials and degradation process of Example 25 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.125 g, the degradable polymer material used is poly (3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB for short), the degradation treatment time is 3 hours, and the organic solvent used to wash the degradation product is dichloromethane. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.05:0.3:1.
  • the model of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is EM 10080 (ECOMRNN).
  • the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the P34HB used were measured by gel permeation chromatography and were 128.9 kDa, 228.6 kDa and 1.77, respectively.
  • the test conditions were the same as those in Example 1.
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 26 The raw materials and degradation process of Example 26 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.125 g, the degradable polymer material used is polybutylene succinate (PBS for short), the degradation treatment time is 4 hours, and the organic solvent used to wash the degradation product is dichloromethane. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.05:0.3:1.
  • the model of polybutylene succinate is BioPBSTM FD72PM (Public Company Limited).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • PDI polydispersity index
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 27 The raw materials and degradation process of Example 27 are basically the same as those of Example 1, except that the degradable polymer material used is a 3D printing material.
  • the 3D printing materials were purchased from an online retail platform (Taobao.com), and the number average molecular weight ( Mn ), weight average molecular weight ( Mw ), and polydispersity index (PDI) of the materials used were measured by gel permeation chromatography and were 10.9 kDa, 18.4 kDa, and 1.69, respectively.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • PDI polydispersity index
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit. The average molecular weight was calculated by hydrogen nuclear magnetic resonance spectrum to be 193 Da, the average degree of polymerization was 2.4, and the conversion rate was 78.2%.
  • Example 28 The raw materials and degradation process of Example 28 are basically the same as those of Example 1, except that the amount of the organic non-metallic catalyst used is 0.125 g, the degradable polymer material used is a plastic straw (mainly composed of polylactic acid and polybutylene succinate), the degradation treatment time is 4 hours, and the organic solvent used to wash the degradation product is dichloromethane. Calculation shows that the mass ratio of the organic non-metallic catalyst: water: degradable polymer material is 0.05:0.3:1.
  • Plastic straws were purchased from an online retail platform (Taobao.com).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • PDI polydispersity index
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • Example 29 The raw materials and degradation process of Example 29 are basically the same as those of Example 1, except that the degradable polymer material used is polytrimethylene carbonate (PTMC for short), the organic solvent used to wash the degradation product is dichloromethane, and the degradation treatment time is 3 hours.
  • the degradable polymer material used is polytrimethylene carbonate (PTMC for short)
  • the organic solvent used to wash the degradation product is dichloromethane
  • the degradation treatment time is 3 hours.
  • Polytrimethylene carbonate was prepared in the laboratory.
  • the number average molecular weight ( Mn ), weight average molecular weight ( Mw ) and polydispersity index (PDI) of the PTMC were measured by gel permeation chromatography and were 23.6 kDa, 36.0 kDa and 1.53, respectively.
  • the washed degradation product was tested in the same manner as in Example 1, and the molecular weight thereof was lower than the lower limit of GPC detection.
  • a regeneration method for degradable polyester/polycarbonate materials is a regeneration method for degradable polyester/polycarbonate materials
  • Example 31 The raw materials and degradation process of Example 31 are basically the same as those of Example 1, except that the catalyst used is bis(4-nitrophenyl) phosphate (BNPP for short), and the degradation treatment time is 0.5 h.
  • the catalyst used is bis(4-nitrophenyl) phosphate (BNPP for short)
  • the degradation treatment time is 0.5 h.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 215 Da, the average degree of polymerization was 2.7, and the conversion rate was 62.4%.
  • Example 32 The raw materials and degradation process of Example 32 are basically the same as those of Example 1, except that the catalyst used is bis(4-nitrophenyl) phosphate (BNPP for short), and the degradation treatment time is 1 hour.
  • the catalyst used is bis(4-nitrophenyl) phosphate (BNPP for short)
  • the degradation treatment time is 1 hour.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 186 Da, the average degree of polymerization was 2.3, and the conversion rate was 85.8%.
  • Example 33 The raw materials and degradation process of Example 33 are basically the same as those of Example 1, except that the catalyst used is binaphthol phosphate (BNDHP for short), and the degradation treatment time is 3.5 h.
  • BNDHP binaphthol phosphate
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 291 Da, the average degree of polymerization was 3.8, and the conversion rate was 74.3%.
  • Example 34 The raw materials and degradation process of Example 34 are basically the same as those of Example 1, except that the catalyst used is R-binaphthol phosphate (R-BNDHP for short), and the degradation treatment time is 5 hours.
  • the catalyst used is R-binaphthol phosphate (R-BNDHP for short)
  • the degradation treatment time is 5 hours.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 247 Da, the average degree of polymerization was 3.2, and the conversion rate was 70.8%.
  • Example 35 The raw materials and degradation treatment process of Example 35 are basically the same as those of Example 1, except that the catalyst used is bis(4-methylphenyl) phosphate (BMPP for short), and the degradation treatment time is 2.0 h.
  • the catalyst used is bis(4-methylphenyl) phosphate (BMPP for short)
  • the degradation treatment time is 2.0 h.
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the GPC detection limit.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 270 Da, the average degree of polymerization was 3.5, and the conversion rate was 77.9%.
  • Example 36 The raw materials and degradation process of Example 36 are basically the same as those of Example 1, except that the catalyst used is bis(4-methoxyphenyl) phosphate (BMOPP for short), and the degradation treatment time is 2.5 h.
  • the catalyst used is bis(4-methoxyphenyl) phosphate (BMOPP for short)
  • BMOPP bis(4-methoxyphenyl) phosphate
  • the washed degradation product was tested in the same manner as in Example 1. Its molecular weight was lower than the detection limit of GPC.
  • the average molecular weight of the degradation product was calculated by hydrogen nuclear magnetic resonance spectrum to be 227 Da, the average degree of polymerization was 2.9, and the conversion rate was 80.2%.
  • the conversion rate of the system was calculated on the 1st day, 2nd day, 3rd day, 4th day and 5th day of each test, and the apparent morphology of the residual polymer in the system was observed regularly:
  • FIG2 is an optical photograph of the polylactic acid film residue of one of the three parallel experiments of Experiment A1 at the 8th hour (8h), 16th hour (16h), 24th hour (24h), 32nd hour (32h), 48th hour (48h) and 72nd hour (72h) after the start of the reaction, wherein the dotted line indicates that there is no solid residue.
  • the conversion rate of the system reached 95.3% after two days of reaction, and reached 100% after three days of reaction (the change in conversion rate can be seen in FIG3 and Table 3).
  • Test A2 The aforementioned polylactic acid film disc was placed in water. The conversion rate of this system was only 5.1% after 5 days of reaction (the change in conversion rate can be seen in Figure 3 and Table 3). The reason why the degradation rate of the polylactic acid film disc in this system was significantly lower than that in Test A1 may be that no organic non-metallic catalyst was added. Even if there was water in the system, without the action of the catalyst, the degradation process was very slow.
  • Test A3 The aforementioned polylactic acid film disc is placed in a dry environment, and 3.5 wt% diphenyl phosphate DPP is mixed in the polylactic acid film disc.
  • the conversion rate of the system after 5 days of reaction is 11.9% (the change in conversion rate can be seen in Figure 3 and Table 3).
  • the reason why the degradation rate of the polylactic acid film disc in this system is significantly lower than that of Test A1 but slightly higher than that of Test A2 may be that although no additional water is added, there is a certain amount of water vapor in the atmospheric environment. When a certain amount of diphenyl phosphate DPP is mixed, the degradation process of the polylactic acid film disc can proceed, but the degradation rate is slow.
  • Test A6 0.5 g of polylactic acid PLA and 0.025 g of diphenyl phosphate DPP were placed in a test tube and placed in an oil bath at 160°C. The tube was left uncovered and 2 drops of deionized water were added every 5 min during the reaction. The test time was 0.5 h.
  • Test A7 0.5 g of polylactic acid was placed in a test tube and placed in an oil bath at 160°C. The tube was left uncovered and 2 drops of deionized water were added every 5 minutes during the reaction. The test time was 0.5 h.
  • test B1 From the test B1, it can be seen that polylactic acid can be degraded relatively quickly in the presence of only water and diphenyl phosphate. From the comparison of tests B1, B2 and B3, it can be seen that the degradation rate of polylactic acid in a system with water as solvent is faster than that in a system with methanol as solvent; the degradation rate of polylactic acid in the former system is similar to that in a system with methanol and water as mixed solvents. From the comparison of test B1 and test B5, as well as the comparison of test B2 and test B4, it can be seen that the addition of tetrahydrofuran is conducive to accelerating the degradation rate of polylactic acid. The reason may be that tetrahydrofuran plays a solubilizing role, making the reaction raw materials evenly distributed in the system, increasing the contact and reaction opportunities, thereby accelerating the reaction process.
  • the degradation product (the substance shown in B of FIG5 ) was characterized by 1 H NMR, and it was found that the degradation product was lactic acid oligomers and/or monomers, with an average molecular weight of 220 Da and an average degree of polymerization of 2.8; polymers such as PET, PP and PE and the corresponding degradation oligomers and/or monomers were not found in the degradation product.
  • FIG5 C is the solid obtained by separation, and DSC tests were performed on different plastics respectively, and compared with the DSC test results of the corresponding raw materials (PET, PP and PE sheets or pellets) before degradation treatment, that is, FIG5 D, E and F were obtained.
  • the melting points (T m ) of the three traditional durable plastics PET, PP and PE are basically unchanged before and after the above-mentioned reaction: the melting point of PET before treatment is 247.7°C, and the melting point after treatment is 248.1°C (D in Figure 5); the melting point of PP before treatment is 161.3°C, and the melting point after treatment is 162.0°C (E in Figure 5); the melting point of PE before treatment is 129.5°C, and the melting point after treatment is 129.6°C (F in Figure 5).
  • DSC test method The thermal properties of plastics are characterized by differential scanning calorimetry (Q2000, TA Instruments). Taking PET as an example, the weighed sample is placed in a sample pan, heated to 320°C in a nitrogen atmosphere, balanced for 5 minutes to remove the thermal history, and then cooled to 20°C at a rate of 10°C/min. After 5 minutes of balancing, the temperature is raised to 320°C at the same rate and the data is recorded. PP and PE are heated to 220°C.
  • V 5 g of PLA pellets (diameter ⁇ 3 mm) purchased from TotalEnergies Corbion with the brand name LX175 were placed in the following three different aqueous solutions (solution mass 5 g) at an ambient temperature of 80°C. 50 mg of the solution was lyophilized 1 day and 3 days after the start of the reaction and subjected to 1 H NMR testing.
  • the first aqueous solution was a 0.1 M (mol/L) HCl solution, in which almost no water-soluble substances were detected. Three days after the reaction began, the system was a suspension with a milky white color.
  • the second aqueous solution is an aqueous solution containing 5 wt% diphenyl phosphate DPP.
  • the solution contained lactic acid oligomers and monomers with an average molecular weight of 385 and an average degree of polymerization of 5.1.
  • the average molecular weight of the degradation product was 108 and the average degree of polymerization was 1.3. At this time, the solution was clear and transparent.
  • the third aqueous solution is a 0.1 M (mol/L) HCl solution containing 5 wt% diphenyl phosphate DPP.
  • the solution contained lactic acid oligomers and monomers with an average molecular weight of 167 and an average degree of polymerization of 2.1.
  • the solution became clear and transparent, and the average molecular weight of the degradation product was 106 and the average degree of polymerization was 1.3.

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Abstract

涉及一种可降解高分子材料的再生处理方法和应用，包括以下步骤：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，得到降解产物；其中，可降解高分子材料包括聚酯材料和聚碳酸酯材料中的一种或多种；有机非金属催化剂选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类中的一种或多种。

Description

可降解高分子材料的再生处理方法及应用
相关申请
本申请要求于2023年7月5日提交的、申请号为CN2023108217699、名称为“可降解高分子材料的再生处理方法及应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及高分子材料回收利用技术领域，特别是涉及一种可降解高分子材料的再生处理方法及应用。
背景技术
随着国内外高分子材料产量和消费量的持续攀升，高分子材料的回收利用成为产业可持续发展的关键所在。可降解高分子材料因其在特定条件下可降解的内在特性得到了广泛关注，尤其是聚乳酸、聚己内酯、聚己二酸/对苯二甲酸丁二酯等，它们作为环境友好材料取代了部分传统高分子材料(聚对苯二甲酸乙二醇酯、聚氯乙烯、聚丙烯等)的市场，并被广泛应用于包装和医药等领域，以期降低高分子材料对环境造成的污染。
可降解高分子材料(如聚酯、聚碳酸酯等)的自然降解速度较慢，在海洋、土壤中降解到低分子状态需要两至三年时间，即便在工业堆肥条件下也需要半年左右的时间才能完全降解。可降解高分子材料的自然降解速度不均会形成破碎的塑料颗粒而非低聚物，引发的微塑料问题甚至比石油基塑料更严重，不仅不能实现资源的再利用，还会造成对环境的二次污染。同时，传统回收方法如热裂解、醇解和水解的处理条件苛刻、单次处理量少且处理速度慢，降解产物需经历繁琐的纯化步骤才能进行有效的二次利用。
发明内容
基于此，根据本申请的各种实施方式和各种实施例，本申请的目的包括提供一种可降解高分子材料的再生处理方法，采用成本较低的特定催化剂实现对可降解高分子材料的高效降解，该方法不但降解速度快，而且转化率高，反应收率也高。本申请还提供了一种采用该再生处理方法的应用。
本申请的第一方面，提供一种可降解高分子材料的再生处理方法。
在一些实施方式中，提供一种可降解高分子材料的再生处理方法，其包括以下步骤：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，得到降解产物；
其中，
所述可降解高分子材料包括聚酯材料和聚碳酸酯材料中的一种或多种；
所述有机非金属催化剂选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类中的一种或多种，所述有机碱类选自含氮杂双环碱类、4-二甲氨基吡啶和磷腈碱类化合物中的一种或多种。
在一些实施方式中，所述的再生处理方法，所述磷酸二苯酯类具有式(Ⅰ)所示的结构：
式(Ⅰ)中，R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、卤素、-NO2、-CN、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：-NO2、-CN、卤素和C1～C4烷基；
可选地，式(Ⅰ)中，R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、卤素、-NO2、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素和C1～C4烷基；
所述联萘酚磷酸酯类具有式(Ⅱ)所示的结构：
式(Ⅱ)中，R3和R3’可以独立地选自-H、-SiPh3或其中，“*”表示共价单键的连接位点；
R41、R42、R43、R44和R45各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基；或R41、R42、R43、R44和R45中的至少两个成环并参与形成稠合环，R41、R42、R43、R44和R45中未成环的基团各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基；
可选地，R41、R42、R43、R44和R45各自独立地选自-H、卤素、-NO2、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、苯基和C1～C4烷基；或R41、R42、R43、R44和R45中的至少两个成环并参与形成稠合环，R41、R42、R43、R44和R45中未成环的基团各自独立地选自-H、卤素、-NO2、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、苯基和C1～C4烷基；
所述含氮杂双环碱类选自具有式(Ⅲ)所示的结构：
式(Ⅲ)中，Y是-CH2-、-NH-或-N(CH3)-；n是1或2；
所述磷腈碱类化合物具有式(Ⅳ)所示的结构：
式(Ⅳ)中，R为卤素、C1～C4烷基或C1～C4烷氧基。
在一些实施方式中，所述的再生处理方法，满足如下特征中的一个或多个：
所述可降解高分子材料的数均分子量为10kDa～250kDa；
所述体系中水相对于所述可降解高分子材料的质量比为(0.01～10):1；
所述有机非金属催化剂相对于所述可降解高分子材料的质量比为(0.001～0.1):1；
所述降解产物的平均聚合度≤20。
在一些实施方式中，所述的再生处理方法，满足如下特征中的一个或多个：
所述可降解高分子材料选自聚乳酸、聚羟基乙酸、聚ε-己内酯、聚乳酸-羟基乙酸共聚物、聚羟基乙酸-ε-己内酯共聚物、聚乳酸-ε-己内酯共聚物、聚δ-戊内酯、聚丁内酯、聚丁二酸丁二醇酯、 聚己二酸/对苯二甲酸丁二酯、聚丁二酸/己二酸丁二醇酯、聚羟基脂肪酸酯和聚三亚甲基碳酸酯中的一种或多种；
可选地，所述可降解高分子材料选自聚乳酸、聚羟基乙酸、聚ε-己内酯、聚乳酸-羟基乙酸共聚物、聚羟基乙酸-ε-己内酯共聚物、聚乳酸-ε-己内酯共聚物、聚δ-戊内酯、聚丁内酯、聚丁二酸丁二醇酯、聚己二酸/对苯二甲酸丁二酯、聚羟基脂肪酸酯和聚三亚甲基碳酸酯中的一种或多种；
所述磷酸二苯酯类催化剂选自磷酸二苯酯、双(4-硝基苯基)磷酸酯、双(4-氟苯基)磷酸酯、双(4-三氟甲基苯基)磷酸酯、双(4-氯苯基)磷酸酯、双(4-甲氧基苯基)磷酸酯和双(4-甲基苯基)磷酸酯中的一种或多种；
可选地，所述磷酸二苯酯类催化剂选自磷酸二苯酯、双(4-硝基苯基)磷酸酯和双(2,6-二甲基苯基)磷酸酯中的一种或多种；
所述联萘酚磷酸酯类催化剂选自联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯和R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯中的一种或多种；
所述有机碱类催化剂选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶、叔丁基亚氨基-三(二甲氨基)正膦、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)和环三磷腈碱和1-叔丁基-4,4,4-三(二甲氨基)-2,2-二[三(二甲氨基)-正膦亚基氨基]-2Λ5,4Λ5-连二(磷氮基化合物)中的一种或多种。
在一些实施方式中，所述的再生处理方法，包括以下步骤：在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行第1次降解处理，得到第1降解产物；
混合第i降解产物和第i+1可降解高分子材料，进行第i+1次降解处理，得到第i+1降解产物，其中，i为≥1的整数，所述第i+1可降解高分子材料至少包括第2可降解高分子材料；至i+1＝n时结束降解处理，得到第n降解产物，其中n为≥2的整数，所述第n降解产物的平均聚合度≤20。
在一些实施方式中，所述的再生处理方法，满足如下特征中的一个或多个：
任一次降解处理的温度独立地为125℃～200℃；
任一次降解处理的时间独立地为0.1h～5h，可选为0.25h～5h；
任一次降解处理的压力独立地为1atm-100atm，可选地，任一次降解处理的压力独立地为100±5kPa。
在一些实施方式中，所述的再生处理方法，还包括以下步骤：采用有机溶剂洗涤所述降解产物；其中，所述有机溶剂选自氯仿、石油醚、二硫化碳、乙醚、二氯甲烷、苯、甲苯和乙酸乙酯中的一种或多种。
本申请的第二方面，提供一种低分子量组合物，所述低分子量组合物为可降解高分子材料的降解产物，所述低分子量组合物根据第一方面所述的再生处理方法制备得到，其中，所述低分子量组合物的平均聚合度≤20。
本申请的第三方面，提供一种可降解高分子材料的回收利用方法，包括以下步骤：以低分子量组合物作为初始原料进行聚合反应；其中，所述低分子量组合物为第一方面所述的再生处理方法制备得到的降解产物或第二方面所述低分子量组合物。
本申请的第四方面，提供一种有机非金属催化剂在可降解高分子材料的降解处理中的应用；
其中，所述有机非金属催化剂和所述可降解高分子材料如第一方面中所定义。
本申请的一个或多个实施方式和实施例的细节在下面的附图和描述中提出。本申请的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本申请实施例1中样品产物经氯仿清洗处理后以及未经清洗时的1H NMR谱图。
图2为本申请的试验A1的聚乳酸薄膜圆片在反应开始后的第8小时(8h)、第16小时(16h)、第24小时(24h)、第32小时(32h)、第48小时(48h)和第72小时(72h)的残余物的光学照片。
图3为本申请一些实施例中反应体系的转化率(平均值)随时间的变化；其中，试验A1～A5分别将聚乳酸薄膜圆片置于溶有3.5wt％的磷酸二苯酯(DPP)的pH＝1的水溶液(试验A1)、去离子水(试验A2)、干燥环境(薄膜中混有3.5wt％的磷酸二苯酯DPP)(试验A3)、pH＝1的 盐酸溶液(试验A4)和pH＝13的NaOH水溶液(试验A5)中。
图4为本申请一些实施例中反应体系的峰值分子量(Mpeak)随时间的变化；其中，试验A6的反应体系为聚乳酸粒料(预先粉碎至直径<1mm)、磷酸二苯酯DPP(DPP相对于聚乳酸粒料的质量比为5％)，反应温度为160℃油浴，每隔5min滴入2滴去离子水，反应0.5h；试验A7与试验A6的不同之处在于没有添加磷酸二苯酯DPP。
图5为以不同高分子材料为底物进行的降解试验；其中，图中A为以混合塑料(聚对苯二甲酸乙二醇酯PET+聚丙烯PP+聚乙烯PE+聚乳酸PLA)为底物，反应前塑料的照片；图中B和C分别为前述混合塑料为底物进行反应后，得到的降解产物(图中B)和未降解的塑料(图中C)的照片；图中D、E和F分别是反应底物(混合塑料)中聚对苯二甲酸乙二醇酯PET、聚丙烯PP和聚乙烯PE在处理前后的DSC曲线，Tm为熔点。
具体实施方式
下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
在这里专用的词语“实施方式”、“实施例”，作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。本申请实施例中性能指标测试，除非特别说明，采用本领域常规试验方法。应理解，本申请中所涉及的术语仅仅是为描述特别的实施方式，并非用于限制本申请公开的内容。
除非另有说明，否则本文使用的技术和科学术语具有本申请所属技术领域的普通技术人员通常理解的相同含义；作为本申请中其它未特别注明的试验方法和技术手段均指本领域内普通技术人员通常采用的实验方法和技术手段。
除非另外说明或存在矛盾之处，本文中使用的术语或短语具有以下含义：
“烷基”，是指碳碳间、碳氢间均以单键相连的烃去掉一个氢原子后剩下的部分。包含该术语的短语，例如，“C1～C6烷基”是指包含1～6个碳原子的烷基，每次出现时，可以互相独立地为C1烷基、C2烷基、C3烷基、C4烷基、C5烷基或C6烷基。合适的实例包括但不限于：乙基(Et、-CH2CH3)、1-丙基(n-Pr、n-丙基、-CH2CH2CH3)、1-甲基乙基(i-Pr、i-丙基、-CH(CH3)2)、1-丁基(n-Bu、n-丁基、-CH2CH2CH2CH3)、1-甲基丙基(s-Bu、s-丁基、-CH(CH3)CH2CH3)、2-甲基丙基(i-Bu、i-丁基、-CH2CH(CH3)2)、1,1-二甲基乙基(t-Bu、t-丁基、-C(CH3)3)、1-戊基(n-戊基、-CH2CH2CH2CH2CH3)、1-甲基丁基(-CH(CH3)CH2CH2CH3)、1-乙基丙基(-CH(CH2CH3)2)、1,1-二甲基丙基(-C(CH3)2CH2CH3)、1,2-二甲基丙基(-CH(CH3)CH(CH3)2)、3-甲基丁基(-CH2CH2CH(CH3)2)、2-甲基丁基(-CH2CH(CH3)CH2CH3)、2,2-二甲基丙基(-CH2C(CH3)3)、1-己基(-CH2CH2CH2CH2CH2CH3)、1-甲基戊基(-CH(CH3)CH2CH2CH2CH3)、1-乙基丁基(-CH(CH2CH3)CH2CH2CH3)、1,1-二甲基丁基(-C(CH3)2CH2CH2CH3)、1，2-二甲基丁基(-CH(CH3)CH(CH3)CH2CH3)、1,3-二甲基丁基(-CH(CH3)CH2CH(CH3)2)、1-甲基-1-乙基丙基(-C(CH3)(CH2CH3)2)、2-甲基-1-乙基丙基(-CH(CH2CH3)CH(CH3)2)、1,1,2-三甲基丙基(-C(CH3)2CH(CH3)2)、1,2,2-三甲基丙基(-CH(CH3)C(CH3)3、2-甲基戊基(-CH2CH(CH3)CH2CH2CH3)、4-甲基戊基(-CH2CH2CH2CH(CH3)2)、3-甲基戊基(-CH2CH2CH(CH3)CH2CH3)、2-乙基丁基(-CH2CH(CH2CH3)2)、2,3-二甲基丁基(-CH2CH(CH3)CH(CH3)2)、3,3-二甲基丁基(-CH2CH2C(CH3)3)、2,2-二甲基丁基(-CH2C(CH3)2CH2CH3)。
“烷氧基”是指具有-O-烷基的基团，即如上所定义的烷基经由氧原子连接至主链结构。包含该术语的短语，例如，“C1～C4烷氧基”是指烷基部分包含1～4个碳原子，每次出现时，可以互相独立地为C1烷氧基、C2烷氧基、C3烷氧基或C4烷氧基。合适的实例包括但不限于：甲氧基(-O-CH3或-OMe)、乙氧基(-O-CH2CH3或-OEt)和叔丁氧基(-O-C(CH3)3或-Ot-Bu)。
“卤素”或“卤基”是指-F、-Cl、-Br或-I。
“苯基”是指-C6H5；烷基取代的苯基包括烷基对苯基的至少一个位点的取代。
本文所使用的术语“和/或”、“或/和”、“及/或”的选择范围包括两个或两个以上相关所列项目中任一个项目，也包括相关所列项目的任意的和所有的组合，所述任意的和所有的组合包括任意的两个相关所列项目、任意的更多个相关所列项目、或者全部相关所列项目的组合。
本申请中，涉及到数值区间(也即数值范围)，如无特别说明，该数值区间内可选的数值的分布视为连续，且包括该数值区间的两个数值端点(即最小值及最大值)，以及这两个数值端点之间的每一个数值。如无特别说明，当数值区间仅仅指向该数值区间内的整数时，包括该数值范围的两个端点整数，以及两个端点之间的每一个整数，相当于直接列举了每一个整数。当提供多个数值范围描述特征或特性时，可以合并这些数值范围。换言之，除非另有指明，否则本文中所公开之数值范围应理解为包括其中所归入的任何及所有的子范围。该数值区间中的“数值”可以为任意的定量值，比如数字、百分比、比例等。“数值区间”允许广义地包括百分比区间，比例区间，比值区间等定量区间。
本文所用的术语“基本”和“大约”用于描述允许数值存在小的波动，应当理解，只要数值范围在允许的波动范围内，都在“基本”或“大约”的语义范畴内，例如，“基本”和“大约”涵盖了无波动的情形。例如，它们可以是指小于或等于±5％，如小于或等于±2％，如小于或等于±1％，如小于或等于±0.5％，如小于或等于±0.2％，如小于或等于±0.1％，如小于或等于±0.05％。在本文中以范围格式表示或呈现的数值数据，仅为方便和简要起见使用，因此应灵活解释为不仅包括作为该范围的界限明确列举的数值，还包括该范围内包含的所有独立的数值或子范围。例如，“1％～5％”的数值范围应被解释为不仅包括1％至5％的明确列举的值，还包括在所示范围内的独立值和子范围。因此，在这一数值范围中包括独立值，如2％、3.5％和4％，和子范围，如1％～3％、2％～4％和3％～5％等。这一原则同样适用于仅列举一个数值的范围。此外，无论该范围的宽度或所述特征如何，这样的解释都适用。
本文中，“优选”、“更好”、“更佳”、“为宜”仅为描述效果更好的实施方式或实施例，应当理解，并不构成对本申请保护范围的限制。如果一个技术方案中出现多处“优选”，如无特别说明，且无矛盾之处或相互制约关系，则每项“优选”各自独立。
本申请中，“进一步”、“更进一步”、“特别”等用于描述目的，表示内容上的差异，但并不应理解为对本申请保护范围的限制。
本申请中，以开放式描述的技术特征中，包括所列举特征组成的封闭式技术方案，也包括所列举特征的开放式技术方案。
本申请中的温度参数，如无特别限定，既允许为恒温处理，也允许在一定温度区间内存在变动。应当理解的是，所述的恒温处理允许温度在仪器控制的精度范围内进行波动。允许在如±5℃、±4℃、±3℃、±2℃、±1℃的范围内波动。
为了更好的说明本申请内容，在下文的一些实施例中给出了众多的细节。本领域技术人员应当理解，没有某些细节，本申请同样可以实施。在实施例中，对于本领域技术人员熟知的一些方法、手段、仪器、设备等未作详细描述，以便凸显本申请的主旨。
在不冲突的前提下，本申请实施例公开的技术特征可以任意组合，得到的技术方案属于本申请实施例公开的内容。
目前市场上主流的传统石油基塑料的替代产品是以聚乳酸为代表的可降解聚酯、聚碳酸酯类材料。尽管这些可降解材料能够在特定条件下降解，但通常需要专业的工业堆肥条件，而目前投入使用的材料已远超现有工业堆肥厂的处理能力。此外，即使是在工业堆肥条件下，材料降解周期通常在3～6个月，且材料及降解产物都直接排入自然环境，无法实现资源的回收再利用。
常用可降解高分子材料例如聚乳酸、聚己内酯、聚丁二酸丁二醇酯、聚己二酸/对苯二甲酸丁二酯等在自然条件下的降解速度极慢，在空气中放置一年也不会发生形态上的明显变化。实现可降解高分子材料的有效降解需要人工干预。
为了更好地实现对可降解高分子材料的处理和回收利用，可以选择化学回收，通常可选用热裂解、醇解和水解等方法。热裂解法的反应温度高、目标产物收率低、副反应较多且产物易发生外消旋化，难以得到高纯度的产品。醇解法通常是在催化剂的作用下，以低烷基醇或乙二醇处理废弃材料以回收其中的羟基酸或酯，例如专利文献(US5264614A、US5264617A)报道了以正丁醇等低烷基醇为溶剂的聚羟基脂肪酸酯(PHA)的醇解回收，但需要加入大量强酸性催化剂(如硫酸)，易对设备产生腐蚀，流程复杂，难以扩大至工业级规模，中和水洗还会产生大量废水。另有技术文献分别使用离子液体(CN102659590A)、液体路易斯酸(CN105017013A)、CaO/MCF介孔碱性分子筛(CN107382718A)、碱性低共熔溶剂(CN108837847A)和固载化离子液体(CN110003009A)作为催化剂，在甲醇等溶剂中将聚乳酸转化成了对应的乳酸酯。这在一定程度上改善了设备腐蚀、废水排放和催化剂无法重复使用的问题，但这些催化剂还未实现市场化的供应，需自行制备、步骤繁琐，短期内不具有产业转化能力。水解法则存在水解速度较慢的问题，难以在有限的时间内对有价值的产品进行回收利用，通常还需要高温高压条件和强酸或强碱的催化，并且单次处理量较少，无法满足实际需求。综合来看，传统化学回收方法中可降解高分子材料的降解速度较慢、聚合物底物的转化率低，而且复杂的反应体系还会造成反应后产物分离难度较大，导致收率低且容易引起环境污染。
因此，亟需开发一种反应速度快、转化率高、收率高且绿色环保的可降解高分子材料的回收方法，以便能够将可降解聚酯/聚碳酸酯材料转化为具有高附加值的产品，实现可降解聚酯/聚碳酸酯材料的回收利用，促进产业绿色发展。
根据本申请的各种实施方式和各种实施例，本申请至少提供一种可降解高分子材料的再生处理方法和应用。
在一些实施方式中，可降解高分子材料的再生处理方法包括以下步骤：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，得到降解产物；其中，可降解高分子材料包括聚酯材料和聚碳酸酯材料中的一种或多种；有机非金属催化剂选自磷酸二苯酯类、联萘酚磷酸酯类和有 机碱类中的一种或多种。该方法采用特定的有机非金属催化剂可实现对可降解高分子材料的高效降解，降解快、转化率高、反应收率高、成本低；降解产物作为有价值的化学品可再次得到有效利用。
本申请一实施方式采用特定的有机非金属催化剂对可降解高分子材料进行再生回收处理，所采用的特定有机非金属催化剂经大量实验筛选发现，该催化剂能够高效催化聚酯、聚碳酸酯等可降解高分子材料的水解。本申请提供的可降解高分子材料的再生处理方法中，可降解高分子材料的转化率较高，降解产物聚合度低(例如可得到单体或接近单体水平)，降解反应后体系中低分子量组合物可实现较高占比(例如95％以上)，另外，后处理操作简单、回收效率高，工艺绿色环保，成本低。
在本申请一实施方式提供的可降解高分子材料的再生处理方法中，可降解高分子材料催化降解过程可以在常压和较低温度下进行，不涉及有机溶剂，也无需强酸、强碱环境，不仅无大量废水产生、对反应容器的腐蚀程度小、对处理设备要求也低，而且无需浓缩、多次纯化等一系列繁琐步骤，便于工业化扩大生产。所用有机非金属催化剂大都已经商品化，价廉易得。同时，这些催化剂性质稳定，对储存环境的温度、湿度等无严格要求，还可多次循环使用，有助于进一步降低成本。
该再生处理方法制得的低分子量组合物可作为反应原料直接用于制备高分子材料或复合材料等，实现塑料废弃物的循环利用。
本申请的第一方面，提供一种可降解高分子材料的再生处理方法，该方法采用特定结构的有机非金属催化剂对可降解高分子材料进行再生回收处理，所采用的特定有机非金属催化剂经大量实验筛选发现，该催化剂能够高效催化聚酯、聚碳酸酯等可降解高分子材料的水解。
在一些实施方式中，该具有特定结构的有机非金属催化剂可选自环状磷酸二酯类和有机碱类化合物。进一步地，环状磷酸二酯类化合物的结构中同时具有酸性位点(-OH)和Lewis碱性位点(P＝O)，从而发挥促进降解的作用，非限制性示例可以包括磷酸二苯酯类有机非金属催化剂和联萘酚磷酸酯类有机非金属催化剂。
在一些实施方式中，提供了一种可降解高分子材料的再生处理方法，包括以下步骤：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，得到降解产物；
其中，
所述可降解高分子材料包括聚酯材料和聚碳酸酯材料中的一种或多种；
所述有机非金属催化剂选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类中的一种或多种进一步地，所述有机碱类选自含氮杂双环碱类、4-二甲氨基吡啶和磷腈碱类化合物中的一种或多种。
在一些实施方式中，环状磷酸二酯类是芳香类磷酸二酯是指具有Ar1-O-(HO)P(＝O)-O-Ar2 结构的一类芳香类磷酸二酯，其中，Ar1和Ar2各自独立地为芳香类基团，进一步地，芳香环的成环原子数可以为12～60个，更进一步的，芳香环的成环原子数可以为12～56个，还可以选自如下任一种或任两种成环原子数构成的区间：12、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48、50、52、54、56、58和60。Ar1和Ar2可以各自独立地为一价基团(可参阅式(Ⅰ)所示结构)，Ar1和Ar2还可以通过共价单键相连，使得Ar1、Ar2及-O(HO)P(＝O)-O-该共价单键成环，例如当Ar1和Ar2均包含萘环时，Ar1和Ar2可以构成联萘型结构，其中一些示例可参阅式(II)。在一些实施例中，Ar1、Ar2及-O(HO)P(＝O)-O-通过Ar1和Ar2之间的共价单键形成七元环结构，进一步地，Ar1和Ar2各自独立地为未取代的萘基或取代的萘基，此时Ar1和Ar2之间形成联萘结构，进一步地，-O-(HO)P(＝O)-两侧的氧基分别连接至一个萘环的成环碳原子，可参阅式(II)。
在本申请的一些实施方式中，磷酸二苯酯类的有机非金属催化剂是指具有如骨架的一类化合物，两个苯环可以各自独立是未取代的或被取代的，进一步地，两个苯环可以各自独立地被0个、一个或多个Q1取代，任一个Q1可以独立地为选自下组的取代基：卤素、-NO2、-CN、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基以及一个或多个Qa取代的苯基，任一个Qa可以独立地多个选自下组的取代基：-NO2、-CN、卤素和C1～C4烷基。
在一些实施方式中，磷酸二苯酯类的有机非金属催化剂是指具有如骨架的一类化合物，两个苯环可以各自独立是未取代的或被取代的，进一步地两个苯环可以各自独立地被0 个、一个或多个Q1取代，任一个Q1可以独立地为选自下组的取代基：卤素、-NO2、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基以及一个或多个Qa取代的苯基，任一个Qa可以独立地多个选自下组的取代基：卤素和C1～C4烷基。
在本申请的一些实施方式中，联萘酚磷酸酯类的有机非金属催化剂是指具有骨架的一类化合物，两个萘环可以各自独立是未取代的或被取代的，进一步地，两个萘环可以各自独立地被0个、一个或多个Q2取代，任一个Q2可以独立地为选自下组的取代基：三苯基硅基(-SiPh3，其中，Ph表示苯基)、苯基和取代基的苯基，更进一步地，所述取代的苯基中的苯环可以被一个或多个选自下组的取代基所取代：卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及一个或多个Qb取代的苯基，任一个Qb可以独立地选自下组的取代：卤素、-NO2、-CN、苯基和C1～C4烷基。
在一些实施方式中，联萘酚磷酸酯类的有机非金属催化剂是指具有骨架的一类化合物，两个萘环可以各自独立是未取代的或被取代的，进一步地，两个萘环可以各自独立地被0个、一个或多个Q2取代，任一个Q2可以独立地为选自下组的取代基：三苯基硅基(-SiPh3，其中，Ph表示苯基)、苯基和取代基的苯基，更进一步地，所述取代的苯基中的苯环可以被一个或多个选自下组的取代基所取代：卤素、-NO2、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及一个或多个Qb取代的苯基，任一个Qb可以独立地选自下组的取代：卤素、-NO2、苯基和C1～C4烷基。
在一些实施方式中，所述的再生处理方法中，所述磷酸二苯酯类具有式(Ⅰ)所示的结构：
式(Ⅰ)中，R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、卤素、-NO2、-CN、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：-NO2、-CN、卤素和C1～C4烷基。
在一些实施方式中，式(Ⅰ)中，R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、卤素、-NO2、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素和C1～C4烷基。
在一些实施方式中，所述的再生处理方法中，所述联萘酚磷酸酯类具有式(Ⅱ)所示的结构：

式(Ⅱ)中，R3和R3’可以独立地选自-H、-SiPh3或其中，“*”表示共价单键的连接位点；
R41、R42、R43、R44和R45各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基；或R41、R42、R43、R44和R45中的至少两个成环并参与形成稠合环，R41、R42、R43、R44和R45中为成环的基团各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基。
在一些实施方式中，式(Ⅱ)中，R41、R42、R43、R44和R45各自独立地选自-H、卤素、-NO2、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、苯基和C1～C4烷基；或R41、R42、R43、R44和R45中的至少两个成环并参与形成稠合环，R41、R42、R43、R44和R45中为成环的基团各自独立地选自-H、卤素、-NO2、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、苯基和C1～C4烷基。
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地为-H、-F、-Cl、-Br、-I、-NO2或-CN。
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、-F、-Cl、-Br、-I、-NO2。
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自C1～C4烷氧基；进一步可以各自独立地选自-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH3)2、-OCH2CH2CH2CH3、-OCH2CH(CH3)2、-OCH(CH3)CH2CH3、-OC(CH3)3。
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自C1～C6烷基，即C1烷基、C2烷基、C3烷基、C4烷基、C5烷基或C6烷基；进一步可以各自独立地选自：乙基(Et、-CH2CH3)、1-丙基(n-Pr、n-丙基、-CH2CH2CH3)、1-甲基乙基(i-Pr、i-丙基、-CH(CH3)2)、1-丁基(n-Bu、n-丁基、-CH2CH2CH2CH3)、1-甲基丙基(s-Bu、s-丁基、-CH(CH3)CH2CH3)、2-甲基丙基(i-Bu、i-丁基、-CH2CH(CH3)2)、1,1-二甲基乙基(t-Bu、t-丁基、-C(CH3)3)、1-戊基(n-戊基、-CH2CH2CH2CH2CH3)、1-甲基丁基(-CH(CH3)CH2CH2CH3)、1-乙基丙基(-CH(CH2CH3)2)、1,1-二甲基丙基(-C(CH3)2CH2CH3)、1,2-二甲基丙基(-CH(CH3)CH(CH3)2)、3-甲基丁基(-CH2CH2CH(CH3)2)、2-甲基丁基(-CH2CH(CH3)CH2CH3)、2,2-二甲基丙基(-CH2C(CH3)3)、1-己基(-CH2CH2CH2CH2CH2CH3)、1-甲基戊基(-CH(CH3)CH2CH2CH2CH3)、1-乙基丁基(-CH(CH2CH3)CH2CH2CH3)、1,1-二甲基丁基(-C(CH3)2CH2CH2CH3)、1，2-二甲基丁基(-CH(CH3)CH(CH3)CH2CH3)、1,3-二甲基丁基(-CH(CH3)CH2CH(CH3)2)、1-甲基-1-乙基丙基(-C(CH3)(CH2CH3)2)、2-甲基-1-乙基丙基(-CH(CH2CH3)CH(CH3)2)、1,1,2-三甲基丙基(-C(CH3)2CH(CH3)2)、1,2,2-三甲基丙基(-CH(CH3)C(CH3)3、2-甲基戊基(-CH2CH(CH3)CH2CH2CH3)、4-甲基戊基(-CH2CH2CH2CH(CH3)2)、3-甲基戊基(-CH2CH2CH(CH3)CH2CH3)、2-乙基丁基(-CH2CH(CH2CH3)2)、2,3-二甲基丁基(-CH2CH(CH3)CH(CH3)2)、3,3-二甲基丁基(-CH2CH2C(CH3)3)和2,2-二甲基丁基(-CH2C(CH3)2CH2CH3)，以及卤素取代的C1～C6烷基；卤素取代的C1～C6烷基，例如-CF3、-CF2CF3、-C(CF3)3等。
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自苯基和取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素和C1～C4烷基。
在一些实施方式中，式(Ⅰ)结构中的R12、R13、R14、R15、R22、R23、R24和R25为H。
在一些实施方式中，式(Ⅰ)结构中的R11和R21选自相同的基团。
在一些实施方式中，所述磷酸二苯酯类具有式(Ⅰ-1)所示的结构：
在一些实施方式中，式(Ⅰ)结构中的R11、R13、R14、R15、R21、R23、R24和R25为H。
在一些实施方式中，式(Ⅰ)结构中的R12和R22选自相同的基团。
在一些实施方式中，所述磷酸二苯酯类具有式(Ⅰ-2)所示的结构：
在一些实施方式中，式(Ⅰ)结构中的R11、R12、R14、R15、R21、R22、R24和R25为H。
在一些实施方式中，式(Ⅰ)结构中的R13和R23选自相同的基团。
在一些实施方式中，所述磷酸二苯酯类具有式(Ⅰ-3)所示的结构：
在一些实施方式中，式(Ⅰ)结构中的R12、R13、R14、R22、R23和R24为H。
在一些实施方式中，式(Ⅰ)结构中的R11、R15、R21和R25选自相同的基团。
在一些实施方式中，所述磷酸二苯酯类具有式(Ⅰ-4)所示的结构：
在一些实施方式中，式(Ⅰ)结构中的R12、R14、R22和R24为H。
在一些实施方式中，式(Ⅰ)结构中的R11、R13、R15、R21、R23和R25选自相同的基团。
在一些实施方式中，所述磷酸二苯酯类具有式(Ⅰ-5)所示的结构：
在一些实施方式中，式(Ⅱ)结构中的R3和R3’各自独立地选自-H、-SiPh3 “*”代表连接位点。
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45各自独立地为-H、-F、-Cl、-Br、-I、-NO2或-CN。
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45各自独立地选自-H、-F、-Cl、-Br、-I、-NO2。
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45各自独立地选自C1～C6烷基，即C1烷基、C2烷基、C3烷基、C4烷基、C5烷基或C6烷基；进一步可以各自独立地选自：乙基(Et、-CH2CH3)、1-丙基(n-Pr、n-丙基、-CH2CH2CH3)、1-甲基乙基(i-Pr、i-丙基、-CH(CH3)2)、1-丁基(n-Bu、n-丁基、-CH2CH2CH2CH3)、1-甲基丙基(s-Bu、s-丁基、-CH(CH3)CH2CH3)、2-甲基丙基(i-Bu、i-丁基、-CH2CH(CH3)2)、1,1-二甲基乙基(t-Bu、t-丁基、-C(CH3)3)、1-戊基(n-戊基、-CH2CH2CH2CH2CH3)、1-甲基丁基(-CH(CH3)CH2CH2CH3)、1-乙基丙基(-CH(CH2CH3)2)、1,1-二甲基丙基(-C(CH3)2CH2CH3)、1,2-二甲基丙基(-CH(CH3)CH(CH3)2)、3-甲基丁基(-CH2CH2CH(CH3)2)、2-甲基丁基(-CH2CH(CH3)CH2CH3)、2,2-二甲基丙基(-CH2C(CH3)3)、1-己基(-CH2CH2CH2CH2CH2CH3)、1-甲基戊基(-CH(CH3)CH2CH2CH2CH3)、1-乙基丁基(-CH(CH2CH3)CH2CH2CH3)、1,1-二甲基丁基(-C(CH3)2CH2CH2CH3)、1，2-二甲基丁基(-CH(CH3)CH(CH3)CH2CH3)、1,3-二甲基丁基(-CH(CH3)CH2CH(CH3)2)、1-甲基-1-乙基丙基(-C(CH3)(CH2CH3)2)、2-甲基-1-乙基丙基(-CH(CH2CH3)CH(CH3)2)、1,1,2-三甲基丙基(-C(CH3)2CH(CH3)2)、1,2,2-三甲基丙基(-CH(CH3)C(CH3)3、2-甲基戊基(-CH2CH(CH3)CH2CH2CH3)、4-甲基戊基(-CH2CH2CH2CH(CH3)2)、3-甲基戊基(-CH2CH2CH(CH3)CH2CH3)、2-乙基丁基(-CH2CH(CH2CH3)2)、2,3-二甲基丁基(-CH2CH(CH3)CH(CH3)2)、3,3-二甲基丁基(-CH2CH2C(CH3)3)和2,2-二甲基丁基(-CH2C(CH3)2CH2CH3)，以及卤素取代的C1～C6烷基；卤素取代的C1～C6烷基，例如-CF3、-CF2CF3、-C(CF3)3等。
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45各自独立地选自苯基和取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基取代的苯基；例如4-ClC6H4、4-NO2C6H4、4-CH3C6H4、4-CF3C6H4、4-t-BuC6H4、4-PhC6H4、4-(2,4,6-(CH3)3C6H2)C6H4、3,5-(CF3)2C6H3、3,5-t-Bu2C6H3、3,5-Ph2C6H3、2,4,6-CH3C6H2、2,4,6-(i-Pr)3C6H2。烷基取代的苯基包括烷基对苯基的至少一个位点的取代，例如R42和R44均选自多个甲基取代的苯基，如2,4,6-(CH3)3C6H2时，R3和R3’可以各自独立地选自-5’-2,2”,4,4”,6,6”-六甲基-1,1’:3”,1”-三联苯基
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45各自独立地选自苯基和取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、苯基和C1～C4烷基取代的苯基；例如4-ClC6H4、4-NO2C6H4、4-CH3C6H4、4-CF3C6H4、4-t-BuC6H4、4-PhC6H4、4-(2,4,6-(CH3)3C6H2)C6H4、3,5-(CF3)2C6H3、3,5-t-Bu2C6H3、3,5-Ph2C6H3、2,4,6-CH3C6H2、2,4,6-(i-Pr)3C6H2。烷基取代的苯基包括烷基对苯基的至少一个位点的取代，例如R42和R44均选自多个甲基取代的苯基，如2,4,6-(CH3)3C6H2时，R3和R3’可以各自独立地选自-5’-2,2”,4,4”,6,6”-六甲基-1,1’:3”,1”-三联苯基。
在一些实施方式中，式(Ⅱ)结构中的R41、R42、R43、R44和R45中的两个及以上取代基形成稠合 环；进一步地，R41、R42、R43、R44和R45形成的稠合环为1-萘基2-萘基4-β-萘基-苯基9-蒽基9-菲基
在一些实施方式中，所述式(Ⅱ)所示的结构式还可以为其R构型或S构型
在一些实施方式中，所述有机碱类选自1,8-二氮杂双环[5.4.0]十一碳-7-烯1,5,7-三叠氮双环[4.4.0]癸-5-烯7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯4-二甲氨基吡啶以及磷腈碱类化合物中的一种或多种。
在一些实施方式中，所述的再生处理方法中，所述有机碱类选自含氮杂双环碱类、4-二甲氨基吡啶和磷腈碱类化合物中的一种或多种。
在一些实施方式中，所述含氮杂双环碱类选自具有式(Ⅲ)所示的结构：
式(Ⅲ)，Y是-CH2-、-NH-或-N(CH3)-；n是1或2。
在一些实施方式中，所述磷腈碱类化合物具有式(Ⅳ)所示的结构：
式(Ⅳ)中，R为卤素、C1～C4烷基或C1～C4烷氧基。磷腈碱类化合物是指单体或其聚合物，例如 叔丁基亚氨基-三(二甲氨基)正膦1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)环三磷腈碱(如)和1-叔丁基-4,4,4-三(二甲氨基)-2,2-二[三(二甲氨基)-正膦亚基氨基]-2Λ5,4Λ5-连二(磷氮基化合物)
在一些实施方式中，所述磷酸二苯酯类催化剂选自磷酸二苯酯、双(4-硝基苯基)磷酸酯、双(4-氟苯基)磷酸酯、双(4-三氟甲基苯基)磷酸酯、双(4-氯苯基)磷酸酯、双(4-甲氧基苯基)磷酸酯和双(4-甲基苯基)磷酸酯中的一种或多种。
在一些实施方式中，所述磷酸二苯酯类催化剂选自磷酸二苯酯、双(4-硝基苯基)磷酸酯和双(2,6-二甲基苯基)磷酸酯中的一种或多种。
在一些实施方式中，所述联萘酚磷酸酯类催化剂选自联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯和R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯中的一种或多种。
在一些实施方式中，所述有机碱类催化剂选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶、叔丁基亚氨基-三(二甲氨基)正膦、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)和环三磷腈碱和1-叔丁基-4,4,4-三(二甲氨基)-2,2-二[三(二甲氨基)-正膦亚基氨基]-2Λ5,4Λ5-连二(磷氮基化合物)中的一种或多种。
在一些实施方式中，所述的再生处理方法中，所述磷酸二苯酯类选自磷酸二苯酯(diphenylphosphate，简称DPP)、双(4-硝基苯基)磷酸酯(bis(4-nitrophenyl)phosphate，简称BNPP)、双(4-氟苯基)磷酸酯(bis(4-fluorophenyl)phosphate，简称BFPP)、双(4-三氟甲基苯基)磷酸酯(bis(4-trifluoromethylphenyl)phosphate，简称BTFPP)、双(4-甲基苯基)磷酸酯(bis(4-methylphenyl)phosphate，简称BMPP)、双(4-甲氧基苯基)磷酸酯(bis(4-methoxyphenyl)phosphate，简称BMOPP)、双(2,6-二甲基苯基)磷酸酯(di(2,6-xylyl)phosphate，简称DXP)，所述联萘酚磷酸酯类选自联萘酚磷酸酯(1,1'-binaphthyl-2,2'-diyl hydrogenphosphate，简称BNDHP)、R-联萘酚磷酸酯((R)-(-)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate，简称R-BNDHP)、R-3,3’-二(三苯基硅基)联萘酚膦酸酯((R)-(-)-3,3'-bis(triphenylsilyl)-1,1'-binaphthyl-2,2'-diylhydrogenphosphate，简称R-TiPSY)、R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯((R)-3,3'-Bis(2,4,6-trisopropylphenyl)-1,1'-binapthyl-2,2'-diyl hydrogenphosphate，简称R-TRIP)，所述有机碱类选自1,8-二氮杂双环[5.4.0]十一碳-7-烯(1,8-diazabicyclo[5.4.0]undec-7-ene，简称DBU)、1,5,7-三叠氮双环[4.4.0]癸-5-烯(1,5,7-triazabicyclo[4.4.0]dec-5-ene，简称TBD)、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯(7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene，简称MTBD)、4-二甲氨基吡啶(4-dimethylaminopyridine，简称DMAP)和环三磷腈碱(cyclic trimeric phosphazenebase，简称CTPB)中的一种或多种。
在一些实施方式中，所述的再生处理方法中，所述磷酸二苯酯类选自磷酸二苯酯、双(4-硝 基苯基)磷酸酯、双(2,6-二甲基苯基)磷酸酯，所述联萘酚磷酸酯类选自联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯、R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯，所述有机碱类选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶和环三磷腈碱中的一种或多种。
在一些实施方式中，有机非金属催化剂可选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类。例如磷酸二苯酯、双(4-硝基苯基)磷酸酯、双(4-氟苯基)磷酸酯、双(4-三氟甲基苯基)磷酸酯、双(4-甲基苯基)磷酸酯、双(4-甲氧基苯基)磷酸酯、双(2,6-二甲基苯基)磷酸酯、联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯、R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯、1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶和环三磷腈碱中的一种或多种。上述选用的有机非金属催化剂大都为成熟的商业化产品，不仅价廉易得而且能够催化可降解高分子材料高效水解，获得聚合度低(例如可以实现接近于单体，也可以是聚合度低于10的低聚物)的降解产物。经本申请提供的方法处理获得的低分子量降解产物可作为原料再次利用，例如可用于聚合物的制备，实现高效地闭环回收利用可降解高分子材料废弃物。
在一些实施方式中，有机非金属催化剂可选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类。例如磷酸二苯酯、双(4-硝基苯基)磷酸酯、双(2,6-二甲基苯基)磷酸酯、联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯、R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯、1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶和环三磷腈碱中的一种或多种。
上述可降解高分子材料的再生处理方法中，可降解高分子材料的转化率较高，降解产物聚合度低(例如接近单体水平)，降解反应后体系中低分子量组合物可实现较高占比(例如超过95％)。另外，该处理方法对设备要求低，后处理操作简单、工艺绿色环保，成本低。
可以理解地，该再生处理方法可以高效地将可降解高分子材料降解为单体和/或低聚物。也可以通过调整反应原料、工艺参数(例如反应体系中水的含量、催化剂的含量、反应时间、反应温度和反应压力等)，将降解的程度控制在一定范围内，即获得具有一定分子量及分布和/或一定转化率的降解产物。该具有一定分子量及分布和/或一定转化率的降解产物可以在不进行纯化等处理的条件下，或者经过简单的分离处理的条件下，直接或便捷地作为聚合反应的原料，经聚合等反应制备可降解高分子材料。
在本申请第一方面的再生处理方法中，经降解处理后，可降解高分子材料被降解成分子量降低的产物。
在一些实施方式中，降解产物基本为低分子量产物。在本申请中，如无其他说明，低分子量产物主要指分子量≤1500Da的降解产物。
如无特别说明，本申请中的“低聚物”和“寡聚物”具有相同含义，可以互换使用。
在一些实施方式中，降解产物可以包括单体和/或接近单体水平的低聚物。
如无特别说明，本申请中的低聚物或寡聚物主要是指分子量≤1500Da的含较少重复单元的聚合物。
降解产物中一部分分子，当分子量较低(如PLA低聚物分子量≤500Da，对应于聚合度≤6.9)时，可以是水溶性的，因此，降解产物中的水溶性分子记为“水溶性小分子”。
如无特别说明，本申请中“接近单体水平低聚物(寡聚物)”主要是指聚合度≤10的低聚物，也可记为“类单体低聚物”或“类单体寡聚物”。
以聚酯材料中的聚乳酸(polylactic acid，简称PLA)为例，聚乳酸在有机非金属催化剂和水存在的条件下，可持续降解，形成基本由单体和/或低聚物(如单体和/或接近单体水平的低聚物)构成的低分子量降解产物。该低分子量降解产物可以直接作为原料进行高效的聚合反应，可用来制备具有一定分子量的聚合产物(如数均分子量≥50kDa)。还可以在采用前述方法对聚乳酸材料进行再生处理的过程中(在有机非金属催化剂和水存在的条件下)，通过适当调整原料配比、工艺参数等将反应体系中降解产物的聚合度控制在一定的水平(例如≤8)，再将降解产物体系中的降解产物先用于制备丙交酯，进而以丙交酯为原料制备得到高分子量的聚合产物(如数均分子量≥150kDa)。
在一些实施方式中，所述的再生处理方法中，所述可降解高分子材料的数均分子量为10kDa～250kDa，进一步可以为10kDa～150kDa，更进一步可以为10kDa～130kDa，还可以选自如下任一种数均分子量数值或任两种数均分子量数值构成的区间：10kDa、20kDa、30kDa、40kDa、50kDa、60kDa、70kDa、80kDa、90kDa、100kDa、110kDa、120kDa、130kDa、140kDa、150kDa、160kDa、170kDa、180kDa、190kDa、200kDa、210kDa、220kDa、230kDa、240kDa、250kDa等。
在一些实施方式中，所述的再生处理方法中，所述可降解高分子材料的重均分子量为10kDa～500kDa，进一步可以为10kDa～250kDa，更进一步可以为30kDa～230kDa，还可以选自如下任一种重均分子量数值或任两种重均分子量数值构成的区间：10kDa、20kDa、30kDa、40kDa、50kDa、60kDa、70kDa、80kDa、90kDa、100kDa、110kDa、120kDa、130kDa、140kDa、150kDa、 160kDa、170kDa、180kDa、190kDa、200kDa、210kDa、220kDa、230kDa、240kDa、250kDa、260kDa、270kDa、280kDa、290kDa、300kDa、310kDa、320kDa、330kDa、340kDa、350kDa、360kDa、370kDa、380kDa、390kDa、400kDa、410kDa、420kDa、430kDa、440kDa、450kDa、460kDa、470kDa、480kDa、490kDa、500kDa等。
在一些实施方式中，所述的再生处理方法中，所述体系中水相对于所述可降解高分子材料的质量比为(0.01～10):1，进一步可以为(0.1～1)：1，更进一步可以为(0.08～0.33)：1：，还可以选自如下任一种质量比或任两种质量比构成的区间：(0.01：1)、(0.02：1)、(0.03：1)、(0.04：1)、(0.05：1)、(0.06：1)、(0.07：1)、(0.08：1)、(0.083：1)、(0.1：1)、(0.15：1)、(0.156：1)(0.2：1)、(0.25：1)、(0.3：1)、(0.31：1)、(0.32：1)、(0.33：1)、(0.34：1)、(0.35：1)、(0.36：1)、(0.37：1)、(0.38：1)、(0.39：1)、(0.4：1)、(0.5：1)、(0.6：1)、(0.7：1)、(0.8：1)、(0.9：1)、(1：1)、(1.3：1)、(1.5：1)、(2：1)、(2.5：1)、(3：1)、(3.5：1)、(4：1)、(4.5：1)、(5：1)、(5.5：1)、(6：1)、(6.5：1)、(7：1)、(7.5：1)、(8：1)、(8.5：1)、(9：1)、(9.5：1)、(10：1)。较合适的水量相对于所述可降解高分子材料的质量比更有利于提高可降解高分子材料的降解速度。若所述体系中水量相对于所述可降解高分子材料的质量比偏高，常压下体系内部温度难以超过溶剂沸点(以水为例，100℃)，减缓反应进程，且作为原料的水会暴沸、大量挥发，存在一定操作危险性；若所述体系中水量相对于所述可降解高分子材料的质量比偏低，可能造成作为原料参与反应的量不足，反应物间接触概率降低，反应速度可能减缓，可能导致最终产物的聚合度较高。
在一些实施方式中，所述的再生处理方法中，所述有机非金属催化剂相对于所述可降解高分子材料的质量比为(0.001～0.1)：1，进一步可以为(0.01～0.05：1)，更进一步可以为(0.035～0.05：1)，还可以选自如下任一种质量比或任两种质量比构成的区间：(0.001：1)、(0.002：1)、(0.003：1)、(0.004：1)、(0.005：1)、(0.006：1)、(0.007：1)、(0.008：1)、(0.0088：1)、(0.009：1)、(0.01：1)、(0.015：1)、(0.02：1)、(0.025：1)、(0.03：1)、(0.031：1)、(0.032：1)、(0.033：1)、(0.034：1)、(0.035：1)、(0.036：1)、(0.037：1)、(0.038：1)、(0.039：1)、(0.04：1)、(0.045：1)、(0.05：1)、(0.06：1)、(0.07：1)、(0.08：1)、(0.09：1)、(0.1：1)等。较合适的催化剂量相对于可降解高分子材料的质量比更有利于降低回收方案的经济成本。若催化剂相对于可降解高分子材料的质量比偏高，大量催化剂的使用增加了再生处理的原料成本；若催化剂相对于可降解高分子材料的质量比偏低，可能造成降解速度过慢，时间成本和能耗增加。
可降解高分子材料的降解处理可以在催化剂用量较小的条件下进行，而且催化效率高，成本较低。
在一些实施方式中，所述的再生处理方法中，所述降解产物的平均聚合度≤20，进一步可以为≤15，更进一步可以为≤10，还可以选自如下任一种平均聚合度数值或任两种平均聚合度数值构成的区间：1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20等。所述降解产物的平均聚合度还可以选自如下任一种范围，例如1～20、1～15、1～10、2～20、2～15、2～12、2～10、2.3～9.6等。
平均聚合度分析方法：数均分子量(Mn)÷重复单元分子量。以聚乳酸(Mn＝121kDa)原料为例，其重复单元分子量为72Da，将数均分子量扣除端基所占分子量18Da后计算得到平均聚合度，
在一些实施方式中，所述的再生处理方法中，所述降解产物中的单体所占摩尔百分比≥30％，进一步可以为≥50％，更进一步可以为≥80％，还可以选自如下任一种单体所占摩尔百分比数值或任两种单体所占摩尔百分比数值构成的区间：30％、35％、40％、45％、50％、55％、60％、65％、80％、90％等。所述降解产物中的单体所占摩尔百分比还可以选自如下任一种范围，例如30％～60％、30％～70％、30％～80％、30％～90％、30％～100％等。可以理解地，采用前述再生处理方法对可降解高分子材料进行降解处理，随着降解处理时间的延长，降解产物中单体所占摩尔百分比的数值可以更高。本申请中，如无特别说明，降解产物中单体所占摩尔百分比指：单体的摩尔数占降解产物总摩尔数的百分比。
以聚乳酸的降解产物为例，将其溶于DMSO-d6中通过傅里叶变换核磁共振波谱仪表征得到1HNMR谱图，通过下式计算得到乳酸的摩尔占比(lactic acid content)：
其中，I1.23是1.23ppm处对应于乳酸单体的甲基(HOOCCH(CH3)OH)特征峰的积分值，I1.27是1.27ppm处对应于乳酸低聚物的端甲基(-COCH(CH3)OH)特征峰的积分值。可以理解，进行不同批次的测试时，上述特征峰峰位1.23ppm及1.27ppm的化学位移有可能发生偏移，不过，本领域技术人员可 以根据特征峰归属方法确定实测得到的1H NMR谱图中与1.23ppm及1.27ppm相对应的特征峰位。
在一些实施方式中，所述的再生处理方法中，在降解产物中，低分子量产物相对于降解产物的质量占比为≥80％，进一步可以为≥90％，更进一步可以为≥95％。
本申请中，如无特别说明，体系中低分子量产物的质量占比指：低分子量产物在所述降解产物中所占的重量百分比。本申请中认为反应体系中均为低分子量产物的标准是通过凝胶渗透色谱(Gel Permeation Chromatography，简称GPC)和傅里叶变换核磁共振(Nuclear Magnetic Resonance，简称NMR)波谱仪检测降解产物，未出现高聚物特征峰。以PLA的降解产物为例，在GPC谱图中流出峰整体后移，基本观察不到分子量超过1500Da的分子对应的峰的信号，在1H NMR谱图中，基本观察不到聚合物对应的甲基特征峰(1.5～1.6ppm)和次甲基特征峰(5.3～5.5ppm)的信号。
在一些实施方式中，所述的再生处理方法中，在降解产物中，低分子量产物的质量相对于降解产物总质量的百分占比为≥80％，进一步可以为≥90％，更进一步可以为≥95％。
在一些实施方式中，所述的再生处理方法中，所述水溶性小分子转化率≥20％，进一步可以为≥23％，还可以选自如下任一种水溶性小分子转化率数值或任两种水溶性小分子转化率数值构成的区间：20％、23.7％、25％、30％、32.6％、35％、40％、45％、50％、53％、55％、60％、61.6％、65％、70％、72.1％、74.1％、75％、80％、85％、86％、88.3％、90％、90.4％、91％、92.8％、95％、99.2％等。可以理解地，采用前述再生处理方法对可降解高分子材料进行降解处理，随着降解处理时间的延长，降解产物中水溶性小分子转化率的数值可以更高。
本申请中，如无特别说明，聚合物原料转化为水溶性小分子的转化率(以下简称为“水溶性小分子转化率”)是指体系持续反应到预设的中止或终止条件，最初原料经过降解反应已经降解并溶于水的量与最初原料的比值，更详细而言可以用质量比作为计算和判断的标准。在数值上，“水溶性小分子的转化率”可根据降解产物中水溶性产物(对应水溶性小分子)相对于被降解原料(也即聚合物原料)的质量百分比计算得到。
水溶性小分子转化率计算方法：将降解后的产物置于去离子水中在室温下搅拌溶解0.5h，离心后收集不溶沉淀物冻干并称量，通过下式计算得到聚合物转化为水溶性小分子的转化率(conversion，质量比)：
其中，minput是反应前聚合物的质量，mresidue是反应后残余不溶物的质量。
在一些实施方式中，所述的再生处理方法，所述可降解高分子材料的多分散系数(PDI)≤3.3，进一步可以为1～3.3，更进一步可以为1～3.27。
本申请中，如无特别说明，多分散系数(polydispersity index，记为PDI)，用于描述聚合物分子量分布。多分散系数(PDI)的计算方法为Mw除以Mn所得的比值；该数值越大，表明分子量分布越宽。在数值上，PDI还可以等于摩尔质量分散度(molar-mass dispersity，记为DM)。
在一些实施方式中，所述可降解高分子材料选自聚乳酸(poly(lactic acid)，简称PLA)、聚羟基乙酸(poly(glycolic acid)，简称PGA)、聚ε-己内酯(poly(ε-caprolactone)，简称PCL)、聚乳酸-羟基乙酸共聚物(poly(lactic-co-glycolic acid)，简称PLGA)、聚羟基乙酸-ε-己内酯共聚物(poly(glycolic acid-co-caprolactone)，简称PCGA)、聚乳酸-ε-己内酯共聚物(poly(lactic acid-co-caprolactone)，简称PCLA)、聚δ-戊内酯(poly(δ-valerolactone)，简称PVL)、聚丁内酯(poly(β-butyrolactone)，简称PBL)、聚丁二酸丁二醇酯(poly(butylene succinate)，简称PBS)、聚己二酸/对苯二甲酸丁二酯(poly(butylene adipate terephthalate)，简称PBAT)、聚羟基脂肪酸酯(polyhydroxyalkanoates，简称PHA)和聚三亚甲基碳酸酯(poly(trimethylene carbonate)，简称PTMC)中的一种或多种。
在一些实施方式中，所述的再生处理方法包括以下步骤：在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行第1次降解处理，得到第1降解产物；混合第i降解产物和第i+1可降解高分子材料，进行第i+1次降解处理，得到第i+1降解产物，其中，i为≥1的整数，所述第i+1可降解高分子材料至少包括第2可降解高分子材料；至i+1＝n时结束降解处理，得到第n降解产物，其中n为≥2的整数，所述第n降解产物的平均聚合度≤10。
本申请中向降解产物中继续添加可降解高分子材料和水，反应体系中催化剂的含量降低，进行二次的降解反应，仍能够得到可降解高分子材料所对应的低聚物和/或单体，也即该可降解高分子材料的再生处理可以连续进行，从而有利于工业化连续生产。
以n＝2为例，所述的再生处理方法，包括以下步骤：
(1)在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行 第1次降解处理，得到第1降解产物；
(2)混合第1降解产物和第2可降解高分子材料，进行第2次降解处理，得到第2降解产物，所述第2降解产物的平均聚合度可参阅前文定义，例如≤20，进一步例如≤10等。
以n＝4为例，在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行第1次降解处理，得到第1降解产物；
混合第1降解产物和第2可降解高分子材料，进行第2次降解处理，得到第2降解产物；
混合第2降解产物和第3可降解高分子材料，进行第3次降解处理，得到第3降解产物；
混合第3降解产物和第4可降解高分子材料，进行第4次降解处理，得到第4降解产物；所述第4降解产物的平均聚合度可参阅前文定义，例如≤20，进一步例如≤10等。
以n＝10为例，所述的再生处理方法，包括以下步骤：
在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行第1次降解处理，得到第1降解产物；
混合第1降解产物和第2可降解高分子材料，进行第2次降解处理，得到第2降解产物；
重复“将降解产物与添加的新的可降解高分子材料，进行降解处理”的步骤8次，结束降解处理，得到第10降解产物，所述第10降解产物的平均聚合度可参阅前文定义，例如≤20，进一步例如≤10等。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的温度独立地为25℃～200℃，进一步可以为50℃～200℃，更进一步可以为125℃～200℃。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的温度独立地为125℃～200℃，进一步可以为130℃～200℃，更进一步可以为140℃～180℃，还可以选自以下任一种温度或任两种温度构成的区间：125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃、200℃等。较合适的反应温度有利于提高可降解高分子材料的降解效率。若反应的温度偏高，可能造成体系中水分蒸发剧烈，一方面损失了反应原料，另一方面使得操作具有一定危险性，对反应设备提出了更高的要求；若反应的温度偏低，可能造成反应速度较慢，可降解高分子材料降解为寡聚物和/或单体耗时较长，增加时间成本和能耗。
本申请中，降解处理的温度可以为反应体系的实际温度，也可以为反应体系的环境温度，例如水浴温度、油浴温度等。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的时间独立地为0.1h～5h，可选为0.25h～5h，进一步可以为0.5h～4h，更进一步可以为1h～4h，更进一步可以为1.5h～4h，还可以选自以下任一种时间或任两种时间构成的区间：0.1h、0.25h、0.5h、0.75h、1h、1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h、4h；还可以选自以下任一种时间或任两种时间构成的区间：0.25h、0.5h、0.75h、1h、1.2h、1.4h、1.6h、1.8h、2h、2.2h、2.4h、2.6h、2.8h、3h、3.2h、3.4h、3.6h、3.8h、4h。较合适的反应时间有利于更高效地得到目标产物。若反应的时间偏长，可能造成时间成本和能耗增加；若反应的时间偏低，可能造成降解产物不符合回收利用的要求。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的温度独立地为125℃～200℃，任一次降解处理的时间独立地为0.1h～5h，可选为0.25h～5h。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的温度独立地为130℃～200℃，任一次降解处理的时间独立地为1h～4h。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的温度独立地为140℃～180℃，任一次降解处理的时间独立地为1.5h～4h。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的压力可以独立地为1atm-100atm。还可以选自以下任一种压力或任两种压力构成的区间：1atm、10atm、20atm、30atm、40atm、50atm、60atm、70atm、80atm、90atm、100atm等。
在一些实施方式中，所述的再生处理方法中，任一次降解处理的压力独立地为100±5kPa。还可以选自以下任一种压力或任两种压力构成的区间：95kPa、96kPa、97kPa、98kPa、100kPa、101kPa、102kPa、103kPa、104kPa、105kPa等。该再生过程可以在非密封环境及非高温高压条件下进行，催化降解的效率高，可降解高分子材料可以迅速转化为可再次利用的寡聚物和/或单体原料。通过调节反应压力，可以影响溶剂沸点进而影响体系内部温度，此外，还会影响分子运动的剧烈程度，这些都会影响反应速率。若反应的压力偏高，体系内部温度上升且分子碰撞更剧烈，反应变快，但对设备提出了更高的要求；若反应的压力偏低，可能造成体系内部温度偏低且分子碰撞概率减小进而发生反应的概率变低，使得反应减缓。
对可降解高分子材料的降解处理可以在非强酸、强碱和无有机溶剂存在的条件下进行，有助 于改善工业化应用中设备腐蚀和废水排放的问题。
在一些实施方式中，所述的再生处理方法，还包括以下步骤：
采用有机溶剂洗涤所述降解产物；其中，所述有机溶剂选自氯仿、石油醚、二硫化碳、乙醚、二氯甲烷、苯、甲苯和乙酸乙酯中的一种或多种。可以理解地，采用有机溶剂洗涤降解产物的过程也称为萃取处理。
经过降解处理的降解产物通过简单的洗涤(例如萃取)，实现与有机非金属催化剂有效分离，经分离的降解产物可直接作为聚合过程的原料，无需浓缩或再次纯化，便于工业化生产。
在一些实施方式中，所述的再生处理方法包括以下步骤：将可降解高分子材料、有机非金属催化剂和水加入反应容器中，在分散条件下(如在搅拌条件下)在125℃～200℃条件下进行降解反应(可选地，降解时间可以如前文定义，例如可以为0.1h～5h，进一步可以为0.25h～5h)；进一步地，有机非金属催化剂：水：可降解高分子材料的质量比可以为(0.001～0.1)：(0.08～10)：1。所述的再生处理方法中，降解反应可以于100±5kP大气环境中进行。在一些实施例中，降解反应可以于1atm-100atm压力环境下中进行。
在一些实施方式中，所述的再生处理方法包括以下步骤：将可降解高分子材料、有机非金属催化剂和水加入反应容器中，在分散条件下(如在搅拌条件下)在125℃～200℃条件下进行降解反应(可选地，降解时间可以如前文定义，例如可以为0.1h～5h，进一步可以为0.25h～5h)，冷却后经有机溶剂洗涤；进一步地，有机非金属催化剂：水：可降解高分子材料的质量比可以为(0.001～0.1)：(0.08～10)：1；更进一步地，有机溶剂可以为氯仿、石油醚、二氯甲烷中的任一种或其任意组合，更进一步地，有机溶剂可以为氯仿、石油醚、二氯甲烷中的任一种。所述的再生处理方法中，降解反应可以于100±5kP大气环境中进行。在一些实施例中，降解反应可以于1atm-100atm压力环境下中进行。
在一些实施方式中，所述的再生处理方法包括以下步骤：将可降解高分子材料、有机非金属催化剂和水加入反应容器中，在分散条件下(如在搅拌条件下)在160±20℃条件下进行降解反应(可选地，降解时间可以如前文定义，例如可以为1.5±1h)，冷却后经有机溶剂洗涤；进一步地，有机非金属催化剂：水：可降解高分子材料的质量比可以为(0.035±0.02)：(0.3±0.1)：1；更进一步地，有机溶剂可以为氯仿、石油醚、二氯甲烷中的任一种。所述的再生处理方法中，降解反应可以于100±5kP大气环境中进行。在一些实施例中，降解反应可以于1atm-100atm压力环境下中进行。
在一些实施方式中，所述的再生处理方法包括以下步骤：将可降解高分子材料、有机非金属催化剂和水加入反应容器中，在分散条件下(如在搅拌条件下)在160±10℃条件下进行降解反应(可选地，降解时间可以如前文定义，例如可以为1.5±0.5h)，冷却后经有机溶剂洗涤；进一步地，有机非金属催化剂：水：可降解高分子材料的质量比可以为(0.035±0.005)：(0.3±0.05)：1；更进一步地，有机溶剂可以为氯仿、石油醚、二氯甲烷中的任一种。所述的再生处理方法中，降解反应可以于100±5kP大气环境中进行。在一些实施例中，降解反应可以于1atm-100atm压力环境下中进行。
在一些实施方式中，所述的再生处理方法包括以下步骤：将可降解高分子材料、有机非金属催化剂和水加入反应容器中，在分散条件下(如在搅拌条件下)在160±10℃条件下进行降解反应(可选地，降解时间可以如前文定义，例如可以为1.5±0.5h)，冷却后经有机溶剂洗涤；进一步地，有机非金属催化剂：水：可降解高分子材料的质量比可以为(0.0035±0.001)：(0.15±0.05)：1；更进一步地，有机溶剂可以为氯仿、石油醚、二氯甲烷中的任一种。所述的再生处理方法中，降解反应可以于100±5kP大气环境中进行。在一些实施例中，降解反应可以于1atm-100atm压力环境下中进行。
本申请的第二方面，提供一种低分子量组合物，其所述低分子量组合物为可降解高分子材料的降解产物，所述低分子量组合物可根据第一方面所述的再生处理方法制备得到。
在一些实施方式中，所述低分子量组合物为第一方面中的低分子量产物。
在一些实施方式中，所述低分子量组合物的平均聚合度≤20，进一步可以为≤15，更进一步可以为≤10，所述低分子量组合物的平均聚合度还可以选自如下任一种平均聚合度数值或任两种平均聚合度数值构成的区间：1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20等。所述降解产物的平均聚合度还可以选自如下任一种范围，例如1～20、1～15、1～10、2～20、2～15、2～12、2～10等。
该低分子量组合物可以由可降解高分子材料(可采用废弃的可降解高分子材料)经过催化剂水解而得到，产物提纯方法简单，过程经济，具有较好的成本优势。
本申请的第三方面，提供一种可降解高分子材料的回收利用方法。
在一些实施方式中，所述的回收利用方法包括如下步骤：以低分子量组合物作为初始原料进行聚合反应；其中，所述低分子量组合物为第一方面所述的再生处理方法制备得到的降解产物或第二方面所述低分子量组合物。
利用可降解高分子材料(可采用废弃的可降解高分子材料)降解得到的低分子量组合物作为原料，可以在传统催化剂的催化下进行聚合反应再次得到该聚合物材料，实现降解高分子材料的二次利用也即回收利用。该回收利用方法不仅具有成本优势而且环境友好。
在一些实施方式中，所述可降解高分子材料的回收利用方法包括如下步骤：S100：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，反应结束后得到含有降解产物的降解产物体系；
S200：将所述降解产物体系作为原料直接用于合成反应。
步骤S100可参阅本申请的第一方面。
步骤S200中的合成反应没有特别限制，只要步骤S100中的降解产物参与反应即可。
在一些实施方式中，步骤S200中，所述降解产物体系作为原料直接用于合成丙交酯，此时，降解产物体系中降解产物的分子量或聚合度要求可参阅前文。例如，降解产物体系中降解产物的平均聚合度≤8，进一步可以平均聚合度≤5等。还例如，可提高降解产物中类单体低聚物所占重量比或摩尔比，例如控制类单体低聚物在降解产物所占重量比或摩尔比大于等于一定数值，例如≥50％、≥80％、≥90％等。
在一些实施方式中，步骤S200中，所述降解产物体系作为原料直接用于聚合反应。可用于制备均聚物或共聚物。
本申请中采用的有机非金属催化剂可以通过简单的分离步骤将其与降解产物分离。此外，根据后续聚合反应或其他处理方式的要求，也可以不将降解产物与有机非金属催化剂分离，而将经过降解处理获得的反应体系直接用于下一步操作。例如，采用有机非金属催化剂磷酸二苯酯DPP催化聚乳酸PLA降解，如果将经过降解处理获得的降解产物体系用于制备丙交酯单体，由于丙交酯的制备过程中通常进行减压蒸馏操作，因此，可以在制备丙交酯的同时实现降解产物体系中的降解产物与有机非金属催化剂磷酸二苯酯DPP的分离，此时，无需预先对降解产物体系进行额外的分离操作；可以直接向体系中添加用于合成丙交酯的催化剂，在催化前述降解产物制备丙交酯的反应过程中，生成的丙交酯可进入接收丙交酯产物的容器中或进入下一步反应流程，实现与降解产物体系各组分及合成丙交酯用催化剂等的分离。
本申请的第四方面，提供一种有机非金属催化剂在对可降解高分子材料进行降解处理中的应用；
其中，所述有机非金属催化剂和所述可降解高分子材料如本申请第一方面中所定义。
采用有机非金属催化剂，可以在温和的条件下将聚酯/聚碳酸酯材料(如废弃的聚酯/聚碳酸酯材料)转化为具有高附加值的产品，获得的产品经过简单除杂即可得到可降解聚酯/聚碳酸酯材料所对应的寡聚物和/或所对应的单体，可以再次用于聚合过程，实现了塑料的循环使用。所得单体水溶液与市售产品的品质相当，经萃取除去催化剂后可用于常规用途。
可以理解地，采用本申请中的技术方案可以将聚酯/聚碳酸酯材料(如废弃的聚酯/聚碳酸酯材料)降解为低分子量的降解产物(例如寡聚物和/或单体)，该降解产物还可以进行下一步合成过程或利用。例如，以聚乳酸为高分子材料(原料)，利用本申请中公开的技术方案，将经过降解处理的降解产物(例如乳酸单体水溶液)经过萃取除杂等常规分离步骤获得乳酸单体。乳酸作为一种用途广泛的平台分子，除制备聚乳酸外，还可用于化工、食品、化妆品、制药等多种行业。以化工领域为例，乳酸可用于制备多种商品和中间化学品，如乳酸酯、1,2-丙二醇、丙烯酸、丙酮酸、乙醛、2,3-戊二酮等。此外，乳酸可用作防冻剂、羊毛织物印花的固定剂，还可以用于软化皮革、除垢、清洁、调节pH等，同时也是一种绿色有机溶剂。以下提供一些实施例。
为更好地理解本申请，下面通过以下实施例对本申请作进一步的阐述，但不可理解为对本申请的限定，对于本领域的技术人员根据上述发明内容所作的一些非本质的改进与调整，也视为落在本申请的保护范围内。
下列实施例中未注明详细条件的实验方法，优先参考本申请中给出的指引，还可以按照本领域的实验手册或常规条件，还可以按照制造厂商所建议的条件，或者参考本领域已知的实验方法。
如无特殊说明，以下各试验所用的原材料皆可从市场上常规购得。
以下各例如无特别限定，本申请中的性能测试方法和评价标准如下所示：
数均分子量(Mn)、重均分子量(Mw)及多分散系数(PDI)测试方法：采用凝胶渗透色谱仪(1260，Agilent)测试得到，将样品以10mg/mL的浓度溶于四氢呋喃(THF)中在35℃下进行测试，流动相为四氢呋喃，流速为1.0mL/min，标样为窄分布的聚苯乙烯(PS)。凝胶渗透色谱仪 测试下限为550Da-600Da。根据样品的1H NMR谱图可计算得到样品的数均分子量(Mn)、平均聚合度和其中单体的摩尔占比，详细测试方法如下：乳酸和/或其寡聚物以100mg/mL的浓度溶于DMSO-d6在25℃下通过傅里叶变换核磁共振波谱仪(400MHz，AVANCE III HD，Bruker)进行测试，测试样中加入少量D2O。其他化合物以10mg/mL的浓度溶于CDCl3进行测试。
实施例1
将2.5g的PLA(可降解高分子材料)，0.0875g的DPP(有机非金属催化剂)和0.75g的去离子水(相当于含水溶剂的体系)加入反应管中，磁子搅拌、通大气下(相当于常压下)，在160℃(环境温度)油浴下反应1.5h，冷却后经氯仿(有机溶剂)洗涤。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.035：0.3：1。
实施例1中所用聚乳酸型号为LX175(TotalEnergies Corbion公司)，采用凝胶渗透色谱仪测得所用PLA的数均分子量(Mn)、重均分子量(Mw)和多分散系数(PDI)分别为121.0kDa、199.7kDa和1.65；所用催化剂为磷酸二苯酯DPP。
采用前述方法进行测试，降解后的产物的分子量低于GPC检测下限，表明其分子量低于600Da。采用核磁共振法测得降解产物的平均分子量为191Da，平均聚合度为2.4，其中90.4％转化为水溶性小分子。经氯仿萃取后的产物的1H NMR谱图如图1所示，处于不同化学环境中的甲基峰位移不同。其中，1.23ppm处为乳酸单体中的甲基(OHCOCH(CH3)OH)峰(图1中标记为a的位置)、1.27ppm处为乳酸低聚物中靠近羟基端的甲基(-COCH(CH3)OH)峰(图1中标记为c的位置)、1.38-1.50ppm处为乳酸低聚物中的其他甲基(-COCH(CH3)O-)峰(图1中标记为f的位置)。4.03-5.50ppm处为乳酸单体及其低聚物中的次甲基对应的峰(图1中标记为b、d、e的位置)，和水峰有所重叠。7.0-7.4ppm处对应于DPP的苯环特征峰(图1中标记为i、h、g的位置)。除2.5ppm处对应于溶剂DMSO-d6的特征峰外，无其他明显信号。降解产物中的单体所占摩尔百分比和聚合物转化为水溶性小分子的转化率的计算方法如前所述，以实施例1为例，计算方法如下：将1.27ppm处对应于乳酸低聚物端甲基的特征峰积分值定为1，1.23ppm处特征峰积分值为1.15，1.38-1.50ppm处特征峰积分值为3.01。计算可得，降解产物数均分子量为(90+72*3.01/(1+1.15)≈191)，降解产物中乳酸单体所占摩尔百分比为1.15/(1+1.15)≈0.535；剩余不溶于水的固体残余物为0.2406g，聚合物转化为水溶性小分子的转化率为(1-0.2406/2.5≈0.904)。
本申请中，如无特别说明，采用凝胶渗透色谱仪对可降解高分子材料进行再生处理(在有机非金属催化剂和水存在条件下)得到的降解产物进行测试，测得的分子量低于GPC检测下限，即说明制得的降解产物中包含的高分子材料的分子量低于600Da。
实施例2
实施例2的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.025g，用于洗涤降解产物的有机溶剂为石油醚。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.01：0.3：1。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为387Da，平均聚合度为5.1，转化率为40.0％。
实施例3
实施例3的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.05g，用于洗涤降解产物的有机溶剂为二氯甲烷。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.02：0.3：1。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为289Da，平均聚合度为3.8，转化率为61.6％。
实施例4
实施例4的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.125g，用于洗涤降解产物的有机溶剂为乙醚。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.05：0.3：1。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为185Da，平均聚合度为2.3，转化率为99.2％。
实施例5～9
实施例5～9的原料和降解处理过程与实施例1基本相同，不同之处在于降解处理的环境温度 不同，分别为120℃、140℃、150℃、170℃和180℃。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量部分低于GPC检测下限，降解产物的转化率及通过测得的核磁共振氢谱计算得到的平均分子量和平均聚合度如表1所示。
表1实施例5～9中洗涤后的降解产物的测试结果
实施例10～13
实施例10～13的原料和降解处理过程与实施例1基本相同，不同之处在于降解处理的时间不同，分别为0.5h、1h、2h和2.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量部分低于GPC检测下限，降解产物的转化率及通过测得的核磁共振氢谱计算得到的平均分子量、平均聚合度和转化率如表2所示。
表2实施例10～实施例13中洗涤后的降解产物的测试结果
实施例14
将2.5g的聚乳酸PLA(相当于第1可降解高分子材料)，0.0875g的磷酸二苯酯DPP，0.75g的去离子水加入反应管中，磁子搅拌、通大气下，在160℃油浴下反应1.5h(相当于第1次降解处理)，所得产物(相当于第1降解产物)的平均分子量以测得的核磁共振氢谱为依据计算得到为191Da再次加入2.5g的PLA(相当于第2可降解高分子材料)和0.35g去离子水，继续反应1.5h(相当于第2次降解处理)，所得降解产物(相当于第2降解产物)的平均分子量以测得的核磁共振氢谱为依据计算得到为181Da重复添加PLA原料进行8次降解的步骤(相当于第3～10次降解处理)，最终降解产物(相当于第10降解产物)的平均分子量以测得的核磁共振氢谱为依据计算得到为193Da其中，投入PLA共计25g(相当于第1～10可降解高分子材料的质量加和)，第3～10次降解处理中还加入水，加入的水与可降解高分子材料的质量比保持与第2次相同。
实施例15
将1000g的聚乳酸PLA(相当于第1可降解高分子材料)，35g的磷酸二苯酯DPP，83g的去离子水加入常压反应釜中，机械搅拌、通大气下，在160℃油浴下反应1.5h(相当于第1次降解处理)，所得降解产物(相当于第1降解产物)的平均分子量以测得的核磁共振氢谱为依据计算得到为347Da再次加入1000g的聚乳酸PLA(相当于第2可降解高分子材料)和83g去离子水，继续反应1.5h(相当于第2次降解处理)，所得降解产物(相当于第2降解产物)的平均分子量以测得的核磁共振氢谱为依据计算得到为284Da重复2次(相当于第3、4次降解处理)，最终产物(相当于第4降解产物)平均分子量以测得的核磁共振氢谱为依据计算得到为287Da其中，投入PLA共计4000g(相当于第1～4可降解高分子材料的质量加和)，第3、4次降解处理中还加入水，加入的水与可降解高分子材料的质量比保持与第1次和第2次相同。
取100g降解产物于二颈瓶中，加入0.75g的ZnO作为催化剂，自180℃起逐渐升高温度至230℃，减压蒸馏得到丙交酯粗产物，经水洗、乙酸乙酯重结晶纯化后，在常规工业催化剂Sn(Oct)2作用下开环聚合丙交酯得到PLA产物(Mn＝390,600，Mw＝505,300)，实现了PLA的闭环回收。
实施例16
实施例16的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4- 硝基苯基)磷酸酯(简称BNPP)。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为182Da，平均聚合度为2.3，转化率为84.6％。
实施例17
实施例17的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-氟苯基)磷酸酯(简称BFPP)，降解处理的时间为0.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为354Da，平均聚合度为4.7，转化率为67.4％。
实施例18
实施例18的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-三氟甲基苯基)磷酸酯(简称BTFPP)，降解处理的时间为0.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为343Da，平均聚合度为4.5，转化率为69.2％。
实施例19
实施例19的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为联萘酚磷酸酯(简称BNDHP)，降解处理的时间为4h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为243Da，平均聚合度为3.1，转化率为73.8％。
实施例20
实施例20的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为1,8-二氮杂双环[5.4.0]十一碳-7-烯(简称DBU)，降解处理的时间为3h，用于洗涤降解产物的有机溶剂为石油醚。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为333Da，平均聚合度为4.4，转化率为68.0％。
实施例21
实施例21的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为1,5,7-三叠氮双环[4.4.0]癸-5-烯(简称TBD)，降解处理的时间为4h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为249Da，平均聚合度为3.2，转化率为73.0％。
实施例22
实施例22的原料和降解处理过程与实施例1基本相同，不同之处在于采用的可降解高分子材料为聚己内酯(简称PCL)，降解处理的时间为3h，用于洗涤降解产物的有机溶剂为二氯甲烷。
聚己内酯型号为6800(Perstorp公司)，采用凝胶渗透色谱仪测得所用PCL的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为65.2kDa、213.1kDa和3.27。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例23
实施例23的原料和降解处理过程与实施例1基本相同，不同之处在于采用的可降解高分子材料为聚乳酸-羟基乙酸共聚物(简称PLGA)，降解处理的时间为2.5h。
聚乳酸-羟基乙酸共聚物为实验室自制，采用凝胶渗透色谱仪测得所用PLGA的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为9.97kDa、15.0kDa和1.50。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例24
实施例24的原料和降解处理过程与实施例1基本相同，不同之处在于采用的可降解高分子材料为聚己二酸/对苯二甲酸丁二酯(简称PBAT)，降解处理的时间为2.5h。
聚己二酸/对苯二甲酸丁二酯型号为F Blend C1200(BASF SE公司)，采用凝胶渗透色谱仪测得所用PBAT的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为17.3kDa、31.0kDa和1.79。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例25
实施例25的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.125g，采用的可降解高分子材料为聚(3-羟基丁酸酯-co-4-羟基丁酸酯)(简称P34HB)，降解处理的时间为3h，用于洗涤降解产物的有机溶剂为二氯甲烷。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.05：0.3：1。
聚(3-羟基丁酸酯-co-4-羟基丁酸酯)型号为EM 10080(ECOMRNN公司)。采用凝胶渗透色谱仪测得所用P34HB的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为128.9kDa、228.6kDa和1.77，测试条件同实施例1。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例26
实施例26的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.125g，采用的可降解高分子材料为聚丁二酸丁二醇酯(简称PBS)，降解处理的时间为4h，用于洗涤降解产物的有机溶剂为二氯甲烷。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.05：0.3：1。
聚丁二酸丁二醇酯型号为BioPBSTM FD72PM(公司Public Company Limited)，采用凝胶渗透色谱仪测得所用PBS的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为25.2kDa、43.2kDa和1.71。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例27
实施例27的原料和降解处理过程与实施例1基本相同，不同之处在于采用的可降解高分子材料为3D打印材料。
3D打印材料购自网络零售平台(淘宝网)店铺，采用凝胶渗透色谱仪测得所用材料的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为10.9kDa、18.4kDa和1.69。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到平均分子量为193Da，平均聚合度为2.4，转化率为78.2％。
实施例28
实施例28的原料和降解处理过程与实施例1基本相同，不同之处在于有机非金属催化剂的用量为0.125g，采用的可降解高分子材料为塑料吸管(主要成分为聚乳酸和聚丁二酸丁二醇酯)，降解处理的时间为4h，用于洗涤降解产物的有机溶剂为二氯甲烷。计算可知，其中的有机非金属催化剂：水：可降解高分子材料的质量比为0.05：0.3：1。
塑料吸管购自网络零售平台(淘宝网)店铺，采用凝胶渗透色谱仪测得所用材料的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI系数分别为122.3kDa、166.6kDa和1.36。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例29
实施例29的原料和降解处理过程与实施例1基本相同，不同之处在于采用的可降解高分子材料为聚三亚甲基碳酸酯(简称PTMC)，用于洗涤降解产物的有机溶剂为二氯甲烷，降解处理的时间为3h。
聚三亚甲基碳酸酯为实验室自制，采用凝胶渗透色谱仪测得所用PTMC的数均分子量(Mn)、重均分子量(Mw)和多分散系数PDI分别为23.6kDa、36.0kDa和1.53。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限。
实施例30
一种可降解聚酯/聚碳酸酯材料的再生处理方法：
将2.5g的聚乳酸PLA，0.0875g的磷酸二苯酯DPP，0.75g的去离子水加入反应管中，磁子搅拌、通大气下，在160℃油浴下反应1.5h，再加入2.5g去离子水，反应1.5h，冷却后经氯仿洗涤，所得产物分子量已低于GPC检测下限，全部转化为水溶性小分子，通过核磁共振法测试，降解产物的平均分子量为108其中86.2mol％为乳酸单体，与市售85％乳酸水溶液(单体占比86.0mol％)相近。
实施例31
实施例31的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-硝基苯基)磷酸酯(简称BNPP)，降解处理的时间为0.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为215Da，平均聚合度为2.7，转化率为62.4％。
实施例32
实施例32的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-硝基苯基)磷酸酯(简称BNPP)，降解处理的时间为1h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为186Da，平均聚合度为2.3，转化率为85.8％。
实施例33
实施例33的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为联萘酚磷酸酯(简称BNDHP)，降解处理的时间为3.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为291Da，平均聚合度为3.8，转化率为74.3％。
实施例34
实施例34的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为R-联萘酚磷酸酯(简称R-BNDHP)，降解处理的时间为5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为247Da，平均聚合度为3.2，转化率为70.8％。
实施例35
实施例35的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-甲基苯基)磷酸酯(简称BMPP)，降解处理的时间为2.0h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为270Da，平均聚合度为3.5，转化率为77.9％。
实施例36
实施例36的原料和降解处理过程与实施例1基本相同，不同之处在于采用的催化剂为双(4-甲氧基苯基)磷酸酯(简称BMOPP)，降解处理的时间为2.5h。
采用与实施例1相同的方法对洗涤后的降解产物进行测试，其分子量低于GPC检测下限，通过测得的核磁共振氢谱计算得到降解产物的平均分子量为227Da，平均聚合度为2.9，转化率为80.2％。
本申请发明人还进行了如下(一)～(五)组试验：
(一)将直径8mm的聚乳酸(Mn＝121.0kDa，Mw＝199.7kDa)薄膜圆片(17±1mg)置于5种不同反应环境中进行5种试验(分别记为A1、A2、A3、A4和A5)，环境温度为70℃，每种试验同时进行3组平行试验。分别在每组试验的第1天、第2天、第3天、第4天和第5天计算体系的转化率，并定时观察体系中残留聚合物的表观形态：
(1)试验A1：将前述聚乳酸薄膜圆片置于磷酸二苯酯(简称DPP)水溶液(3.5wt％，10mL，pH＝1)中，反应1天后可以观察到聚乳酸薄膜圆片已破碎；2天后在体系中已难以观察到明显的不溶物，聚乳酸薄膜圆片基本全部转化为水溶性小分子产物(经计算，转化率>95％)；图2为试验A1的3组平行试验中之一的聚乳酸薄膜圆片在反应开始后的第8小时(8h)、第16小时(16h)、第24小时(24h)、第32小时(32h)、第48小时(48h)和第72小时(72h)的聚乳酸薄膜残余物的光学照片，其中的虚线表示已无固体残余物。该体系在反应进行2天后转化率已达到95.3％，在反应进行3天后转化率已达到100％(转化率变化可参见图3和表3)。
(2)试验A2：将前述聚乳酸薄膜圆片置于水中。该体系在反应进行5天后转化率仅为5.1％(转化率变化可参见图3和表3)，该体系中的聚乳酸薄膜圆片降解速度明显低于试验A1的原因可能是未添加有机非金属催化剂，即便体系中有水，但无催化剂的作用时，该降解过程十分缓慢。
(3)试验A3：将前述聚乳酸薄膜圆片置于干燥环境中，在聚乳酸薄膜圆片中混有3.5wt％的磷酸二苯酯DPP。该混有3.5wt％DPP的聚乳酸薄膜圆片的制备方法为：在溶有PLA的DCM溶液中加入DPP，溶剂挥发后得到含有均匀分布的磷酸二苯酯DPP的样品薄膜(Mn＝84.3kDa，Mw＝136.8kDa)，将薄膜置于放有五氧化二磷的密闭玻璃容器中以尽量除去环境中的水分。该体系在反应进行5天后转化率为11.9％(转化率变化可参见图3和表3)，该体系中的聚乳酸薄膜圆片降解速度明显低于试验A1但略高于试验A2的原因可能是虽然没有额外添加水，但大气环境中有一定的水蒸气，在混入了一定含量的磷酸二苯酯DPP的情况下，聚乳酸薄膜圆片的降解过程可以进行，但降解速度较慢。
(4)试验A4：将前述聚乳酸薄膜圆片置于稀释的盐酸水溶液(pH＝1)中。该体系在反应进行5天后转化率为10.4％(转化率变化可参见图3和表3)。
(5)试验A5：将前述聚乳酸薄膜圆片置于氢氧化钠水溶液(pH＝13)中。该体系在反应进行5天后转化率为65.7％(转化率变化可参见图3和表3)。
表3试验A1～试验A5的3组平行试验中体系中的聚乳酸薄膜圆片在第1天～第5天的转化为水溶性小分子的转化率
由试验A1和试验A3的对比可知，磷酸二苯酯催化PLA的降解主要通过水解的方式进行，当体系中含水量极少(仅原料残余水分、环境中的水分)时，PLA的降解速度大大减缓，当体系中水分被基本耗尽后，PLA基本不降解，而在含水溶剂中，磷酸二苯酯可显著催化PLA的水解。
由试验A1、试验A4和试验A5的对比可知，磷酸二苯酯催化PLA水解的效果远好于传统的酸碱催化剂。
(二)进行聚乳酸降解的两组试验，两组试验的区别仅在于其中一组试验不添加催化剂磷酸二苯酯(试验A7)，所用聚乳酸样品测得的初始峰值分子量(Mpeak)为146.8kDa(凝胶渗透色谱测试，四氢呋喃流动相，聚苯乙烯为标样)。在采用凝胶渗透色谱对样品进行测试时，流出曲线或分子量分布曲线图中的峰的顶端对应的分子量即为峰值分子量(Mpeak)。通过峰值分子量可初步判断聚合物的分子量大小。
(6)试验A6：取0.5g的聚乳酸PLA和0.025g的磷酸二苯酯DPP投入试管中，置于160℃油浴，敞口放置，反应过程中每隔5min滴入2滴去离子水，试验时间为0.5h；
(7)试验A7：取0.5g的聚乳酸投入试管中，置于160℃油浴，敞口放置，反应过程中每隔5min滴入2滴去离子水，试验时间为0.5h。
在反应开始后每隔5min取样测试，测试方法同前(凝胶渗透色谱法，四氢呋喃流动相，聚苯乙烯为标样)；测得0.5h后试验A6和A7制得产物的峰值分子量(Mpeak)分别为0.5kDa和83.7kDa。由试验A6和A7可知，即便在水的添加量较少的情况下，磷酸二苯酯仍能有效催化聚乳酸降解(参见图4)。
(三)将购自TotalEnergies Corbion的牌号为LX175的聚乳酸PLA粒料(直径～3mm)各1g置于5种不同的溶有0.035g的磷酸二苯酯DPP的溶液中(溶液质量为20g)，环境温度为80℃，在2天后将全部组分取出冻干，进行GPC测试。
(1)试验B1：去离子水，2天后冻干样GPC测试结果：Mn＝6.3kDa，Mw＝9.1kDa，PDI＝1.44；
(2)试验B2：甲醇，2天后冻干样GPC测试结果：Mn＝26.7kDa，Mw＝33.1kDa，PDI＝1.24；
(3)试验B3：甲醇/水混合溶剂(m/m＝1:3)，2天后冻干样GPC测试结果：Mn＝7.4kDa，Mw＝10.7kDa，PDI＝1.45；其中，m/m表示相应两种成分的质量比；
(4)试验B4：甲醇/四氢呋喃混合溶剂(m/m＝1:3)，2天后冻干样GPC测试结果：Mn＝8.6kDa，Mw＝13.5kDa，PDI＝1.57；
(5)试验B5：水/四氢呋喃混合溶剂(m/m＝1:3)，2天后冻干样GPC测试结果：Mn＝0.5kDa，Mw＝0.7kDa，PDI＝1.4，样品分子量已接近GPC检测下限。
从试验B1可知，聚乳酸在仅有水和磷酸二苯酯存在的条件下可以较快地降解。对比试验B1、B2和B3可知，聚乳酸在以水为溶剂的体系中的降解速度比在以甲醇为溶剂的体系中的降解速度更快；聚乳酸在前者的体系中的降解速度与在以甲醇和水为混合溶剂的体系中的降解速度相近。从试验B1和试验B5的比较，以及试验B2和试验B4的比较，都可以看出四氢呋喃的加入有利于加快聚乳酸的降解速度，原因可能是四氢呋喃起到助溶作用，使得反应原料在体系中均匀分布，接触、反应机会增加，从而加快反应进程。
(四)以不同高分子材料为底物进行的降解试验。
将3种牌号的PLA粒料(均购自TotalEnergies Corbion，牌号分别为LX175、LX530和L105)各15g，2种PLA制品(购自网络零售平台(淘宝网)店铺)碎片各10g，3种常见的可机械回收的耐用塑料(聚对苯二甲酸乙二醇酯PET、聚丙烯PP和聚乙烯PE)(购自网络零售平台(淘宝网)店铺)各10g混合，混合塑料中包含1种聚对苯二甲酸乙二醇酯PET、1种聚丙烯PP、1种聚乙烯PE和5种聚乳酸PLA(图5的A)。向前述混合塑料体系中加入2.275g的磷酸二苯酯DPP(与聚乳酸PLA的质量比为0.035)和8g水，在160℃下反应1.5h后结束反应；将反应后的产物 中不溶于反应体系的固态物与可流动物质分离，分离得到的可流动物质(图5的B中所示的容器内乘装的物质)为降解产物。
对降解产物(图5的B所示的物质)进行1H NMR表征，发现降解产物为乳酸寡聚物和/或单体，测得平均分子量为220Da，平均聚合度为2.8；降解产物中未发现PET、PP和PE等聚合物及相应的降解寡聚物和/或单体。图5的C为分离得到的固态物，分别对不同的塑料进行DSC测试，并与进行降解处理前的相应的原料(PET、PP和PE的片材或粒料)的DSC测试结果进行比较，即得到图5的D、E和F。
通过DSC表征，可知PET、PP和PE这三种传统耐用塑料在经历过前述反应前后，熔点(Tm)基本不变：PET处理前熔点为247.7℃，处理后熔点为248.1℃(图5的D)；PP处理前熔点为161.3℃，处理后熔点为162.0℃(图5的E)；PE处理前熔点为129.5℃，处理后熔点为129.6℃(图5的F)，
通过对混合塑料进行的降解试验可知，对含有传统耐用塑料和聚乳酸在内的混合塑料进行前述条件下(也即在水和特定有机非金属催化剂存在的条件下，例如DPP)的处理，不仅其中的可降解高分子材料如聚乳酸的降解未受影响，而且PET、PP和PE这些传统耐用塑料可以不受该处理的影响(PET、PP和PE的表观形貌未见明显变化(见图5的A与C对比)、熔点未明显变化(见图5的D、E和F))而较好地保持原始性能，后续还可以继续对传统耐用塑料PET、PP和PE进行进一步的机械回收，从而获得相应的质量较好的回收物。
DSC测试方法：通过差式扫描量热仪(Q2000，TA Instruments)对塑料的热性能进行表征。以PET为例，将称量后的样品置于样品盘中，在氮气氛围下加热到320℃，平衡5分钟以去除热历史，再以10℃/min的速度进行降温至20℃，平衡5分钟后，以同样的速度升温至320℃并记录数据。PP和PE升温至220℃。
(五)将购自TotalEnergies Corbion的牌号为LX175的PLA粒料(直径～3mm)各5g置于如下3种不同的水溶液中(溶液质量为5g)，环境温度为80℃，在反应开始的1天和3天后分别取50mg溶液冻干，进行1H NMR测试。
(1)第一种水溶液为0.1M(mol/L)的HCl溶液，基本未测得水溶性物质，反应开始3天后体系为悬浊液，呈乳白色；
(2)第二种水溶液为溶有5wt％磷酸二苯酯DPP的水溶液，反应开始1天后测得溶液中含乳酸寡聚物和单体，平均分子量为385，平均聚合度为5.1，反应开始3天后，降解产物的平均分子量为108，平均聚合度为1.3，此时溶液呈澄清透明状；
(3)第三种水溶液为溶有5wt％磷酸二苯酯DPP的0.1M(mol/L)的HCl溶液，反应开始1天后测得溶液中含乳酸寡聚物和单体，平均分子量为167，平均聚合度为2.1，反应开始3天后呈澄清透明，降解产物的平均分子量为106，平均聚合度为1.3。
通过将聚乳酸PLA置于3种不同的水溶液进行试验的反应结果可知，一方面，单纯的HCl不能有效地催化PLA的降解；另一方面，聚乳酸在有水和有机非金属催化剂磷酸二苯酯DPP存在的条件下已经能够较快速地降解，加入额外的盐酸虽然在反应前期对降解有一定的加速作用，但是最终制备得到的降解产物的分子量和平均聚合度均相差不大。因此，聚乳酸可以在不含盐酸的条件下，仅仅在有水和有机非金属催化剂例如磷酸二苯酯DPP存在时，即可较快速地降解，实现较好的回收利用。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本申请。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准，说明书可以用于解释权利要求的内容。

Claims (10)

  1. 一种可降解高分子材料的再生处理方法，其包括以下步骤：在有机非金属催化剂和含水溶剂存在的体系中，对可降解高分子材料进行降解处理，得到降解产物；
    其中，
    所述可降解高分子材料包括聚酯材料和聚碳酸酯材料中的一种或多种；
    所述有机非金属催化剂选自磷酸二苯酯类、联萘酚磷酸酯类和有机碱类中的一种或多种，所述有机碱类选自含氮杂双环碱类、4-二甲氨基吡啶和磷腈碱类化合物中的一种或多种。
  2. 根据权利要求1所述的再生处理方法，其中，所述磷酸二苯酯类具有式(Ⅰ)所示的结构：
    式(Ⅰ)中，R11、R12、R13、R14、R15、R21、R22、R23、R24和R25各自独立地选自-H、卤素、-NO2、-CN、C1～C4烷氧基、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：-NO2、-CN、卤素和C1～C4烷基；
    所述联萘酚磷酸酯类具有式(Ⅱ)所示的结构：
    式(Ⅱ)中，R3和R3’各自独立地选自-H、-SiPh3或其中，“*”表示共价单键的连接位点；
    R41、R42、R43、R44和R45各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基；或R41、R42、R43、R44和R45中的至少两个成环并参与形成稠合环，R41、R42、R43、R44和R45中未成环的基团各自独立地选自-H、卤素、-NO2、-CN、C1～C6烷基、卤素取代的C1～C6烷基、苯基，以及取代的苯基中的任一种，所述取代的苯基中的苯环被一个或多个选自下组的取代基取代：卤素、-NO2、-CN、苯基和C1～C4烷基；
    所述含氮杂双环碱类选自具有式(Ⅲ)所示的结构：
    式(Ⅲ)中，Y是-CH2-、-NH-或-N(CH3)-；n是1或2；
    所述磷腈碱类化合物具有式(Ⅳ)所示的结构：
    式(Ⅳ)中，R为卤素、C1～C4烷基或C1～C4烷氧基。
  3. 根据权利要求1或2所述的再生处理方法，其满足如下特征中的一个或多个：
    所述可降解高分子材料的数均分子量为10kDa～250kDa；
    所述体系中水相对于所述可降解高分子材料的质量比为(0.01～10):1；
    所述有机非金属催化剂相对于所述可降解高分子材料的质量比为(0.001～0.1)：1；
    所述降解产物的平均聚合度≤20。
  4. 根据权利要求1～3中任一项所述的再生处理方法，其满足如下特征中的一个或多个：
    所述可降解高分子材料选自聚乳酸、聚羟基乙酸、聚ε-己内酯、聚乳酸-羟基乙酸共聚物、聚羟基乙酸-ε-己内酯共聚物、聚乳酸-ε-己内酯共聚物、聚δ-戊内酯、聚丁内酯、聚丁二酸丁二醇酯、聚己二酸/对苯二甲酸丁二酯、聚丁二酸/己二酸丁二醇酯、聚羟基脂肪酸酯和聚三亚甲基碳酸酯中的一种或多种；
    所述磷酸二苯酯类催化剂选自磷酸二苯酯、双(4-硝基苯基)磷酸酯、双(4-氟苯基)磷酸酯、双(4-三氟甲基苯基)磷酸酯、双(4-氯苯基)磷酸酯、双(4-甲氧基苯基)磷酸酯和双(4-甲基苯基)磷酸酯中的一种或多种；
    所述联萘酚磷酸酯类催化剂选自联萘酚磷酸酯、R-联萘酚磷酸酯、R-3,3’-二(三苯基硅基)联萘酚膦酸酯和R-3,3’-二(2,4,6-三异丙基苯基)联萘酚膦酸酯中的一种或多种；
    所述有机碱类催化剂选自1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三叠氮双环[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、4-二甲氨基吡啶、叔丁基亚氨基-三(二甲氨基)正膦、1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物)和环三磷腈碱和1-叔丁基-4,4,4-三(二甲氨基)-2,2-二[三(二甲氨基)-正膦亚基氨基]-2Λ5,4Λ5-连二(磷氮基化合物)中的一种或多种。
  5. 根据权利要求1所述的再生处理方法，其包括以下步骤：在所述有机非金属催化剂和所述含水溶剂存在的体系中，对第1可降解高分子材料进行第1次降解处理，得到第1降解产物；
    混合第i降解产物和第i+1可降解高分子材料，进行第i+1次降解处理，得到第i+1降解产物，其中，i为≥1的整数，所述第i+1可降解高分子材料至少包括第2可降解高分子材料；至i+1＝n时结束降解处理，得到第n降解产物，其中n为≥2的整数，所述第n降解产物的平均聚合度≤20。
  6. 根据权利要求1～5中任一项所述的再生处理方法，其满足如下特征中的一个或多个：
    任一次降解处理的温度独立地为125℃～200℃；
    任一次降解处理的时间独立地为0.1h～5h，可选为0.25h～5h；
    任一次降解处理的压力独立地为1atm-100atm，可选为100±5kPa。
  7. 根据权利要求1～5、6中任一项所述的再生处理方法，其还包括以下步骤：采用有机溶剂洗涤所述降解产物；其中，所述有机溶剂选自氯仿、石油醚、二硫化碳、乙醚、二氯甲烷、苯、甲苯和乙酸乙酯中的一种或多种。
  8. 一种低分子量组合物，其中，所述低分子量组合物为可降解高分子材料的降解产物，所述低分子量组合物根据权利要求1～7中任一项所述的再生处理方法制备得到，其中，所述低分子量组合物的平均聚合度≤20。
  9. 一种可降解高分子材料的回收利用方法，其包括以下步骤：以低分子量组合物为初始原料进行聚合反应；其中，所述低分子量组合物为权利要求1～7中所述的再生处理方法制备得到的降解产物或权利要求8所述低分子量组合物。
  10. 有机非金属催化剂在可降解高分子材料的降解处理中的应用；
    其中，所述有机非金属催化剂和所述可降解高分子材料如权利要求1～4任一项中所定义。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578510A (en) * 1984-12-11 1986-03-25 Celanese Corporation Process for minimizing formation of low molecular weight oligomers during hydrolytic depolymerization of condensation polymers
CN105658611A (zh) * 2013-10-15 2016-06-08 国际商业机器公司 用于使聚酯解聚的方法和材料
CN105873895A (zh) * 2013-12-31 2016-08-17 Bp北美公司 从含聚酯原料形成芳香二酸和/或芳香二酸前体的方法
CN107915832A (zh) * 2017-10-19 2018-04-17 复旦大学 X‑射线显影的含碘聚碳酸酯/聚酯材料及其制备方法与应用
CN113831588A (zh) * 2021-09-17 2021-12-24 中国科学院山西煤炭化学研究所 一种水相体系降解不饱和聚酯树脂材料制化学品的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4578510A (en) * 1984-12-11 1986-03-25 Celanese Corporation Process for minimizing formation of low molecular weight oligomers during hydrolytic depolymerization of condensation polymers
CN105658611A (zh) * 2013-10-15 2016-06-08 国际商业机器公司 用于使聚酯解聚的方法和材料
CN105873895A (zh) * 2013-12-31 2016-08-17 Bp北美公司 从含聚酯原料形成芳香二酸和/或芳香二酸前体的方法
CN107915832A (zh) * 2017-10-19 2018-04-17 复旦大学 X‑射线显影的含碘聚碳酸酯/聚酯材料及其制备方法与应用
CN113831588A (zh) * 2021-09-17 2021-12-24 中国科学院山西煤炭化学研究所 一种水相体系降解不饱和聚酯树脂材料制化学品的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WU WANHUA, ZHAI HUAJUAN, WU KAITING, WANG XIN, RAO WEIHAN, DING JIANDONG, YU LIN: "Cheap organocatalyst diphenyl phosphate for efficient chemical recycling of poly(lactic acid), other polyesters and polycarbonates", CHEMICAL ENGENEERING JOURNAL, vol. 480, 15 January 2024 (2024-01-15), AMSTERDAM, NL , pages 1 - 12, XP093257952, ISSN: 1385-8947, DOI: 10.1016/j.cej.2023.148131 *

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