WO2023093810A1 - 一种聚酯高分子化合物及其制备方法和应用 - Google Patents

一种聚酯高分子化合物及其制备方法和应用 Download PDF

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WO2023093810A1
WO2023093810A1 PCT/CN2022/134072 CN2022134072W WO2023093810A1 WO 2023093810 A1 WO2023093810 A1 WO 2023093810A1 CN 2022134072 W CN2022134072 W CN 2022134072W WO 2023093810 A1 WO2023093810 A1 WO 2023093810A1
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formula
substituted
group
δlh
alkyl
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PCT/CN2022/134072
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English (en)
French (fr)
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林柏霖
胥嘉麟
徐路燕
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上海科技大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

Definitions

  • the invention belongs to the technical field of polymer synthesis, relates to a polyester polymer compound and its preparation method and application, in particular to a chemically recyclable polymer based on CO 2 , H 2 and 1,3-butadiene (CO 2 -based chemical recyclable polymer) and its preparation method and application.
  • Chemical recycling is a promising strategy to reduce the environmental and economic impacts and considerations of polymeric materials. Chemical recycling can realize a closed loop of material economy through the strategy of "synthesis, utilization and recovery". This circular economy model is a very promising means of solving white pollution. At the same time, the synthesis of chemically recyclable polymers from cheap and readily available bulk chemicals, such as CO2 and olefins, can reduce material costs and drive them towards industrial mass production. Therefore, the development of efficient conversion and utilization of carbon dioxide is of great significance for industrial production and sustainable development.
  • CO 2 is very suitable for the synthesis of a variety of polymer materials, including polycarbonate, polyurethane, polyurea and polyester.
  • the synthesis of new polymers, especially ethylene and 1,3-butadiene, through CO 2 and cheap bulk chemicals has been a very promising direction since the 1970s.
  • CO 2 and 1,3-butadiene realize the coupling reaction catalyzed by Pd, and generate the six-membered ring lactone intermediate 3-ethylene-6- vinyltetrahydro-2H-pyran-2-one ( ⁇ -L).
  • the raw materials for copolymerization with CO2 should be cheap bulk chemical raw materials;
  • the polymer should be easily processed into desired properties and have commercial performance indicators;
  • the new polymer In order to solve the increasingly serious problem of plastic pollution, the new polymer must be degradable.
  • the commercialized CO 2 -based polymer materials synthesized by CO 2 in the market are mainly polycarbonate and polypolyol, which cannot meet the requirements of materials in terms of cost, material performance and degradability at the same time, and among them, CO 2
  • the amount of usage is not large, and it cannot meet the demand for CO2 emission reduction.
  • the present invention proposes a polyester polymer compound and a synthesis method thereof for the first time, which is prepared by performing ring-opening polymerization (ROP) with a heterocyclic lactone to obtain the polyester polymer compound , such as the method by derivatizing CO 2 , H 2 and 1,3-butadiene to a diethyl-substituted six-membered ring lactone that is 3,6-diethyltetrahydro-2h-pyran-2 - Ketone (HL) is prepared by ring-opening polymerization (ROP) to obtain polyHL, which is used to solve the problems of complex preparation steps, low yield and high cost in the prior art, the prepared polyester has low molecular weight, and the performance of related polyester products is not high, such as Low transparency, low stability, etc.; another example is the use of heterocyclic lactones as raw materials to synthesize the cyclic polymer through anionic ring-opening polymerization, which can be
  • the present invention provides a polyester polymer compound, which comprises a repeating unit shown in the following formula 4:
  • R 1 and R 2 are independently selected from hydrogen, halogen, alkyl, substituted alkyl (linear alkyl, branched alkyl, cycloalkyl), alkenyl, substituted alkenyl, alkynyl, substituted alkyne Any one of radicals, monocyclic aromatic groups, substituted monocyclic aromatic groups, polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, and substituted polyheterocyclic aromatic groups; the monocyclic aromatic group Including phenyl, azaaryl, sparse heteroaryl, oxaaryl; said polycyclic aromatic group and polyheterocyclic aromatic group refer to groups comprising two or more monocyclic aromatic groups; R 1. R2 can be the same or different, and must exist at the same time;
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfenamide group, sulfonamide group, morpholino group, Piperazinyl.
  • X is selected from heteroatoms.
  • the number of repeating units shown in the formula 4 is n, and the n is a positive integer greater than or equal to 1.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 ), and the carbon dioxide-based polyester poly( ⁇ LH 2 ) contains repeating units as shown in Formula 6 below:
  • n is a positive integer greater than or equal to 1.
  • the polyester polymer compound described in the present invention includes topological structures such as linear, ring, and star.
  • R 1 , R 2 , X, n, m are as defined in the compound of formula 4 above.
  • R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl , polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, any one of polymer groups with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol and polyethylene glycol repeating unit structures.
  • polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the structure of the carbon dioxide-based polyester poly( ⁇ LH 2 ) is shown in Formula 7:
  • R is selected from C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 alkynyl, substituted C2-C20 alkynyl, monocyclic Aryl groups, substituted monocyclic aromatic groups, polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, polyvinyl alcohol, poly Any one of the macromolecular groups of the ethylene glycol repeating unit structure;
  • n is a positive integer greater than or equal to 1;
  • n is a positive integer greater than or equal to 1.
  • Another aspect of the present invention is to provide one or more applications of the polyester compound in the preparation of polyurethane, polymer film, pressure-sensitive adhesive, adhesive tape and thermoplastic elastomer.
  • the polyester compound when the polyester polymer compound has a linear structure, the polyester compound is used in the preparation of polyurethane or pressure-sensitive adhesives.
  • the structure of the polyester polymer compound is a ring structure
  • the application of the polyester compound in the preparation of polymer films, pressure-sensitive adhesives, and thermoplastic elastomers is a polymer film.
  • the structure of the polyester polymer compound is an adhesive tape.
  • Another aspect of the present invention is to provide a synthetic method of polyester polymer compound, selected from any one or both of the following methods:
  • the method includes: a heterocyclic lactone shown in formula 1, an organic base as a catalyst, and a reagent R(OH) m that can provide an active proton as a trigger Under the condition of reagent, synthesis obtains the polyester macromolecular compound shown in formula 2; Reaction process is shown in reaction formula 1:
  • the method includes: the heterocyclic lactone shown in Formula 1, under the catalysis of an organic base, synthesizes the polyester polymer compound shown in Formula 3 ;
  • the reaction process is shown in Reaction Formula II:
  • R 1 and R 2 are independently selected from hydrogen, halogen, alkyl, substituted alkyl (linear alkyl, branched chain alkyl, cycloalkyl), alkenyl, substituted Alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl, polyheteroaryl, substituted polyheteroaryl any one of;
  • the monocyclic aryl group includes phenyl, azaaryl, sparse heteroaryl, oxaaryl;
  • the polycyclic aryl and polyheteroaryl refer to two or more A monocyclic aromatic group;
  • R 1 and R 2 can be the same or different, and must exist at the same time;
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfinamide group, sulfonamide group, morpholino group, Piperazinyl.
  • X is selected from heteroatoms
  • n is a positive integer greater than or equal to 1;
  • the organic base includes phosphazene, a compound containing a guanidino group, a compound containing an amidino group;
  • R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted Any one of polycyclic aromatic groups, polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, polymer groups with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol and polyethylene glycol repeating unit structures;
  • n is a positive integer greater than or equal to 1.
  • the method when the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 ), the method includes: ⁇ LH 2 shown in formula 8, using an organic base as a catalyst , under the condition that the reagent R 14 (OH)m and/or (MO) m R 14 that provides active protons is used as the initiator, the carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in formula 7 is synthesized; the reaction process is shown in the reaction formula As shown in III:
  • R is selected from C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 alkynyl, substituted C2-C20 alkynyl, monocyclic Aryl groups, substituted monocyclic aromatic groups, polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, polyvinyl alcohol, poly Any one of the macromolecular groups of the ethylene glycol repeating unit structure;
  • M is K, Na, Li, Rb or Cs
  • n is a positive integer greater than or equal to 1;
  • n is a positive integer greater than or equal to 1;
  • the organic base is selected from one or more of phosphazenes, compounds containing guanidino groups, and compounds containing amidino groups.
  • R 3 -R 10 are independently selected from C1-C10 alkyl groups; y is a positive integer greater than or equal to 1.
  • the phosphazenes are selected from tBu -P 1 , tBu -P 2 , and tBu -P 4 , and the structures are shown below:
  • Another aspect of the present invention is to provide a polyester polymer compound, which is synthesized by the above-mentioned method.
  • Another aspect of the present invention is to provide the purposes of organic bases in catalyzing the synthesis of polyester polymer compounds shown in Formula 2 and/or Formula 3 from compounds of Formula 1 as described above.
  • the compound, the compound containing amidino group; Wherein, the heterocyclic lactone shown in formula 1, the polyester polymer compound structure shown in formula 2 and/or formula 3 are as follows respectively:
  • the present invention provides the use of an organic base in catalyzing ⁇ LH 2 shown in Formula 8 to synthesize carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in Formula 7.
  • ⁇ LH 2 shown in Formula 8 and carbon dioxide shown in Formula 7 The structures of the base polyester poly( ⁇ LH 2 ) are as follows:
  • described organic base is phosphazene, and the structure of described phosphazene is shown in following formula 5:
  • R 3 -R 10 are independently selected from C1-C10 alkyl groups
  • y is 1, 2 or 3.
  • Another aspect of the present invention is to provide a method for catalyzing the above-mentioned polyester polymer compound shown in formula 2/or formula 3 to reclaim heterocyclic monomers, said method being selected from any one or both of the following:
  • catalytic formula 2 comprises catalytic method and pyrolysis method
  • catalytic formula 3 includes inorganic salt pyrolysis catalytic method and La[N(SiMe 3 ) 2 ] 3 mild catalytic method;
  • the catalytic method includes: using at least one compound in inorganic salts, metal organic compounds, and organic compound catalysts to degrade the polyester polymer compound of formula 2, and reclaim the heterocyclic monomer shown in formula 1 or Its oligomers or derivatives thereof;
  • the pyrolysis method includes: thermally cracking the polyester polymer compound of formula 2, and recovering the heterocyclic monomer or its oligomer or its derivative shown in formula 1;
  • the inorganic salt pyrolysis catalytic method includes: using inorganic salts to catalyze the degradation of polyester polymer compounds shown in formula 3 to obtain heterocyclic compounds shown in formula 1 or their oligomers or the corresponding derivative;
  • the La[N(SiMe 3 ) 2 ] 3 mild catalytic method includes: using La[N(SiMe 3 ) 2 ] 3 to catalytically crack the polyester polymer compound shown in formula 3 under mild conditions to obtain formula 1
  • the shown heterocyclic compound or its oligomer is also the corresponding derivative of Formula 1.
  • polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the catalytic method includes: degrading the carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in Formula 8 by using at least one compound among inorganic salts, metal-organic compounds or organic compound catalysts, and recovering ⁇ LH 2 shown in Formula 7 or its oligomers or derivatives thereof;
  • the pyrolysis method includes: thermally cracking the carbon dioxide-based polyester poly( ⁇ LH 2 ) represented by the formula 8, and recovering the ⁇ LH 2 represented by the formula 7 or its oligomer or its derivatives.
  • Another aspect of the present invention is to provide a method for preparing a disubstituted ⁇ , ⁇ -saturated six-membered ring lactone when the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 ), the method is represented by the formula
  • the disubstituted ⁇ , ⁇ -unsaturated six-membered ring lactone shown in 9 is used as a raw material, using Stryker reagent or a mixed reagent that can generate Stryker reagent in situ as a catalyst, and organosilane as a hydrogen source, through the selective reduction of conjugated olefins
  • the reaction prepares the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone shown in Formula 10; the selective reduction reaction is shown in Reaction Formula A:
  • R 1 and R 2 are independently selected from hydrogen, halogen, C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 alkynyl, Any one of substituted C2-C20 alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl, polyheterocyclic aryl, substituted polyheterocyclic aryl;
  • the monocyclic aryl group is selected from phenyl, azaaryl, sparse heteroaryl, and oxaaryl; the polycyclic aryl and polyheteroaryl refer to a single ring comprising two or more An aromatic group; R 1 and R 2 may be the same or different.
  • Another object of the present invention is to provide an application of the above-mentioned ⁇ LH 2 preparation method in the preparation of carbon dioxide-based polyester poly( ⁇ LH 2 ) or polyurethane or pressure-sensitive adhesive shown in formula 8, represented by formula 10
  • the structure of the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone shown is as follows:
  • the carbon dioxide-based polyester polymer compound of the present invention and its preparation method and application have the following beneficial effects:
  • the preparation method of the carbon dioxide-based polyester macromolecular compound provided by the present invention takes the heterocyclic monomer of formula 1 as a raw material, and adopts two kinds of initiation modes: 1. organic base is a catalyst, and a reagent that can provide active protons such as R(OH )m is an initiator; 2. Using alkoxide alone as an initiator, for example, performing ring-opening polymerization under the condition of -100-200° C. to obtain a polyester polymer compound with controllable polymer molecules in one-step method.
  • the method is simple, the raw materials are easy to obtain, and the raw materials come from cheap carbon dioxide gas, which can effectively alleviate the greenhouse effect.
  • the molecular weight of the polyester polymer compound can be controlled.
  • the method of the invention obtains polymers with good physical and chemical properties (such as mechanical properties) and recyclability through ring-opening polymerization, increasing its application potential.
  • the raw material heterocyclic lactone adopted in the method of the present invention has a wide range of sources and is simple to prepare; when the heterocyclic lactone is HL, the HL can be prepared by CO and 1,3 -butadiene, and then can alleviate CO caused by Harm caused by the greenhouse effect.
  • the catalyst adopted in the method of the invention has good catalytic activity, simple preparation method and low cost.
  • the method of the present invention can synthesize and obtain the cyclic polymer of ultrahigh molecular weight and medium molecular weight distribution, in some embodiments, the molecular weight of described cyclic polymer can reach 613.8kg mol-1, molecular weight distribution is 1.45.
  • the cyclic polymer can be used to prepare various polymer products, such as polymer film, adhesive tape, etc.; the prepared polymer film is colorless and transparent, and has good properties such as flexibility and viscoelasticity.
  • the method provided by the invention has strong substrate broad spectrum, can effectively recover various cyclic polymers including but not limited to monomers in the cyclic polymers prepared by the method of the invention, and has wide application prospects.
  • the preparation method of the carbon dioxide-based polyester poly( ⁇ LH 2 ) provided by the present invention uses ⁇ LH 2 shown in Formula 1 as a raw material, and adopts two initiation modes: 1. organic base is a catalyst, and a reagent that can provide active protons such as R( OH) m is the initiator; 2. Use alkoxide alone as the initiator to carry out the ring-opening polymerization reaction, and obtain the polyester polymer compound with controllable polymer molecules in one step.
  • the preparation method of poly( ⁇ LH 2 ) has simple steps, high yield and strong controllability; the catalyst adopted is simple to prepare, low in cost and good in activity.
  • the invention can control the molecular weight and molecular weight distribution of the polyester compound poly( ⁇ LH 2 ) by adjusting the types of raw materials, the dosage of each reagent, the reaction temperature and the reaction time and other conditions.
  • the prepared poly( ⁇ LH 2 ) is a flexible material that can be completely degraded into monomers, and the polyester material has good physical and chemical properties, such as high transparency, high molecular weight, strong thermal stability, ductility Good sex and other characteristics.
  • the method provided by the present invention can use cheap and easy-to-obtain C1 source carbon dioxide and bulk chemical product 1,3-butadiene as raw materials to first synthesize six-membered ring lactone ⁇ LH 2 , and then synthesize the poly( ⁇ LH 2 ), which can effectively alleviate the greenhouse effect. Through chemical recovery of poly( ⁇ LH 2 ), to obtain monomer ⁇ LH 2 , a closed-loop green cycle is realized.
  • the polyester material prepared by the present invention has excellent post-polymerization modification and modification capabilities, and poly( ⁇ LH 2 ) can be post-polymerized and modified by a post-modification modification method, such as photoinduced thiol-alkene click reaction.
  • Poly( ⁇ LH 2 ) olefin side chains can be grafted to adjust the properties of polymers.
  • the preparation method of disubstituted ⁇ , ⁇ -saturated six-membered ring lactone such as ⁇ LH 2 uses disubstituted ⁇ , ⁇ -unsaturated six-membered ring lactone such as ⁇ -L as raw material, and uses Stryker reagent or original
  • the mixed reagent for forming Stryker reagent is catalyst, organosilane is hydrogen source, and it is prepared by selective reduction reaction of conjugated olefin.
  • the preparation method of ⁇ LH 2 has high yield, simple steps and low cost.
  • the method for preparing poly( ⁇ LH 2 ) and the method for preparing ⁇ LH 2 described in the present invention have great application prospects in the field of materials, especially in the field of polymer materials.
  • Figure 1 shows the possible chain initiation mechanism during the ring-opening polymerization of HL catalyzed by tBu -P 4 /BnOH ( 1 H NMR spectrum of equivalent experiment).
  • a Phosphazene t Bu-P 4 ;
  • Figure 2 shows the MALDI-TOF characterization diagram of the product of Example 18.
  • Figure 3 shows the MALDI-TOF characterization diagram of the product of Example 19.
  • Figure 4 shows the active polymerization analysis of HL-ROP catalyzed by tBu - P4 /BnOH of Example 20.
  • a HL conversion curve with time;
  • b ln([M]/[M] 0 );
  • c The molecular weight and molecular weight distribution of polyHL with the change curve of HL monomer conversion rate;
  • d Obtained under different polymerization time Overlay of polyHL GPC curves.
  • Figure 5 shows the MALDI-TOF characterization of the linear polyHL polymer of Example 21, which was confirmed to be a BnOH-terminated product.
  • Figure 6 shows the1H NMR characterization of the linear polyHL polymer of Example 21.
  • Figure 7 shows the13C NMR characterization of the linear polyHL polymer of Example 21.
  • Figure 8 shows the MALDI-TOF characterization of the linear polyHL diol prepared with 1,4-BDM as the initiator in Example 21.
  • Figure 9 shows the TGA and DTG plots of the linear polyHL of Example 23.
  • Figure 10 shows the DSC plot of the linear polyHL of Example 23.
  • Fig. 11 is a graph showing the variation of HL monomer concentration over time under different temperature conditions in Example 24.
  • Figure 12 shows the Van't Hoff analysis curve of HL in Example 24.
  • Figure 13 shows the 1 H NMR pattern of the linear polyHL chemical recovery of Example 25.
  • Figure 14 shows the results of recovery of polymer monomers by pyrolysis method in Example 26.
  • Fig. 15 is a route diagram for the preparation of cyclic polymers and the chemical recovery of cyclic polymers from CO2 and butadiene.
  • Fig. 16 is a schematic diagram of the mechanism for synthesizing cyclic polymers from HL ring-opening polymers.
  • Figure 17 is the kinetic data of HL ring-opening polymerization catalyzed by tBu-P4.
  • a The change curve of conversion rate with time;
  • c The change curve of number average molecular weight and molecular weight distribution with conversion rate;
  • d Different examples Overlay of GPC curves.
  • Figure 18 is the MALDI-TOF characterization data of the cyclic PolyHL product prepared in Example 44.
  • Fig. 19 is the 1H NMR spectrogram (embodiment 29) of cyclic polyHL polymer.
  • Fig. 20 is the 13C NMR spectrogram (embodiment 29) of cyclic polyHL polymer.
  • Figure 21 is the MALDI-TOF characterization of the polyHL product when the system is not strictly dewatered.
  • Fig. 22 is a mixing experiment of HL and tBu -P 4 at different ratios ( 31 P NMR spectrum).
  • Fig. 23 is a mixing experiment of HL and tBu -P 4 at different ratios ( 1 H NMR spectrum, partially enlarged).
  • Fig. 24 is a mixing experiment of HL and tBu -P 4 at different ratios ( 1 H NMR spectrum, overview).
  • Figure 25 is the free energy calculation data of tBu-P4 for BnOH, HL and water deprotonation.
  • Figure 26 is the TGA and DTG curves of the cyclic polyHL product.
  • Figure 27 is the DSC curve of the cyclic polyHL product.
  • Figure 28 is the measurement of the pressure-sensitive adhesive properties of the ring-shaped polyHL sample.
  • a Schematic diagram of 180 ° peeling measurement;
  • b cross-sectional SEM image of annular polyHL film (embodiment 29);
  • c 180 ° peeling performance measurement results of annular polyHL sample and three kinds of commercial adhesive tapes (see Table 29 for data);
  • d Sample demonstration of colorlessness and light transmission of polyHL film (Example 29).
  • Figure 29 is the H NMR spectrum of the polyHL polymer prepared in Example 30.
  • Figure 30 is the H NMR spectrum of the polyHL polymer prepared in Example 31.
  • Figure 31 is the H NMR spectrum of the polyHL polymer prepared in Example 32.
  • Figure 32 is the H NMR spectrum of the degraded product of Example 50.
  • Figure 33 is the H NMR spectrum of the degraded product of Example 51.
  • Figure 34 is the H NMR spectrum of the degraded product of Example 52.
  • Figure 35 is the H NMR spectrum of the degraded product of Example 53.
  • Figure 36 is the H NMR spectrum of the degraded product of Example 54.
  • Figure 37 is the H NMR spectrum of the degraded product of Example 55.
  • Figure 38 is the H NMR spectrum of the degraded product of Example 56.
  • Figure 39 is the H NMR spectrum of the degraded product of Example 57.
  • Figure 40 is the H NMR spectrum of the degraded product of Example 58.
  • Figure 41 is the H NMR spectrum of the degraded product of Example 59.
  • Figure 42 is the H NMR spectrum of the degraded product of Example 60.
  • Figure 43 is the H NMR spectrum of the degraded product of Example 61.
  • Figure 44 is the H NMR spectrum of the degraded product of Example 62.
  • Figure 45 is the H NMR spectrum of the degraded product of Example 63.
  • Figure 46 is the H NMR spectrum of the degraded product of Example 64.
  • Figure 47 is the H NMR spectrum of the degraded product of Example 65.
  • Figure 48 is the H NMR spectrum of the degraded product of Example 66.
  • Figure 49 is the H NMR spectrum of the degraded product of Example 67.
  • Figure 50 is the H NMR spectrum of the degraded product of Example 68.
  • Figure 51 is the H NMR spectrum of the degraded product of Example 69.
  • Figure 52 is the H NMR spectrum of the degraded product of Example 70.
  • Figure 53 is the H NMR spectrum of the degraded product of Example 71.
  • Figure 54 is the H NMR spectrum of the degraded product of Example 72.
  • Fig. 55 is the overlay NMR spectrum of the starting material, polymer and degradation product of Example 73.
  • Figure 56 is the GPC raw data of polyHL_160 prepared in Example 49.
  • Figure 57 is the GPC raw data of polyHL_319 prepared in Example 49.
  • Figure 58 is the GPC raw data of polyHL_562 prepared in Example 49.
  • Figure 59 shows the current situation and technical route of poly( ⁇ LH 2 ) synthesis.
  • FIG. 60 is the proton nuclear magnetic resonance spectrum of ⁇ LH 2 prepared in Example 74.
  • FIG. 61 is a carbon nuclear magnetic resonance spectrum of ⁇ LH 2 prepared in Example 74.
  • Figure 62 is the H NMR spectrum of poly( ⁇ LH 2 ) prepared in Example 81.
  • Example 63 is a GPC curve of poly( ⁇ LH 2 ) prepared in Example 82.
  • Figure 64 is an overlay of the GPC curves of poly( ⁇ LH 2 ) prepared in Examples 83, 86-89; KOMe corresponds to Example 83, NaOMe corresponds to Example 86, KO t Bu corresponds to Example 87, and NaO t Bu corresponds to Example 87.
  • Figure 65 is the H NMR spectrum of poly( ⁇ LH 2 ) prepared in Example 83.
  • Figure 66 is the carbon NMR spectrum of poly( ⁇ LH 2 ) prepared in Example 83.
  • Figure 67 is the NMR hydrocarbon HSQC chart of poly( ⁇ LH 2 ) prepared in Example 83.
  • Fig. 68 is the GPC chart of poly( ⁇ LH 2 ) prepared in Examples 83-85.
  • FIG. 69 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 79.
  • FIG. 69 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 79.
  • FIG. 70 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 82.
  • FIG. 70 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 82.
  • FIG. 71 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 83.
  • FIG. 71 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 83.
  • FIG. 72 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 84.
  • FIG. 72 is a TGA curve corresponding to poly( ⁇ LH 2 ) prepared in Example 84.
  • FIG. 73 is a DSC curve corresponding to poly( ⁇ LH 2 ) prepared in Example 79.
  • FIG. 73 is a DSC curve corresponding to poly( ⁇ LH 2 ) prepared in Example 79.
  • FIG. 74 is a DSC curve corresponding to poly( ⁇ LH 2 ) prepared in Example 84.
  • FIG. 74 is a DSC curve corresponding to poly( ⁇ LH 2 ) prepared in Example 84.
  • Fig. 75 is a graph showing the appearance and light transmittance results of poly( ⁇ LH 2 ) prepared in Example 85 used in Application Example 1.
  • Fig. 76 is the degradation result of poly( ⁇ LH 2 ) prepared in Example 81 used in Example 91.
  • Fig. 77 is a diagram showing the change of the GPC curve before and after the post-modification sample of poly( ⁇ LH 2 ) prepared in Example 81 used in the post-polymerization modification experiment of Application Example 3/Example 92.
  • Figure 78 is the H NMR spectrum of purified poly( ⁇ LH 2 -SAr) in the post-polymerization modification experiment of Application Example 3/Example 92.
  • Fig. 79 is the fluorescence emission spectrum of the poly( ⁇ LH 2 ) sample prepared in Example 81 used in the post-polymerization modification experiment of Application Example 3/Example 92 before and after post-modification.
  • Fig. 80 is a schematic diagram of a pattern imprinting experiment and an actual photo of a mask in the post-polymerization modification experiment of Application Example 3/Example 92.
  • Figure 81 is the pattern imprinting experiment in the post-polymerization modification experiment of Application Example 3/Example 92.
  • Figure 82 shows the contact angle (55.7°) between water and the glass substrate in the post-polymerization modification experiment of Application Example 3/Example 92 (the scale bar in the upper left corner is 1 mm; the marked angle values are 55.7° (left), 55.5° ( right).
  • Figure 83 is a graph of the hydrophilic and hydrophobic properties of one poly( ⁇ LH 2 ) sample in the post-polymerization modification experiment of Application Example 3/Example 92 (the contact angles of the three poly( ⁇ LH 2 ) samples with water are 72.8 ⁇ 0.08°) , the scale bar in the upper left corner is 0.5mm, and the marked angle values are 72.8° (left) and 73.3° (right).
  • Figure 84 is a graph of the hydrophilic and hydrophobic properties of one poly( ⁇ LH 2 -SAr) sample in the post-polymerization modification experiment of Application Example 3/Example 92 (the contact angle between the three poly( ⁇ LH 2 -SAr) samples and water is 93.0 ⁇ 0.99°), the scale bar in the upper left corner is 1mm, and the marked angle values are 94.4° (left) and 94.6° (right).
  • Fig. 85 is the H NMR spectrum of the polyurethane synthesized by the one-pot two-step method using HL as the monomer prepared in Example 93.
  • Fig. 86 is the GPC raw data of the polyurethane synthesized in one pot and two steps using HL as a monomer prepared in Example 93.
  • the present invention breaks through the technical bottleneck of the prior art, and reports a chemically recyclable polymer and its synthesis method for the first time.
  • the polymer can have a single-hydroxyl-terminated or double-hydroxyl-terminated structure, and the molecular weight can be regulated according to the degree of polymerization. , the carbon dioxide content can be 28wt%.
  • the method of the present invention can realize the active polymerization of heterocyclic lactone such as six-membered lactone 3,6-diethyltetrahydro-2h-pyran-2-one (HL).
  • the HL can be prepared using carbon dioxide and cheap bulk chemicals as starting materials, as shown in Reaction Scheme 1, using palladium-catalyzed two-step process from CO 2 , H 2 and 1,3-butane Diene is synthesized into HL; the HL is then catalyzed by an organic base (such as tBu -P 4 ) for anion ring-opening polymerization (AROP) to obtain a polyester polymer compound.
  • an organic base such as tBu -P 4
  • AROP anion ring-opening polymerization
  • the present invention also develops a series of catalytic methods to chemically degrade polyester macromolecule compounds such as polyHL, so as to recover heterocyclic lactone monomers such as HL monomers.
  • the present invention also proposes a very efficient multi-step reaction strategy for the first time, thereby realizing the synthesis of chemically recyclable polymer carbon dioxide-based polyester poly( ⁇ LH 2 ) using CO 2 and butadiene as raw materials.
  • the present invention uses CO2 and butadiene as raw materials to synthesize ⁇ -L, and prepares a six-membered ring lactone containing terminal olefin groups in the side chain——3-ethyl- 6 -vinyltetrahydro-2H-pyran-2-one ( ⁇ LH 2 ), and for the first time achieved carbon dioxide-based polyester poly Synthesis of ( ⁇ LH 2 ).
  • the polyester has the characteristics of high CO2 content (for example, up to 29 wt%), good transparency, high molecular weight, high thermal stability and the like.
  • the polyester can be completely degraded back to the monomer with the participation of the catalyst, and because of the presence of terminal olefin side chains in the repeating unit of the polyester, the present invention can easily modify the polymer poly( ⁇ LH 2 ) after polymerization ;
  • the poly( ⁇ LH 2 ) olefin side chain can be grafted through the photoinduced thiol-alkene click reaction, thereby regulating the properties of the polymer.
  • the synthesis route of carbon dioxide-based polyester poly( ⁇ LH 2 ) of the present invention is shown in Reaction Scheme 2; the synthesis status of carbon dioxide-based polyester poly( ⁇ LH 2 ) and the technical route of the present invention are shown in Figure 59.
  • the present invention aims to propose a cyclic polymer with recyclable monomers and a synthesis method thereof for the first time, using heterocyclic lactones as raw materials, and preparing cyclic polymers through anionic ring-opening polymerization of the heterocyclic lactones.
  • the synthesis method can regulate the degree of polymerization of the cyclic polymer according to the degree of polymerization, and then regulate the Mn (number average molecular weight) and (The molecular weight distribution).
  • the present invention also provides a series of methods to recover cyclic polymer monomers.
  • the synthesis method of the present invention can adopt simple and easy-to-obtain raw materials to prepare cyclic polymers; for example, when the raw material heterocyclic lactone is 3,6-diethyltetrahydro-2H-pyran-2-one (HL), the HL can be It is prepared by palladium-catalyzed two-step method using CO 2 , H 2 and cheap bulk chemical 1,3-butadiene, that is, the side chain containing two CC double bonds is synthesized by CO 2 and 1,3-butadiene
  • the unsaturated lactone ⁇ -lactone, ⁇ -lactone reacts with hydrogen in the presence of a transition metal catalyst to obtain HL, as shown in Reaction Scheme 3; the prepared HL is then catalyzed by an organic base (such as t Bu-P 4 ) to open the anion Cyclic polymer polyHL is obtained by ring polymerization (AROP), and polyHL can be further cracked by the catalytic method of the present invention to obtain monomer HL
  • the present invention provides a kind of polyester polymer compound, and described polyester polymer compound comprises the repeating unit shown in following formula 4:
  • R 1 and R 2 can be the same or different, and the two groups R 1 and R 2 must meet the requirement of simultaneously existing on the six-membered heterocyclic ring, and the substituted positions are any two of the four methylene carbons, That is, must exist at the same time.
  • R 1 and R 2 are independently selected from hydrogen, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, Any one of polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, and substituted polycyclic aromatic groups; the monocyclic aromatic groups are selected from phenyl, azaaryl groups, and heteroaryl groups , Oxyaromatic group; said polycyclic aromatic group and polyheterocyclic aromatic group refer to groups comprising two or more than two monocyclic aromatic groups;
  • the halogen is selected from fluorine, chlorine, bromine and iodine.
  • the alkyl group is a linear alkyl group, a branched chain alkyl group, a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; it can also be a C1-C10 alkyl group, including methyl, ethyl , propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, ethyl.
  • the substituted alkyl is substituted linear alkyl, branched chain alkyl, cycloalkyl.
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfenamide group, sulfonamide group, morpholino group, piperazinyl.
  • substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one of the following groups or more: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amine, cycloalkoxy, cycloamino, C2-C12 alkenyl , C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkylcarbonyl, C2-C12 alkenylcarbonyl, C3-C12 cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester group , sulfoxide group, sulfone group, sulfinamide group,
  • R 1 is C1-C20 alkyl
  • R 2 is selected from C1-C20 alkyl
  • R 1 is C1-C10 alkyl
  • R 2 is selected from C1-C10 alkyl
  • R1 and R2 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl, respectively.
  • R 1 and R 2 are each ethyl.
  • X is selected from heteroatoms, including heteroatoms including O, S, N, P, etc.; preferably, X is O.
  • n is a positive integer greater than or equal to 1
  • n is a positive integer greater than or equal to 1; for example, n can be 1-100, 100-1000, 1000-5000, 5000-10000, 10000-15000, 15000-20000, 20000-30000 , 30000-40000, 40000-50000, 50000-100000, 100000-200000, etc.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 ), and the carbon dioxide-based polyester poly( ⁇ LH 2 ) contains repeating units shown in the following formula 6:
  • n is a positive integer greater than or equal to 1.
  • the polyester polymer compound includes linear, ring and star topologies.
  • R 1 , R 2 , X, n, m are as defined in the compound of formula 4 above.
  • R is selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl , polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, any one of polymer groups with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol and polyethylene glycol repeating unit structures.
  • R can represent an aromatic group, including phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, benzopyrene and its derivatives, etc.; specifically, R can be selected from phenyl, benzyl, homo Tribenzyl, o-dibenzyl, m-dibenzyl, p-dibenzyl, 1,2,3-tribenzyl, 1,2,4-tribenzyl, 1,2,3,4-tetrabenzyl , 1,2,3,5-tetrabenzyl, 1,2,4,5-tetrabenzyl, pentabenzyl, hexabenzyl, phenethyl, s-triethylphenyl, o-diethylphenyl , m-diethylphenyl, p-diethylphenyl, 1,2,3-triethylphenyl, 1,2,4-triethylphenyl,
  • R can also be a linear or branched alkane; more preferably, R can be a linear or branched alkane with carbon atoms within 10 and an alkyl substituent containing individual unsaturated bonds (unsaturated bonds refer to It is the carbon-carbon double bond of SP2 hybridization and the carbon-carbon triple bond of SP hybridization).
  • R may also be a polymer group with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol or polyethylene glycol repeating unit structure.
  • R is benzyl, p-dibenzyl, (CH2)3, (CH2)4.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the structure of the carbon dioxide-based polyester poly( ⁇ LH 2 ) is shown in Formula 7:
  • R is selected from C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 alkynyl, substituted C2-C20 alkynyl, monocyclic Aryl groups, substituted monocyclic aromatic groups, polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, substituted polyheterocyclic aromatic groups, polyvinyl alcohol, poly Any one of the macromolecular groups of the ethylene glycol repeating unit structure;
  • n is a positive integer greater than or equal to 1;
  • n is a positive integer greater than or equal to 1.
  • R 14 may represent an aromatic group, including phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, benzopyrene and derivatives thereof; specifically, R 14 may be selected from phenyl, benzyl base, mes-tribenzyl, o-dibenzyl, m-dibenzyl, p-dibenzyl, 1,2,3-tribenzyl, 1,2,4-tribenzyl, 1,2,3,4- Tetrabenzyl, 1,2,3,5-tetrabenzyl, 1,2,4,5-tetrabenzyl, pentabenzyl, hexabenzyl, phenethyl, s-triethylphenyl, o-diethyl phenyl, m-diethylphenyl, p-diethylphenyl, 1,2,3-triethylphenyl, 1,2,4-triethylphenyl, 1,2,2,3
  • R 14 can also be a linear or branched chain alkane; more preferably, R 14 can be a linear or branched chain alkane with carbon atoms within 10 and an alkyl substituent containing individual unsaturated bonds (unsaturated The bond refers to the carbon-carbon double bond with SP hybridization and the carbon-carbon triple bond with SP hybridization).
  • R 14 can also be a polymer group with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol or polyethylene glycol repeating unit structure.
  • R 14 is benzyl, p-dibenzyl, (CH 2 ) 3 , (CH 2 ) 4 .
  • n represents the number of repeating units, and n is a positive integer greater than or equal to 1; 20000-30000, 30000-40000, 40000-50000, 50000-100000, 100000-200000, etc.
  • m is the degree of branching, and m is a positive integer greater than or equal to 1.
  • m is a positive integer greater than or equal to 1.
  • 1 ⁇ m ⁇ 10, 10 ⁇ m ⁇ 20; preferably, 1 ⁇ m ⁇ 10 (m can also represent the functionality of the initiator R 14 (OH)m and/or (MO) m R 14 ).
  • R 1 , R 2 , X, and n are as described in the compound of formula 4 above.
  • the present invention provides a kind of synthetic method of polyester polymer compound, is selected from any one or both in following method:
  • the method includes: a heterocyclic lactone shown in formula 1, an organic base as a catalyst, and a reagent R(OH) m that can provide an active proton as a trigger Under the condition of reagent, synthesis obtains the polyester macromolecular compound shown in formula 2; Reaction process is shown in reaction formula 1:
  • the method includes: the heterocyclic lactone shown in Formula 1, under the catalysis of an organic base, synthesizes the polyester polymer compound shown in Formula 3 ;
  • the reaction process is shown in Reaction Formula II:
  • R 1 and R 2 can be the same or different, and the two groups R 1 and R 2 must be present on the six-membered heterocycle at the same time, and the substitution positions are four methylenes Any two of the base carbons must exist simultaneously.
  • R 1 and R 2 are independently selected from hydrogen, halogen, alkyl (linear alkyl, branched alkyl, cycloalkyl), substituted alkyl (linear alkyl, branched chain alkyl, cycloalkyl), alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl, Any one of polyheterocyclic aryl groups and substituted polyheterocyclic aryl groups; the monocyclic aryl group includes phenyl, azaaryl, sparse heteroaryl, oxaaryl; the polycyclic aryl and A polyheterocyclic aromatic group refers to a group containing two or more monocyclic aromatic groups;
  • the halogen is selected from fluorine, chlorine, bromine and iodine.
  • the alkyl group is a linear alkyl group, a branched chain alkyl group, a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; it can also be a C1-C10 alkyl group, including methyl, ethyl , propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, ethyl.
  • the substituted alkyl is substituted linear alkyl, branched chain alkyl, cycloalkyl.
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfenamide group, sulfonamide group, morpholino group, piperazinyl.
  • substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one of the following groups or more: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amine, cycloalkoxy, cycloamino, C2-C12 alkenyl , C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkylcarbonyl, C2-C12 alkenylcarbonyl, C3-C12 cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester group , sulfoxide group, sulfone group, sulfinamide group,
  • R 1 is C1-C20 alkyl
  • R 2 is selected from C1-C20 alkyl
  • R 1 is C1-C10 alkyl
  • R 2 is selected from C1-C10 alkyl
  • R1 and R2 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl, respectively.
  • R 1 and R 2 are each ethyl.
  • X is selected from heteroatoms including O, S, N, P, etc.; preferably, X is O.
  • n value represents the number of repeating units, and n is a positive integer greater than or equal to 1; for example, n can be 1-100, 100-1000, 1000-5000, 5000-10000, 10000-15000, 15000 -20000, 20000-30000, 30000-40000, 40000-50000, 50000-100000, 100000-200000, etc.
  • m is the degree of branching, and m is a positive integer greater than or equal to 1.
  • m is a positive integer greater than or equal to 1.
  • the organic base can be bulky or non-nucleophilic base.
  • the method when the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 ), the method includes: ⁇ LH 2 shown in Formula 8, when an organic base is used as a catalyst, a reagent R that provides an active proton Under the condition of 14 (OH)m and/or (MO) m R 14 as the initiator, the carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in formula 7 is synthesized; the reaction process is shown in reaction formula III:
  • R 14 is as defined above.
  • an organic base as a catalyst and/or a reagent providing an active proton as an initiator means that the method of the present invention can be synthesized under the condition that the catalyst and the initiator exist simultaneously, or can be carried out only under the condition of the initiator.
  • the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:
  • ammonium salt has the formula R 11 R 12 R 13 N + H, wherein R 11 , R 12 and R 13 each represent hydrogen (H), C1-C20 alkyl, C5-C20 cycloalkyl or C7-C20 Alkaryl groups, each of which may optionally contain one or more heteroatoms (such as oxygen, phosphorus or sulfur atoms) and/or substituents, and between R 11 and R 12 , between R 12 and R 13 There may be a ring between R 11 and R 13, and/or between R 11 and R 13 , which ring may contain heteroatoms.
  • R 11 , R 12 and R 13 each represent hydrogen (H), C1-C20 alkyl, C5-C20 cycloalkyl or C7-C20 Alkaryl groups, each of which may optionally contain one or more heteroatoms (such as oxygen, phosphorus or sulfur atoms) and/or substituents, and between R 11 and R 12 , between R 12 and R 13 There may be a ring between R 11
  • the organic base is selected from one or more of phosphazenes, compounds containing guanidino groups, and compounds containing amidino groups.
  • the organic base is selected from tBu -P 1 , tBu -P 2 , tBu -P 4 , 1,5,7-triazabicyclo[4.4.0]dec-5- ene (TBD), 1,8-diazabicycloundec-7-ene (DBU), diethylamine, dimethylamine, triethylamine, N,N ⁇ diisopropylethylamine, N ⁇ Methylmorpholine, n-octylamine, tri-n-butylamine, laurylamine, stearylamine, tetrapropylammonium hydroxide (TPAOH), tetrabutylammonium hydroxide (TBAOH), sodium or potassium alcoholate of C1 ⁇ C5, three Ethanolamine, choline, N
  • the catalyst is one or more of phosphazene and TBD.
  • R 3 -R 10 are independently selected from alkyl groups, preferably C1-C10 alkyl groups, such as C1 (methyl), C2 (ethyl), C3 (propyl, isopropyl), C4 ( butyl, tert-butyl), C5, C6, C7, C8, C9, C10 alkyl.
  • y is a positive integer greater than or equal to 1. Preferably, 1 ⁇ y ⁇ 3.
  • the phosphazenes are selected from tBu -P 1 , tBu -P 2 , and tBu -P 4 , and the structures are shown below:
  • the initiator is a reagent capable of providing active protons, specifically alcohols; preferably, the initiator is an alkoxide.
  • the alkoxide is R(OH)m, wherein R is selected from alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl , polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, substituted polycyclic aromatic groups, polymers containing polyvinyl alcohol and polyethylene glycol repeating unit structures with a molecular weight of 100,000 g/mol or less any one of the groups.
  • m can also represent the functionality of the initiator, and m is a positive integer greater than or equal to 1; for example, 1 ⁇ m ⁇ 10, 10 ⁇ m ⁇ 20; preferably, 1 ⁇ m ⁇ 10.
  • the initiator is (MO) m R 14 , or a mixture of R 14 (OH) m and (MO) m R 14 , in which Contains one or several R 14 (OH)m and one or several (MO) m R 14 ; in some preferred embodiments, the mixture contains one R 14 (OH) m and one (MO) m R 14 .
  • carbon dioxide-based polyester poly( ⁇ LH 2 ) can also be synthesized only under the condition of an organic base catalyst without adding an initiator.
  • the initiator is a reagent R 14 (OH)m and/or (MO) m R 14 capable of providing active protons, wherein R 14 is selected from the group consisting of alkyl, substituted alkyl, alkenyl substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl, polyheterocyclic aryl, substituted polyheterocyclic Aryl groups, any one of polymer groups with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol and polyethylene glycol repeating unit structures.
  • R 14 is selected from the group consisting of alkyl, substituted alkyl, alkenyl substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, polycyclic aryl, substituted polycyclic aryl, polyhetero
  • R can represent an aromatic group, including phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, benzopyrene and its derivatives, etc.; specifically, R can be selected from phenyl, benzyl, homo Tribenzyl, o-dibenzyl, m-dibenzyl, p-dibenzyl, 1,2,3-tribenzyl, 1,2,4-tribenzyl, 1,2,3,4-tetrabenzyl , 1,2,3,5-tetrabenzyl, 1,2,4,5-tetrabenzyl, pentabenzyl, hexabenzyl, phenethyl, s-triethylphenyl, o-diethylphenyl , m-diethylphenyl, p-diethylphenyl, 1,2,3-triethylphenyl, 1,2,4-triethylphenyl,
  • R can also be a linear or branched alkane; more preferably, R can be a linear or branched alkane with carbon atoms within 10 and an alkyl substituent containing individual unsaturated bonds (unsaturated bonds refer to It is the carbon-carbon double bond of SP2 hybridization and the carbon-carbon triple bond of SP hybridization).
  • R may also be a polymer group with a molecular weight of 100,000 g/mol or less containing polyvinyl alcohol or polyethylene glycol repeating unit structure.
  • R is benzyl, p-dibenzyl, (CH2)3, (CH2)4, that is, the initiator is selected from benzyl alcohol (BnOH), 1,4-benzenedimethanol (1,4-BDM ), 1,3-propanediol, 1,4-butanediol.
  • R 14 can represent linear or branched alkanes with carbon atoms within 10 and alkyl substituents containing individual unsaturated bonds (unsaturated bonds refer to carbon-carbon double bonds and SP hybridized carbon-carbon double bonds and SP hybridized Carbon-carbon triple bond), aromatic group.
  • R can represent C1-C10 alkyl ; aromatic groups, including phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, benzopyrene and derivatives thereof; specifically, R can be From methyl, ethyl, propyl, isopropyl, phenyl, benzyl, mes-tribenzyl, o-dibenzyl, m-dibenzyl, p-dibenzyl, 1,2,3-tribenzyl, 1,2,4-Tribenzyl, 1,2,3,4-Tetrabenzyl, 1,2,3,5-Tetrabenzyl, 1,2,4,5-Tetrabenzyl, Pentabenzyl, Hexabenzyl, phenethyl, s-triethylphenyl, o-diethylphenyl, m-diethylphenyl, p-diethylphenyl, 1,2,
  • R 14 is benzyl, methyl.
  • M is K, Na, Li, Rb or H.
  • the initiator is selected from benzyl alcohol (BnOH), potassium methylate (KOMe), sodium methylate (NaOMe), potassium tert-butoxide (KO t Bu), sodium tert-butoxide (NaO t Bu), tert-butyl Lithium alkoxide ( LiOtBu ).
  • n value represents the number of repeating units, and n is a positive integer greater than or equal to 1; for example, n can be 1-100, 100-1000, 1000-5000, 5000-10000, 10000-15000, 15000-20000 , 20000-30000, 30000-40000, 40000-50000, 50000-100000, 100000-200000, etc.
  • m is the degree of branching, and m is a positive integer greater than or equal to 1.
  • m is a positive integer greater than or equal to 1.
  • 1 ⁇ m ⁇ 10, 10 ⁇ m ⁇ 20; preferably, 1 ⁇ m ⁇ 10 (m can also represent the functionality of the initiator R 14 (OH)m and/or (MO) m R 14 ).
  • the molar dosage ratio of described formula 1, catalyst, initiator is (5-200): (0.01-5): 1;
  • the molar ratio of formula 8, catalyst and initiator is (5-200):(0-5):(0-1); the catalyst and initiator are not 0 at the same time.
  • it is (25-200):(0-1):(0-1); further preferably, it is (50-200):(0-1):(0-1), for example, it can be (50 -55):(0-1):(0-1), (55-60):(0-1):(0-1), (65-70):(0-1):(0-1 ), (75-80):(0-1):(0-1), (85-90):(0-1):(0-1), (95-100):(0-0.1): (0-1), (100-110):(0.1-0.2):(0-1), (110-120):(0.2-0.3):(0-1), (120-130):(0.3 -0.4):(0-1), (130-140):(0.4-0.5):(0-1), (140-150):(0.5
  • the molar dosage ratio of the formula 1 and the catalyst is (10-500):(0.01-5); preferably, it is (20-40):(0.1-4) , more preferably, is (30-350):(0.3-3), is still more preferably, is (40-300):(0.8-1.5), is still more preferably, is (50-260):1;
  • it can be 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1 , 170:1, 180:1, 190:1, 200:1, 210:1, 220:1, 230:1, 240:1, 250:1, 260:1.
  • the method of the present invention can be carried out under solvent-free conditions (ie bulk conditions) and solvent conditions.
  • the solvent of the reaction is selected from the group consisting of tetrahydrofuran (THF), TBD, benzene, toluene, xylene, dichlorobenzene, mesitylene, methylene chloride, chloroform, 1,2-dichloro Ethane, tetrahydropyrrole, tetrahydropyran, hexahydropyridine, ethyl acetate, diethyl ether, dimethyl ether, methyl ethyl ether, n-hexane, cyclohexane, cyclopentane, acetonitrile, dioxane, N,N - one or more of dimethylformamide, dimethyl sulfoxide, etc.; preferably, the reaction solvent is tetrahydrofuran (THF) and/or TBD. Even more preferably, the solvent is THF.
  • the initial concentration [M] 0 of the polyester polymer compound represented by formula 1 is not particularly limited, as long as the preparation of the polyester polymer compound can be realized.
  • the initial concentration [M] of the polyester polymer compound shown in Formula 1 is 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20mol L -1 ; preferably, [M] 0 is 3.0-10.0mol L -1 ; more preferably, 4.0-8.0mol L -1 1 ; more preferably, 5.0-6.3 mol L -1 ; still more preferably, 5.0, 5.3 or 6.3 mol L -1 .
  • the initial concentration [M] 0 of the heterocyclic lactone shown in Formula 1 is 0.1-20mol L -1 , for example, it can be 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 mol L -1 .
  • the initial concentration [M] 0 of the heterocyclic lactone is 3-6 mol L -1 .
  • the initial concentration [M] 0 of the heterocyclic lactone is 4-5 mol L - 1 .
  • the initial concentration [M] 0 of the heterocyclic lactone is 4.0 mol L -1 .
  • the initial concentration [ ⁇ LH 2 ] 0 of the solvent of Formula 8 in the reaction is 1-7M; preferably, 3-7M; more preferably, 5- 6M; more preferably, 5.5-6M; still more preferably, 5.62 or 5.82M.
  • the reaction temperature is not particularly limited, as long as the preparation of the polyester polymer compound can be realized.
  • the reaction temperature is -100 to 200°C, which can be -100 to 180, -80 to 200, -100 to 150, -100 to 130, -100 to 120, -100 ⁇ 100°C, -80 ⁇ 80, -70 ⁇ 70, -60 ⁇ 60, -50 ⁇ 50, -50 ⁇ 60, -40 ⁇ 40, -30 ⁇ 30, -20 ⁇ 20, -10 ⁇ 10°C.
  • it is -50 to 60°C.
  • it is -25 ⁇ 45°C, for example, it can be -25, -24, -23, -22, -21, -20, -19, -18, -17, -16, -15, -14, -13, -12, -11, -10, -9, -8, -7, -6, -5, -4, -3, -2, -1, 0, 1, 2, 3, 4, 5 , 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 , 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45°C. Still more preferably, it is -25 to -9°C. Still more preferably, it is -25°C.
  • the reaction temperature is -100-220°C, which can be -100-180, -80-200, -100-150, -100-130, -100-120, -100 ⁇ 100°C, -80 ⁇ 80, -70 ⁇ 70, -60 ⁇ 60, -50 ⁇ 50, -50 ⁇ 60, -40 ⁇ 40, -30 ⁇ 30, -20 ⁇ 20, -10 ⁇ 10 °C.
  • it is -80 to 80°C. More preferably, it is -50 to 60°C.
  • the temperature of the reaction is -30 to -10°C. In some preferred embodiments, the temperature of
  • the reaction time is not particularly limited, as long as the preparation of the polyester polymer compound can be realized.
  • the reaction time is 10s-360h; it can be 10s-360h, 20s-340h, 30s-320h, 40s-300h, 1min-280h, 1min-260h, 1min-240h ,1min-220h,1min-200h,1min-180h,1min-160h,1min-140h,1min-120h,2min-260h,3min-240h,4min-220h,5min-200h,10min-180h,30min s-160h, 1-150h, 1h-140h, 5h-120h, 10h-100h.
  • the reaction time is 1-150h.
  • it is 8-120h, such as 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 60, 70, 72, 80, 90, 96, 100, 110, 120h. Even more preferably, it is 8-12h.
  • the reaction time is 10s-360h; it can be 10s-360h, 20s-340h, 30s-320h, 40s-300h, 1min-280h, 1min-260h, 1min-240h ,1min-220h,1min-200h,1min-180h,1min-160h,1min-140h,1min-120h,2min-260h,3min-240h,4min-220h,5min-200h,10min-180h,30min s-160h, 1-150h, 1h-140h, 5h-120h, 10h-100h.
  • the reaction time is 1-150h.
  • it is 8-120h, such as 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 60, 70, 72, 80, 90, 96, 100, 110, 120h. Even more preferably, it is 12-48h.
  • the reaction time is 5s-400h; it can be 10s-380h, 20s-36e40h, 40s-320h, 1min-300h, 1min-280h, 1min-260h, 1min-240h , 1min-220h, 1min-200h, 1min-180h, 1min-160h, 1min-140h, 1min-120h, 1min-100h, 1min-80h, 1min-60h, 1min-40h, 5min-40h, 11min-40h, 16min -40h, 1min-40h, 1min-40h, 1min-40h, 1min-40h, 1min-40h, 1min-40h, 5min-100h, 2min-260h, 3min-240h, 4min-220h, 5min-200h, 10min-180h, 30min-160h , 1h-150h, 1h-120h, 1h-100h, 1h-80h, 1h-60h, 1h-40h, 1h-20h, 1h-10h
  • the reaction time is 10min-20h, such as 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, 30min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h.
  • the reaction time is 11min; in other preferred embodiments, the reaction time is 16min; in other preferred embodiments, the reaction time is 0.5h; in other preferred embodiments way, the reaction time is 2h; in other preferred embodiments, the reaction time is 2.5h; in other preferred embodiments, the reaction time is 3h; in other preferred embodiments, the The reaction time is 4h; in other preferred embodiments, the reaction time is 6-8h; in other preferred embodiments, the reaction time is 7h; in other preferred embodiments, the reaction time is 10h; in other preferred embodiments, the reaction time is 12h.
  • R 1 when R 1 is ethyl, R 2 is ethyl, that is, formula 1 is HL, and when the initiator is R 1 OH, a monohydroxyl-terminated polyester polymer compound is generated; when R 1 is ethyl base, R 2 is ethyl, that is, formula 1 is HL, and when the initiator is HO-R 2 -OH, a double hydroxyl end-capped polyester polymer compound is generated; the reaction formula is as follows:
  • Fig. 1 The possible chain initiation mechanism during the ring-opening polymerization of HL catalyzed by tBu -P 4 /BnOH of the present invention is shown in Fig. 1 .
  • the stoichiometric reaction of tBu -P 4 with BnOH at room temperature was monitored by 1 H NMR, and the formation of the complex [ tBu -P 4 H+...OBn] was found.
  • the present invention observed the disappearance of ⁇ 0.92ppm hydroxyl H and other signal chemical shift changes of tBu-P4 and BnOH.
  • n is defined as above.
  • the present invention also provides the cyclic polyester polymer compound prepared by the above method.
  • the method can regulate the degree of polymerization of the cyclic polymer according to the degree of polymerization, and then regulate the Mn (number average molecular weight) and (The molecular weight distribution).
  • the M n of the cyclic polymer is between 30-2000 kg mol ⁇ 1 .
  • the M n of the cyclic polymer is between 30-100 kg mol ⁇ 1 .
  • the M n of the cyclic polymer is between 100-200 kg mol ⁇ 1 .
  • the M n of the cyclic polymer is between 200-400 kg mol ⁇ 1 .
  • the M n of the cyclic polymer is between 500-600 kg mol ⁇ 1 . In other preferred embodiments, the M n of the cyclic polymer is between 500-800 kg mol ⁇ 1 . In other preferred embodiments, the M n of the cyclic polymer is between 400-1500 kg mol ⁇ 1 . In other preferred embodiments, the M n of the cyclic polymer is between 300-2000 kg mol ⁇ 1 .
  • the present invention also provides the cyclic polyester polymer compound shown in formula 3 or the cyclic polyester polymer compound prepared by the above method in the preparation of polymer films, pressure-sensitive adhesives (such as tapes), thermoplastic elastic Any one or several applications in the body; wherein, the pressure-sensitive adhesive can be further used to prepare products such as adhesive tapes.
  • the polymer film is colorless, transparent and has good flexibility and viscoelasticity.
  • the adhesive tape is colorless, transparent and has good flexibility and viscoelasticity.
  • the present invention also provides the polyester polymer compound prepared by the above method.
  • the present invention also provides the carbon dioxide-based polyester poly( ⁇ LH 2 ) prepared by the above method.
  • the present invention also provides the polyester polymer compound or the polyester polymer compound prepared by the above method in the preparation of one or more of polyurethane, polymer film, pressure-sensitive adhesive, adhesive tape, thermoplastic elastomer application.
  • the poly( ⁇ LH 2 ) in the present invention is a flexible material with various excellent physical and chemical properties, including high transparency, high molecular weight, strong thermal stability, good ductility and the like. Based on this, the present invention also provides the application of the carbon dioxide-based polyester poly( ⁇ LH 2 ) or the carbon dioxide-based polyester poly( ⁇ LH 2 ) prepared by the above method in the fields of polyurethane and pressure-sensitive adhesives.
  • Polyurethane field The full name of polyurethane is polyurethane, which is a kind of polymer compound, mainly including polyester type and polyether type. Polyurethane is mainly obtained by the reaction of polyester polyol or polyether polyol with multifunctional isocyanate (such as diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, etc.) Or polyether polyol is an indispensable raw material in the field of polyurethane synthesis.
  • multifunctional isocyanate such as diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, etc.
  • Polyurethane is divided into hard foam, soft foam, polyurethane elastomer, thermoplastic, polyurethane adhesive, polyurethane coating and paint according to its material properties, and is widely used in automobile manufacturing, furniture, construction, insulation materials, and shoes It has very important application value in many fields such as manufacturing industry.
  • Polyester polyols and polyether polyols are important precursors for the synthesis of polyurethane materials in industry, and polyurethane materials based on polyester polyols tend to have better mechanical properties than polyether polyol polyurethanes.
  • polyurethane materials based on polyester polyols tend to have better mechanical properties than polyether polyol polyurethanes.
  • the production cost of polyester polyol is much higher than that of polyether polyol, the large-scale application of polyester polyol is limited. Therefore, the polyHL prepared by the present invention, a cheap and easy-to-obtain polyester material with a new chemical structure, and the corresponding polyester polyol have great and far-reaching significance for the polyurethane field and even the chemical industry.
  • Pressure-sensitive adhesive full name of pressure-sensitive adhesive, commonly known as self-adhesive, referred to as pressure-sensitive adhesive, is an indispensable functional material in the polymer industry.
  • the main pressure-sensitive adhesives currently on the market are mainly polyolefins, so polyolefins cannot be degraded after use, and polyHL has relatively good pressure-sensitive adhesives through the preliminary experimental results of the present invention.
  • the tape can be transparent tape, opaque tape, single-sided tape, double-sided tape, protective tape, thermal insulation tape, high temperature tape, masking tape, electrical tape, electroplating tape, packing tape, cloth tape, fiber tape, PE foam Tape, kraft paper tape, protective film tape, special tape, etc.
  • the adhesive tape is scotch adhesive tape. In other preferred embodiments, the adhesive tape is 3M commercial scotch adhesive tape.
  • the polymer film is colorless and transparent, and has good flexibility and viscoelasticity (peel strength).
  • the present invention also provides the application of organic bases such as phosphazene in catalyzing the compound of formula 1 to synthesize the polyester polymer compound shown in formula 2 and/or formula 3.
  • organic bases such as phosphazene in catalyzing the compound of formula 1 to synthesize the polyester polymer compound shown in formula 2 and/or formula 3.
  • the organic base can be a bulky or non-nucleophilic base.
  • the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:
  • ammonium salt has the formula R 11 R 12 R 13 N + H, wherein R 11 , R 12 and R 13 each represent hydrogen (H), C1-C20 alkyl, C5-C20 cycloalkyl or C7-C20 Alkaryl groups, each of which may optionally contain one or more heteroatoms (such as oxygen, phosphorus or sulfur atoms) and/or substituents, and between R 11 and R 12 , between R 12 and R 13 There may be a ring between R 11 and R 13, and/or between R 11 and R 13 , which ring may contain heteroatoms.
  • R 11 , R 12 and R 13 each represent hydrogen (H), C1-C20 alkyl, C5-C20 cycloalkyl or C7-C20 Alkaryl groups, each of which may optionally contain one or more heteroatoms (such as oxygen, phosphorus or sulfur atoms) and/or substituents, and between R 11 and R 12 , between R 12 and R 13 There may be a ring between R 11
  • the organic base is selected from one or more of phosphazenes, compounds containing guanidino groups, and compounds containing amidino groups.
  • the organic base is selected from tBu -P 4 , 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diaza Dicycloundec-7-ene (DBU), diethylamine, dimethylamine, triethylamine, N,N ⁇ diisopropylethylamine, N ⁇ methylmorpholine, n-octylamine, tri-n-butyl Amine, Laurylamine, Stearylamine, Tetrapropylammonium Hydroxide (TPAOH), Tetrabutylammonium Hydroxide (TBAOH), C1 ⁇ C5 Sodium or Potassium Alkoxide, Triethanolamine, Choline, N-Methylmorpholine, Pyridine, dimethylaminopyridine, N, N'-
  • the organic base is one or more of phosphazene and TBD.
  • R 3 -R 10 are independently selected from alkyl groups, preferably C1-C10 alkyl groups, such as C1 (methyl), C2 (ethyl), C3 (propyl, isopropyl), C4 ( butyl, tert-butyl), C5, C6, C7, C8, C9, C10 alkyl.
  • y is a positive integer greater than or equal to 1. For example, 1 ⁇ y ⁇ 10, 10 ⁇ y ⁇ 20; preferably, 1 ⁇ y ⁇ 3.
  • the phosphazenes are selected from tBu -P 1 , tBu -P 2 , and tBu -P 4 , and the structures are shown below:
  • the present invention also provides a method for catalyzing polymer recovery monomers, said method being selected from any one or both of the following:
  • catalytic formula 2 includes catalytic method and pyrolysis method (thermolysis);
  • catalytic formula 3 includes inorganic salt pyrolysis catalytic method and La[N(SiMe 3 ) 2 ] 3 mild catalytic method.
  • the catalytic method includes: using inorganic salts, metal organic compounds, organic compound catalysts to degrade the polyester polymer compound of formula 2, and recovering the heterocyclic monomer or its oligomeric compound shown in formula 1 polymers or their derivatives;
  • the catalytic method includes: degrading the carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in Formula 8 by using at least one compound among inorganic salts, metal-organic compounds or organic compound catalysts, and recovering ⁇ LH 2 shown in Formula 7 or its oligomers or derivatives thereof;
  • the pyrolysis method includes: thermally cracking the polyester polymer compound of the formula 2, and recovering the heterocyclic monomer shown in the formula 1 or its oligomer or its derivative; the catalytic method Including: in a solvent, using catalysts such as inorganic salts, metal organic compounds, and organic compounds to degrade the polyester polymer compound shown in formula 2 to obtain the heterocyclic compound shown in formula 1 or its oligomer or the corresponding compound of formula 1 derivative.
  • the pyrolysis method includes: for the carbon dioxide-based polyester poly( ⁇ LH 2 ) shown in the formula 8 ⁇ LH 2 ) is thermally cracked, and the ⁇ LH 2 represented by formula 7 or its oligomer or its derivative is recovered.
  • the solvent is selected from benzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, o-dichlorobenzene, o-dibromobenzene, m-dichlorobenzene, m-dibromobenzene, p-dichlorobenzene, In p-dibromobenzylbenzene, m-xylene, p-xylene, o-xylene, mesitylene, dimethylsulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.
  • polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the solvent is more preferably toluene.
  • the salt is an inorganic salt
  • the inorganic salt is selected from zinc chloride, tin chloride, cupric chloride, nickel chloride, cuprous chloride, palladium chloride, platinum chloride, yttrium chloride, Ferric chloride, ferrous chloride, titanium trichloride, zirconium chloride, lanthanum trichloride, lanthanum alumina, lanthanum fluoride, lanthanum boride, lanthanum sulfate, lanthanum hydroxide, lanthanum carbonate, lanthanum oxalate, lanthanum acetate , lanthanum bromide, lanthanum nitrate, etc.; preferably, zinc chloride.
  • the organometallic compound is selected from stannous octoate, stannous isooctanoate, dibutyltin dilaurate, bis[bis(trimethylsilyl)amino]tin, triisopropyloxylanthanum, tri[ N,N-bis(trimethylsilane)amine]lanthanum, lanthanum triflate, silver triflate, copper triflate, iron triflate, scandium triflate, One or more of yttrium trifluoromethanesulfonate, etc.; preferably, stannous octoate, tris[N,N-bis(trimethylsilane)amine]lanthanum.
  • the organic compound is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1 5 7-triazidebicyclo(4.4.0)dec-5
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-ene
  • TBD 1,5 7-triazidebicyclo(4.4.0)dec-5
  • -ene TBD
  • IMes 1,3-di-me-trimethylimidazolium-2-ylidene
  • tBu -P 1 , tBu -P 2 , tBu -P 4 is DBU.
  • the catalyst is an inorganic salt; more preferably, a lanthanum salt; even more preferably, La[N(SiMe 3 ) 2 ] 3 .
  • the degradation condition is a thermal bath method such as oil bath or sand bath, and the temperature range is 100-300°C; preferably 120-300°C; more preferably 160°C.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the temperature range is preferably 120-180°C; more preferably 120°C.
  • the degradation time is 8-24h; preferably 12h.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the degradation time is 0.5-24h; preferably 0.5-8h; preferably 1-5h; preferably 2h.
  • the pyrolysis method includes: thermally cracking the polyester polymer compound as described above to obtain the heterocyclic compound shown in Formula 1 or its oligomer or the corresponding derivative.
  • the thermal cracking is preferably carried out in a nitrogen atmosphere.
  • the thermal cracking is carried out under sealed conditions.
  • the thermal cracking is carried out under vacuum conditions.
  • the thermal cracking is preferably carried out in a sand bath.
  • the present invention does not limit the heating temperature, as long as the purpose of thermal cracking can be achieved to recover the monomers of the polyester polymer compound.
  • the temperature of the heating is greater than 100°C.
  • the temperature of the heating is 100-1000°C; 800, 800-900, 900-1000°C.
  • the heating temperature is 150-300°C. More preferably, it is 150-260°C. More preferably, it is 180-230°C. More preferably, it is 200-230°C. Still more preferably, it is 220°C.
  • the present invention does not limit the heating time, as long as the purpose of thermal cracking can be achieved to recover the monomers of the polyester polymer compound.
  • the heating time is greater than 0.5h.
  • the heating time is 1-50h; it can be 1-5, 5-10, 10-15, 15-20, 1-20, 20-25, 25-30, 30-35 , 35-40, 40-45, 45-50h.
  • the heating time is 1-20h. More preferably, it is 1-10h. Even more preferably, it is 1-5h. Even more preferably, it is 3h.
  • the step includes: in toluene, at 120°C, for the carbon dioxide-based poly
  • the ester poly( ⁇ LH 2 ) is catalytically cracked with La[N(SiMe 3 ) 2 ] 3 for 2 hours to obtain ⁇ LH 2 shown in Formula 7 or its oligomer or the corresponding derivative of Formula 7.
  • the inorganic salt pyrolysis catalytic method includes: using inorganic salts to catalyze the degradation of polyester polymer compounds shown in formula 3 to obtain heterocyclic compounds shown in formula 1 or their oligomers or the corresponding derivative;
  • the La[N(SiMe 3 ) 2 ] 3 mild catalytic method includes: using La[N(SiMe 3 ) 2 ] 3 to catalytically crack the polyester polymer compound shown in formula 3 under mild conditions , to obtain the heterocyclic compound represented by formula 1 or its oligomer or the corresponding derivative of formula 1.
  • the pyrolysis catalytic method can be carried out under solvent or solvent-free conditions.
  • the solvent when degrading in a solvent, can be selected from toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, o-dichlorobenzene, o-dibromobenzene, m-dichlorobenzene , m-dibromobenzene, p-dichlorobenzene, p-dibromobenzene toluene, m-xylene, p-xylene, o-xylene, mesitylene, dimethyl sulfoxide, N,N-dimethylformamide, N , one or more of N-dimethylacetamide, etc.
  • the solvent is toluene.
  • the solvent is mesitylene.
  • the solvent is o-dichlorobenzene.
  • the pyrolysis catalytic method has no special limitation on the initial concentration [M] 0 of the cyclic polymer of formula (2), as long as the preparation of the cyclic polymer can be realized.
  • the initial concentration [M] 0 of the cyclic polymer of formula (2) is 1-50 mol L -1 , such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 mol L -1 .
  • it is 2-40 mol L -1 ; more preferably, it is 3-30 mol L -1 ; even more preferably, it is 4-20 mol L -1 .
  • the initial concentration [M] 0 of the cyclic polymer is 3-6 mol L -1 .
  • the initial concentration [M] 0 of the heterocyclic lactone is 4.0 mol L -1 .
  • the conditions for pyrolysis and catalysis are heat bath methods such as oil bath or sand bath, and the temperature range is 100-350°C.
  • it is 110-300°C; more preferably, it is 120-240°C; it can be 120, 30, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240°C.
  • the temperature of the pyrolysis catalysis is 120°C.
  • the temperature of the pyrolysis catalysis is 130°C.
  • the temperature of the pyrolysis catalysis is 140°C.
  • the temperature of the pyrolysis catalysis is 150°C.
  • the temperature of the pyrolysis catalysis is 160°C.
  • the temperature of the pyrolysis catalysis is 180°C.
  • the time of the pyrolysis catalysis is 6-45h; preferably, it is 8-36h, which can be 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36h.
  • the pyrolysis catalysis time is 10 hours. In some preferred embodiments, the pyrolysis catalysis time is 12 hours. In some preferred embodiments, the pyrolysis catalysis time is 16 hours. In some preferred embodiments, the pyrolysis catalysis time is 24 hours.
  • the physical and chemical properties of the applicable cyclic polymers of the inorganic salt catalytic cracking method of the present invention are not particularly limited, as long as the cyclic polymers obtained by the above-mentioned method or other methods of the present invention can be recovered by the cracking method of the present invention. body.
  • the inorganic salt catalytic cracking method of the present invention is suitable for cyclic polymers with M n in the range of 300-2000 kg mol ⁇ 1 .
  • the inorganic salt catalytic cracking method of the present invention is suitable for cyclic polymers with M n in the range of 400-1500 kg mol ⁇ 1 .
  • the inorganic salt catalytic cracking method of the present invention is suitable for cyclic polymers with M n in the range of 500-800 kg mol ⁇ 1 . In some preferred embodiments, the inorganic salt catalytic cracking method of the present invention is suitable for cyclic polymers whose M n is in the range of 500-600 kg mol ⁇ 1 . In some preferred embodiments, the inorganic salt catalytic cracking method of the present invention is applicable to the cyclic polymers prepared in Examples 1-17 of the present invention.
  • the pyrolysis catalysis is carried out in a nitrogen atmosphere.
  • the pyrolysis catalysis is carried out under sealed conditions.
  • the pyrolysis catalysis is carried out under vacuum conditions.
  • the La[N(SiMe 3 ) 2 ] 3 mild catalytic method includes: using La[N(SiMe 3 ) 2 ] 3 to carry out catalytic cracking of the above-mentioned cyclic polymer under mild conditions to obtain
  • the heterocyclic compound represented by Formula 1 or its oligomer is also the corresponding derivative of Formula 1.
  • the La[N(SiMe 3 ) 2 ] 3 mild catalytic method can be carried out under solvent or solvent-free conditions.
  • the solvent can be selected from toluene, benzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, o-dichlorobenzene, o-dibromobenzene, m-dichlorobenzene, m-dibromobenzene Benzene, p-dichlorobenzene, p-dibromobenzene, m-xylene, p-xylene, o-xylene, mesitylene, dimethylsulfoxide, N,N-dimethylformamide, N,N-di One or more of methyl acetamide, etc.
  • the solvent is toluene.
  • the solvent is mesitylene.
  • the mild catalytic method has no special limitation on the initial concentration [M] 0 of the cyclic polymer of formula (2), as long as the preparation of the cyclic polymer can be realized.
  • the initial concentration [M] 0 of the cyclic polymer of formula (2) is 1-50 mol L -1 , such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50 mol L -1 .
  • it is 2-40 mol L -1 ; more preferably, it is 3-30 mol L -1 ; even more preferably, it is 4-20 mol L -1 .
  • the initial concentration [M] 0 of the cyclic polymer is 3-6 mol L -1 .
  • the initial concentration [M] 0 of the heterocyclic lactone is 4.0 mol L -1 .
  • the condition of the mild catalysis is a thermal bath method such as an oil bath or a sand bath, and the temperature range is 40-90°C; preferably, 50-80°C, which can be 50, 55, 60, 65, 70 , 75, 80°C.
  • the degradation temperature is 50°C.
  • the degradation temperature is 60°C.
  • the degradation temperature is 70°C.
  • the degradation temperature is 80°C.
  • the time of the mild catalysis is 1-45h, which can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 , 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43 , 44, 45h.
  • the degradation time is 3 hours. In some preferred embodiments, the degradation time is 6 hours. In some preferred embodiments, the degradation time is 9 hours. In some preferred embodiments, the degradation time is 12 hours. In some preferred embodiments, the degradation time is 15 hours. In some preferred embodiments, the degradation time is 18 hours. In some preferred embodiments, the degradation time is 21 hours. In some preferred embodiments, the degradation time is 24 hours.
  • the physical and chemical properties of the cyclic polymers suitable for the mild catalytic method of the present invention are not particularly limited, as long as the cyclic polymers obtained by the above-mentioned method or other methods of the present invention can adopt the mild catalytic method of the present invention to reclaim monomers .
  • the mild catalytic method of the present invention is suitable for cyclic polymers with M n in the range of 300-2000 kg mol ⁇ 1 .
  • the mild catalytic method of the present invention is suitable for cyclic polymers with M n in the range of 400-1500 kg mol ⁇ 1 .
  • the mild catalytic method of the present invention is suitable for cyclic polymers with M n in the range of 500-800 kg mol ⁇ 1 . In some preferred embodiments, the mild catalytic method of the present invention is suitable for cyclic polymers with M n in the range of 500-600 kg mol ⁇ 1 . In some preferred embodiments, the mild catalytic method of the present invention is applicable to the cyclic polymers prepared in Examples 1-17 of the present invention.
  • the mild catalysis is carried out in a nitrogen atmosphere.
  • the mild catalysis is carried out under sealed conditions.
  • the mild catalysis is performed under vacuum conditions.
  • reaction process is selected from any one or both of the following reaction formula VII or reaction formula VIII:
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the present invention does not limit the ⁇ -L raw materials used in the following examples, which can be obtained commercially or prepared by the following method: CO 2 and 1,4-butadiene were synthesized under Pd-catalyzed conditions to synthesize ⁇ -L, and ⁇ -L was synthesized under the conditions of Stryker reagent catalyzed and triethoxysilane (HSi(OEt)3) as a hydrogen source, The reaction process is shown in reaction scheme 4 below.
  • the polyester polymer compound is carbon dioxide-based polyester poly( ⁇ LH 2 )
  • the present invention provides a disubstituted ⁇ , ⁇ -saturated six-membered ring lactone, the structure of which is shown in formula 10 below:
  • R 1 and R 2 are independently selected from hydrogen, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aryl, substituted monocyclic aryl, Any one of polycyclic aromatic groups, substituted polycyclic aromatic groups, polyheterocyclic aromatic groups, and substituted polycyclic aromatic groups; the monocyclic aromatic groups are selected from phenyl, azaaryl groups, and heteroaryl groups , Oxyaromatic group; said polycyclic aromatic group and polyheterocyclic aromatic group refer to groups containing two or more monocyclic aromatic groups; R 1 and R 2 may be the same or different.
  • the halogen is selected from fluorine, chlorine, bromine and iodine.
  • the alkyl group is a linear alkyl group, a branched chain alkyl group, a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; it can also be a C1-C10 alkyl group, including methyl, ethyl , propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, ethyl.
  • the substituted alkyl is substituted linear alkyl, branched chain alkyl, cycloalkyl.
  • the alkenyl is a linear alkyl, branched alkyl, cycloalkyl; further, the alkenyl can be a C2-C20 alkenyl; it can also be a C2-C10 alkenyl, including vinyl, propenyl , butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl; preferably vinyl.
  • the substituted alkenyl is substituted linear alkenyl, branched alkenyl, cycloalkenyl.
  • the alkynyl is a linear alkynyl, a branched alkynyl, a cycloalkynyl; further, the alkynyl can be a C2-C20 alkynyl; it can also be a C2-C10 alkynyl, including ethynyl, propynyl radical, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl; preferably, ethynyl.
  • the substituted alkynyl is substituted linear alkynyl, branched alkynyl, cycloalkynyl.
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfenamide group, sulfonamide group, morpholino group, piperazinyl.
  • substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one of the following groups or more: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amine, cycloalkoxy, cycloamino, C2-C12 alkenyl , C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkylcarbonyl, C2-C12 alkenylcarbonyl, C3-C12 cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester group , sulfoxide group, sulfone group, sulfinamide group,
  • R 1 is C1-C20 alkyl
  • R 2 is selected from C2-C20 alkenyl
  • R 1 is C1-C10 alkyl (can be C1, C2, C3, C4, C5 , C6, C7, C8, C9, C10 alkyl)
  • R 2 is selected from C1-C10 alkenyl (can be C2, C3, C4, C5, C6, C7, C8, C9, C10 alkenyl).
  • R 1 is methyl and R 2 is vinyl.
  • the present invention also provides a method for preparing a disubstituted ⁇ , ⁇ -saturated six-membered ring lactone as shown in formula 10, the method Using the disubstituted ⁇ , ⁇ -unsaturated six-membered ring lactone shown in Formula 9 as the raw material, using the Stryker reagent or a mixed reagent capable of generating Stryker reagent in situ as the catalyst, and organosilane as the hydrogen source, through the selection of conjugated olefins The selective reduction reaction prepares the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone shown in Formula 10; the selective reduction reaction is shown in Reaction Formula A,
  • R 1 and R 2 are the same as those described in formula 10 above.
  • the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone is a six-membered ring lactone with a double group substitution.
  • the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone is a mixture of diastereomers.
  • the chemical formula of the Stryker reagent is [(Ph 3 P)CuH] 6 .
  • halogen atoms such as F, Cl, Br, I
  • anion species such as sulfate, sulfite, bisulfite, nitrate, acetate, etc.
  • ligand compounds such as acetylaceton
  • the group can represent halogen atoms such as fluorine, chlorine, bromine and iodine, and can also refer to different substituents such as alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic
  • the monocyclic aryl group is selected from phenyl, azaaryl, sparse heteroaryl, oxaaryl; the polycyclic aryl and polyheteroaryl refer to two or more A group of monocyclic aromatic groups.
  • the halogen is selected from fluorine, chlorine, bromine and iodine.
  • the alkyl group is a linear alkyl group, a branched chain alkyl group, a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; it can also be a C1-C10 alkyl group, including methyl, ethyl , propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, ethyl.
  • the substituted alkyl is substituted linear alkyl, branched chain alkyl, cycloalkyl.
  • the substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one or more of the following groups : hydrogen, heteroatom, amino, cyano, benzyl, alkylcarbonyl, alkenylcarbonyl, cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester, sulfoxide, alkenyl, alkyne group, cycloalkyl group, sulfone group, hydroxyl group, nitro group, halogen group, carboxyl group, alkyl group, alkoxy group, amino group, cycloalkoxy group, cyclic amino group, sulfenamide group, sulfonamide group, morpholino group, piperazinyl.
  • substituents on the alkyl group, alkenyl group, alkynyl group, monocyclic aromatic group, polycyclic aromatic group, and polyheterocyclic aromatic group are mono-substituted or multi-substituted, and are independently selected from one of the following groups or more: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amine, cycloalkoxy, cycloamino, C2-C12 alkenyl , C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkylcarbonyl, C2-C12 alkenylcarbonyl, C3-C12 cycloalkylcarbonyl, phenylcarbonyl, benzylcarbonyl, alkoxycarbonyl, ester group , sulfoxide group, sulfone group, sulfinamide group,
  • R 0 is an alkyl group of C1-C20, even more preferably, R 0 is an alkyl group of C1-C10, which can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 alkyl.
  • the preparation method of the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone shown in formula 10 is shown in the following reaction formula A-1:
  • the mass ratio of the disubstituted ⁇ , ⁇ -unsaturated six-membered ring lactone, Stryker reagent, and organosilane is (0.5-30):(0.05-5):(3-40); preferably, it is (2- 15):(0.06-1):(6-20), such as (2-5):(0.06-1):(6-20), (5-8):(0.06-1):(6 -20), (8-10):(0.06-1):(6-20), (10-15):(0.06-1):(6-20), (2-15):(0.08-0.1 ):(6-20), (2-15):(0.1-0.3):(6-20), (2-15):(0.3-0.5):(6-20), (2-15): (0.5-0.8):(6-20), (2-15):(0.8-1):(6-20), (2-15):(0.06-1):(6-8), (2 -15):(0.06-1):(8-10), (2-15):(0.06-1):(10-12), (2-15
  • the temperature of the selective reduction reaction is not particularly limited, as long as the preparation of the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone can be realized.
  • the temperature of the reaction is 0-50°C, and may be 0-10, 10-20, 20-30, 30-40, 40-50°C.
  • it is 10-40°C.
  • it is 15-35°C, such as 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 , 34, 35°C.
  • it is normal temperature 25 ⁇ 5°C. Still more preferably, it is 25°C.
  • the time of the selective reduction reaction is not particularly limited, as long as the preparation of the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone can be realized.
  • the reaction time is 30s-160h; it can be 30s-10min, 10min-30min, 30min-1h, 1h-3h, 3h-6h, 6h-10h, 10h-30h, 30h-60h, 60h-90h, 90h-120h, 120h-160h.
  • the reaction time is 1h-10h. More preferably, it is 2-8h. Even more preferably, it is 6h.
  • the solvent of the selective reduction reaction is selected from toluene, xylene, dichlorobenzene, mesitylene, dichloromethane, chloroform, tetrahydrofuran (THF), TBD, benzene, 1,2-dichloroethane, tetrahydropyrrole , tetrahydropyran, hexahydropyridine, ethyl acetate, diethyl ether, dimethyl ether, methyl ethyl ether, n-hexane, cyclohexane, cyclopentane, acetonitrile, dioxane, N,N-dimethylformamide , dimethyl sulfoxide, etc. one or more.
  • it is toluene.
  • the process of preparing the disubstituted ⁇ , ⁇ -saturated six-membered ring lactone in the present invention is carried out under stirring conditions.
  • the process for preparing a disubstituted ⁇ , ⁇ -saturated six-membered ring lactone in the present invention specifically includes dissolving Stryker reagent and organosilane in a solvent, and then adding ⁇ -L dropwise to the mixture for reaction.
  • the present invention does not limit the HL raw materials used in the following examples, which can be obtained commercially, or prepared by the following method: CO 2 and 1,4-butadiene synthesize ⁇ -L, ⁇ - L and H2 synthesize the six-membered lactone 3,6-diethyltetrahydro-2h-pyran-2-one (HL) under Pd/C catalytic conditions, and the reaction process is shown in the following reaction scheme 2.
  • the raw material is HL
  • the compound polyHL is prepared by ring-opening polymerization of HL and BnOH, and the reaction formula is as follows
  • the raw material is HL
  • the cyclic compound polyHL is prepared by ring-opening polymerization of HL under the catalysis of an organic base.
  • the reaction formula is as follows
  • Polymer number average molecular weight Mn and molecular weight distribution Determination method take out 200 ⁇ L reaction solution from reaction system, solvent rotary evaporation is removed, by GPC method, under 40 °C of conditions, in tetrahydrofuran mobile phase, measure the Mn (number average molecular weight) and the Mn (number average molecular weight) and (The molecular weight distribution).
  • Embodiment 1 TBD, DBU catalyze the ROP reaction of HL
  • Concrete synthetic steps include:
  • the present inventors For the ring-opening polymerization (ROP) of HL to generate polyHL, the present inventors initially tried catalysts with a complex insertion mechanism, including tin(II) 2-ethylhexanoate [Sn(Oct) 2 ] and dilaurate Dibutyltin dibutyltin (DBTDL), etc., but no polymer was obtained.
  • the present invention also uses the organic acid diphenyl phosphate (DPP), and no polymer is obtained.
  • Example 1 represents the solvent-free condition; [M] 0 (mol/L) is the initial concentration of the HL monomer in the system, and refers to the concentration of the monomer in the system when the reaction is fed.
  • the quenched reaction solution was added dropwise to 20 mL ice methanol, and the supernatant was discarded after centrifugation, and the precipitate was polyHL.
  • M n number average molecular weight
  • M m Molecular weight distribution
  • the preparation steps are as in Example 1, except that, in a nitrogen atmosphere glove box, 0.0158 mmol of TBD catalyst and 0.0158 mmol of BnOH are added to a flame-dried 10 mL Schlenk tube, and 0.02 mL of tetrahydrofuran (THF) needs to be added Dissolve it.
  • THF tetrahydrofuran
  • Embodiment 3 ⁇ 17 researches the catalytic activity in the ROP of HL after three kinds of phosphazenes are combined with BnOH
  • the pKa of t Bu-P 1 , t Bu-P 2 and t Bu-P 4 in acetonitrile are 26.9, 33.5 and 42.7, respectively, which may be caused by the large difference in basicity among the three phosphazenes.
  • gradually reducing the loading of tBu - P4 from 2 mol% to 0.2 mol% can make the polymerization more controllable.
  • the ROP of HL became less controlled: the conversion decreased significantly, and the Mn increased with the dispersion (Table 2, run 8-10).
  • Increasing the reaction temperature from -25 °C to 41 °C also resulted in a more uncontrollable polymerization.
  • the present invention has also designed two groups of experiments that the ratio of [HL]/[BnOH] is 25/1 and 100/1, both polymerization conditions can reach the highest monomer conversion rate of 88%, and the Mn of the obtained polymer varies with [ HL]/[BnOH] ratio increases linearly, and the dispersion of the polymer remains low.
  • [M] 0 refers to the initial concentration of the HL monomer in the system, and refers to the concentration of the monomer in the entire system when the reaction is fed.
  • Example 19 The preparation steps are the same as in Example 4, except that the molar concentration of the catalyst is adjusted in the range of 0.0126-0.126 mmol, and other conditions refer to Table 2. Wherein, the characterization of the polymer sample obtained in Example 9 can be found in Example 19.
  • the preparation steps were the same as in Example 9, except that the reaction temperature was increased from -25°C to -9°C, 28°C, and 41°C respectively, and refer to Table 2 for other conditions.
  • Example 19 The preparation steps are the same as in Example 9, except that the feeding ratios of HL, tBu -P 4 , and BnOH are adjusted to 25/0.1/1 and 100/0.2/1 respectively, and refer to Table 2 for other conditions. Wherein, the characterization of the polymer sample obtained in Example 16 refers to Example 19.
  • j and k are positive integers greater than 1, and j and k may be the same or different.
  • t and r are positive integers greater than 1, and t and r may be the same or different.
  • Embodiment 20 is researched on the ring-opening polymerization ROP reaction characteristic of embodiment 9
  • Example 9 for the reaction system, reaction conditions, reaction steps, etc. used for the research on the characteristics of the ring-opening polymerization reaction. Only the reaction time was changed, and multiple parallel polymerization reactions were carried out to study the change of the conversion rate over time; in the predetermined reaction Quench the reaction after a certain period of time to avoid systematic errors in the conversion rate caused by continuous sampling and testing from the same reaction system.
  • the data in Figures 4a and 4b are derived from conversion data characterized by 1 H NMR, and the data in Figures 4c and 4d are derived from GPC analysis.
  • Polymerization kinetics data support that the polymerization under this condition is a living polymerization: monomer conversion increases linearly with reaction time (Fig. 4a).
  • the time-dependent curve of ln[M] 0 /[M] exhibits very clear first-order kinetics (Fig. 4b).
  • the M n of polyHL is linearly related to the monomer conversion rate, and the dispersity of the obtained polyHL is always low during the chain growth stage ( ⁇ 1.1) (Fig. 4c).
  • the GPC curve of the unimodal distribution given in Fig. 4d also confirms this conclusion.
  • Example 21 Characterizes the polymer molecules obtained in Examples 9 and 16
  • polyHL end-group fidelity of the synthesized polyester chains was investigated using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS).
  • MALDI-TOF MS matrix-assisted laser desorption ionization time-of-flight mass spectrometry
  • polyHL catalyzed by the tBu-P4/BnOH system was further characterized by NMR spectroscopy, and the proton signal ( ⁇ 5.12ppm) on the methylene on BnO- in the 1H NMR spectrum ( Figure 6) and the hydroxyl group
  • the proton signal ( ⁇ 3.49ppm) on the methine group connected to the end group, and the corresponding signal can also be observed in the 13 C NMR spectrum (Fig. 7).
  • the selected sample is the purified polymer sample in Example 9.
  • the experiment was tested by a Bruker Autoflex Speed MALDI-TOF mass spectrometer, and the test mode was positive ion and reflection mode.
  • the external calibration of MALDI-TOF to the molecular weight of the instrument is calibrated by adding an additional peptide calibration standard sample next to the sample well on the target plate.
  • the processing of the raw data was carried out in the FlexAnalysis software, and the collected raw data was used to draw the above-mentioned spectrum 5, and the drawing was all done by Origin Pro 2019b.
  • Example 16 The samples used in the NMR tests of Figures 6 and 7 are obtained in Example 16. Since the polymers initiated by BnOH belong to the same substance (the chemical structure is exactly the same), the difference in molecular weight has no effect on the chemical shifts and characteristic peaks in the NMR spectra. Only the polymerization Therefore, the characteristic spectrum of the polymer obtained under the preferred conditions in the examples is used as a representative for illustration.
  • p and q are positive integers greater than 1, and p and q may be the same or different.
  • Embodiment 23 polyHL physical performance measurement
  • the present invention analyzes the thermal stability of polyHL prepared by the Bu-P 4 /BnOH system in Example 17 by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).
  • TGA thermogravimetric analysis
  • DSC differential scanning calorimetry
  • Example 24 The chemical recyclability determination of PolyHL in a solvent
  • the present invention further investigates the ROP reaction of HL catalyzed by t Bu-P 4 /BnOH at different temperatures (-25, -16, -9, 28, 41°C) to calculate its polymerization thermodynamic parameters ( Figures 11 and 12).
  • This Tc is significantly lower compared to other monosubstituted and unsubstituted six-membered ring lactones. Therefore, introducing substituents at the ⁇ - and ⁇ -positions of ⁇ -VL is an effective strategy that can improve the chemical recyclability of monomers.
  • Example 25 The determination of the chemical recyclability of PolyHL in a solvent
  • the quenched reaction solution was added dropwise to 20 mL ice methanol, and the supernatant was discarded after centrifugation, and the precipitate was polyHL.
  • the precipitate obtained in the last time into a vacuum drying oven and dry to constant weight, and the obtained polyHL sample is purified under this condition. Simultaneously determine the M n (number average molecular weight) and (The molecular weight distribution).
  • Example 30 The preparation steps are as in Example 29, except that the catalyst equivalent is adjusted from 2 mol% to 1 mol% (Example 30), 0.67 mol% (Example 31, wherein HL/catalyst is 150/1), 0.5 mol% (implementation Example 32), see Table 3 for details.
  • Example 34 The preparation steps are as in Example 33, the difference is that the time of the stirring reaction is adjusted from 11min to about 0.267h (i.e. 16min) (Example 34), 0.5h (Example 35), 1h (Example 36), 2h ( Example 37), 2.5h (Example 38), 3h (Example 39), 4h (Example 40), 7h (Example 41), 10h (Example 42), 12h (Example 43).
  • step (1.1) of this example into a vacuum drying oven and dry to constant weight, take out a small amount for MALDI-TOF measurement, the measurement results are shown in Figure 18, and the results only show that one group can be assigned to the ring Signal of polyHL mass peak.
  • Example 45 When HL did not strictly remove residual water, the MALDI-TOF spectrum characteristics of the synthesized cyclic polymer
  • the preparation method is the same as (1.1) in Example 44, except that the HL monomer used has not undergone strict water removal, and the water content of the HL monomer is about 100 ppm as detected by a Karl Fischer moisture meter.
  • the sample to be tested was put into a vacuum drying oven and dried to constant weight, and a small amount was taken out for MALDI-TOF measurement.
  • the measurement results are shown in Figure 21. It can be seen from the figure that it is only possible to detect the water-induced linear mass peak if the residual water in the HL monomer or in the preparation system is not strictly removed.
  • Figure 22 Experimental method: In a nitrogen atmosphere glove box, weigh the equivalent tBu -P 4 catalyst as shown in Figure 22, and add 0.6 mL of dry deuterated toluene to dissolve it. Add a definite equivalent amount of HL monomer to the solution, and after a little stirring, transfer the solution to a flame-dried J-Young NMR tube, and perform NMR spectrum characterization immediately, and the results are shown in Figure 22.
  • Figure 23-24 Experimental method: in a nitrogen atmosphere glove box, weigh the equivalent tBu -P 4 catalyst as shown in Figure 23-24, and add 0.6 mL of dry deuterated toluene to dissolve it. Add a definite equivalent of HL monomer to the solution, stir for the time shown in the figure, then transfer the solution to a flame-dried J-Young NMR tube, and perform NMR spectrum characterization immediately, the result is shown in the figure 23-24.
  • the present invention uses quantum mechanical calculations to evaluate the Gibbs free energy of t Bu-P 4 capturing protons from HL monomers to generate cyclic polymers, and the Gibbs free energy of t Bu-P 4 capturing protons from BnOH and water molecules.
  • the difference in Booth free energy was calculated to verify the feasibility of the process of generating cyclic polyHL through deprotonation.
  • the reaction process and free energy data are shown in Figure 25.
  • the Gibbs free energy order of the deprotonation reaction is BnOH(3.9kcal mol-1) ⁇ HL(5.7kcal mol-1) ⁇ H 2 O(9.3kcal mol -1 ), indicating that BnO - is the most likely to generate the active species Initiator, while the energy of HL to initiate the active species is only 1.8kcal mol -1 higher than that of BnOH, indicating that HL can generate cyclic polyHL through the deprotonation mechanism under the catalysis of t Bu-P 4 .
  • thermogravimetric analysis TGA
  • derivative thermogravimetry DSC
  • DSC differential scanning calorimetry
  • polyHL is an amorphous polymer material with good thermal stability.
  • the ring-opening polymerization of HL catalyzed by tBu - P4 alone can obtain polyHL with very high molecular weight, which provides a very promising way to obtain pressure-sensitive adhesives with potential application value.
  • a simple 180° peeling test is used to measure the peel strength of polyHL with different molecular weights, and the preparation process is as follows:
  • PolyHL_160 (molecular weight M n is 160 respectively) cyclic polymer sample preparation: In a nitrogen atmosphere glove box, take 0.025mmol of tBu -P 4 catalyst and add it to a flame-dried 10mL Schlenk tube, then add 0.025mL The THF will dissolve the catalyst. Afterwards, the Schlenk tube was sealed with a rubber stopper, wrapped with a parafilm, taken out of the glove box, and placed in a pre-set -25°C low temperature bath until the temperature reached equilibrium.
  • the quenched reaction solution was added dropwise to 20 mL ice methanol, and the supernatant was discarded after centrifugation, and the precipitate was polyHL.
  • the precipitate obtained in the last time into a vacuum drying oven and dry to constant weight, and the obtained sample is polyHL_160.
  • the raw data of GPC is shown in Figure 56, and the Mn of polyHL_160 is measured at the same time and .
  • polyHL_319 (molecular weight M n is respectively 319) cyclic polymer sample preparation: preparation steps are as embodiment polyHL_160, difference is, change catalyst equivalent to 0.013mmol, reaction time is changed to 4h, obtain polyHL_319 sample, its GPC raw data see As shown in Figure 57, the M n and .
  • polyHL_562 (molecular weight M n is respectively 562) cyclic polymer sample preparation: preparation steps are as embodiment polyHL_160, difference is, change catalyst equivalent to 0.0063mmol, reaction time is changed into 6h, obtain polyHL_562 sample, its GPC raw data see As shown in Figure 57, the M n and .
  • a glass slide was used as the hard substrate, A4 paper (15 ⁇ 2.6cm) was used as the surface substrate (Figure 28a), and the polyHL sample was evenly coated on the glass slide with a coated blade (3M 665, 3M810, 3M1600 for comparison).
  • Cross-sectional scanning electron microscopy (SEM) showed a uniform film thickness of 36.9 ⁇ 1.2 ⁇ m (Fig. 28b).
  • the experiment was carried out on an Instron5966 universal mechanical tester at 25°C, with a peeling angle of 180° and a peeling speed of 10mm min -1 .
  • the adhesion forces of polyHL_319, 562, and 160 were 3.8 ⁇ 0.12, 3.5 ⁇ 0.20, and 1.5 ⁇ 0.65 N cm -1 (Fig. 28c and Table 5).
  • the peel strengths of polyHL_319 and polyHL_562 were higher than Commercial scotch tape ( 2.4 ⁇ 0.40N cm -1 ; 1.9 ⁇ 0.31N cm -1 ) and vinyl electrical tape ( is 0.8 ⁇ 0.17N cm - 1 ).
  • the peel strength of PolyHL_160 is 1.5 ⁇ 0.65N cm -1 , with commercial scotch tape quite.
  • the polyHL sample prepared in Example 30 was used to measure its chemical recyclability, and its M n was in the range of 500-600 kg mol -1 , which was 571.5 kg mol -1 .
  • Example 50 the catalyst, solvent and reaction temperature were changed, and a recovery experiment was carried out.
  • the experimental conditions are specifically shown in Table 6.
  • the results show that only FeCl can reclaim HL monomer, the rate of recovery is 21% (embodiment 55); Sn (Oct) The rate of recovery is only 5 %; Heating at 150° for 12 hours also showed no significant reactivity (Examples 55-59).
  • Example 50 The experimental conditions refer to Example 50, except that AgCF 3 SO 3 is replaced by Cu(CF 3 SO 3 ) 2 (Example 51), Fe(CF 3 SO 3 ) 3 (Example 52), Sc(CF 3 SO 3 ) 3 (Example 53), Y(CF 3 SO 3 ) 3 (Example 54).
  • the experimental conditions refer to Example 50, except that the catalyst type is changed, the reaction temperature is increased to 150°C, the reaction time is shortened to 12h, and the solvent is replaced by mesitylene.
  • the catalyst types are respectively: FeCl 2 (Example 55), Fe(acac) 2 (Example 56), Sn(Oct) 2 (Example 57), DBTDL (Example 58), tBu -P 4 (Example 58) 59).
  • Example 60 The experimental conditions refer to Example 60, except that the reaction temperature is increased to 140°C (Example 61) and 150°C (Example 62).
  • Example 60 The experimental conditions refer to Example 60, the difference is that the reaction temperature and solvent are changed; 150°C, o-dichlorobenzene (Example 63), 160°C, o-dichlorobenzene (Example 64).
  • the present invention also measures the catalytic activity of IMes, DBU, TBD and La(La[N(SiMe 3 ) 2 ] 3 ).
  • IMes catalytic activity
  • DBU deoxyribonate
  • TBD trimethyl methacrylate
  • La(La[N(SiMe 3 ) 2 ] 3 the catalytic activity of IMes, DBU, TBD and La(La[N(SiMe 3 ) 2 ] 3 ).
  • [HL] 0 0.5M
  • La[N(SiMe 3 ) 2 ] 3 showed good HL recovery: 47% in 3h, 81% in 12h, And reached 88% in 24 hours (Examples 65-67).
  • Example 65 The experimental conditions refer to Example 65, the difference is that the amount of reaction solvent added and/or the reaction time are changed: 2.6mL toluene, 12h (Example 66); 2.6mL toluene, 24h (Example 67); 12.8mL toluene, 3h (Example 68); 12.8 mL of toluene, 24h (Example 69).
  • Example 70 The experimental conditions refer to Example 70, the difference is that the amount of reaction solvent added and/or the reaction time are changed: 2.6mL toluene, 12h (Example 71); 12.8mL toluene, 3h (Example 72); 12.8mL toluene, 12h (Example 73).
  • the present invention uses ⁇ -L as raw material, by using Stryker reagent ([(Ph 3 P)CuH] 6 ) as catalyst, and triethoxysilane (His(OEt) 3 ) as hydrogen Source, at room temperature, stirred in toluene solution for 6h, successfully realized the preparation of ⁇ LH 2 monomer for the first time.
  • the present invention uses tBu -P 4 phosphazene catalyst as a catalyst for ⁇ LH 2 anionic ring-opening polymerization to attempt polymerization.
  • tBu -P 4 phosphazene catalyst As a catalyst for ⁇ LH 2 anionic ring-opening polymerization to attempt polymerization.
  • the addition equivalent of phosphazene catalyst was continuously reduced (from 2,1,0.4 to 0.2mol%), the molecular weight and molecular weight distribution of the polymer obtained had a tendency to decrease, that is, the molecular weight approached the calculated molecular weight of the charging ratio ( Example 76 ⁇ 79 ).
  • M n number average molecular weight
  • Molecular weight distribution is measured by GPC method under the condition of 40° C. in tetrahydrofuran mobile phase after calibration based on PMMA standard samples.
  • 0.0134 mmol of tBu -P 4 catalyst and 0.0134 mmol of BnOH initiator were added to a flame-dried 10 mL Schlenk tube, and then 0.016 mL of THF was added to dissolve them. Afterwards, the Schlenk tube was sealed with a rubber stopper, wrapped with a parafilm, taken out of the glove box, and placed in a pre-set -25°C low temperature bath until the temperature reached equilibrium.
  • M n number average molecular weight
  • Molecular weight distribution is measured by GPC method under the condition of 40° C. in tetrahydrofuran mobile phase after calibration based on PMMA standard samples.
  • Example 77 (0.0067 mmol)
  • Example 78 (0.00268 mmol)
  • Example 79 (0.00134 mmol).
  • Example 76 The preparation steps refer to Example 76, the difference is that the BnOH initiator in Example 76 is replaced by diphenylmethanol (Ph 2 CHOH) initiator.
  • Example 79 The preparation steps refer to Example 79, the difference is that the BnOH initiator in Example 79 is replaced by diphenylmethanol (Ph 2 CHOH) initiator.
  • the present inventors next investigated the feasibility of using several alkali metal alkoxides as ROP initiators.
  • M n number average molecular weight
  • Molecular weight distribution is measured by GPC method under the condition of 40° C. in tetrahydrofuran mobile phase after calibration based on PMMA standard samples.
  • the quenched reaction solution was added dropwise to 20 mL ice methanol, and the supernatant was discarded after centrifugation, and the precipitate was poly( ⁇ LH 2 ).
  • the above purification steps were repeated 3-5 times, and after the precipitate was obtained for the last time, it was put into a vacuum drying oven and dried to constant weight, and the obtained poly( ⁇ LH 2 ) sample was purified under this condition.
  • M n number average molecular weight
  • (Molecular weight distribution) is measured by GPC method under the condition of 40° C. in tetrahydrofuran mobile phase after calibration based on PMMA standard samples.
  • the preparation steps refer to Example 83, except that the equivalent weight of the KOMe initiator is reduced to 0.0067 mmol.
  • the preparation steps refer to Example 83, except that the reaction time is extended to 48 h, and the equivalent weight of the KOMe initiator is reduced to 0.00335 mmol.
  • the present invention screened several other common alkali metal alkoxides, including NaOMe, KO t Bu, NaO t Bu and LiO t Bu ( Figure 64 ).
  • Embodiment 86 ⁇ 89 ⁇ LH 2 ring-opening polymerization participated in by different alkali metal alkoxide initiators
  • Example 83 The preparation steps refer to Example 83, the difference is that KOMe is replaced:
  • Example 86 sodium methoxide, NaOMe
  • Example 87 potassium tert-butoxide, KO t Bu
  • example 88 sodium tert-butoxide, NaO t Bu
  • Example 89 lithium tert-butoxide, LiO t Bu
  • thermogravimetric analysis TGA
  • DSC differential scanning calorimetry
  • the poly( ⁇ LH 2 ) prepared by using tBu -P 4 as the catalyst, BnOH as the initiator (Example 79), and adding only the initiator KOMe (Examples 82-84 ) without adding a catalyst all have good Thermal stability (5% thermal weight loss temperature is greater than 300 ° C).
  • TGA curves reveal that T d,5% and T max of different samples are related to the molecular weight of the samples. Its T max is between 370 and 376°C ( Figures 69 to 72, respectively corresponding to Examples 79, 82, 83, and 84 ).
  • Example 79 uses t Bu-P 4 t Bu-P 4 as the catalyst, and BnOH is The T d,5% of the sample prepared by the initiator is 20-30°C lower than that of the sample prepared by using only the initiator KOMe (Example 82-84 ).
  • the main reason for this difference may be that the polymers prepared by the two systems due to the large molecular weight difference.
  • the DSC curves show that the T g of poly( ⁇ LH 2 ) prepared in Examples 79 and 84 are -30.5 and -27.0°C respectively ( Figures 73-74, corresponding to Examples 6 and 11 respectively), and the samples are heated at 10°C/min
  • the second heating and the first cooling curves only have glass transition temperature (T g ) but no crystallization and melting endothermic peaks, indicating that this poly( ⁇ LH 2 ) material is an amorphous polymer.
  • the present invention prepared a strip-shaped material from the sample prepared in Example 85 by hot pressing, which is a flexible and ductile non- color transparent material ( Figure 75 ).
  • Embodiment 91 chemical recovery experiment
  • the present invention can regulate the properties of the polymer through post-polymerization modification, and the click chemical reaction between photo-induced thiol-alkenes is a good Post-polymerization modification methods.
  • a poly( ⁇ LH 2 ) sample, p-trifluoromethylthiophenol, and benzoin dimethyl ether are formulated into a solution, which is then coated into a uniform film, and the film is irradiated with ultraviolet light of 254 and 365 nm wavelength for 12 hours ( Example 92 ).
  • the film After being irradiated for a long enough time, the film was dissolved with a small amount of dichloromethane, reprecipitated with n-hexane several times and dried, and the obtained product was poly( ⁇ LH 2 -SAr) modified after polymerization.
  • the present invention finds that the film will produce very obvious blue fluorescence under ultraviolet light with a wavelength of 365nm when the photo-induced thiol-alkene click chemical reaction is carried out. Therefore, the present invention further characterized the optical properties of the synthesized poly( ⁇ LH 2 -SAr) by using photoluminescence spectroscopy. Under the excitation of ultraviolet light with a wavelength of 360nm, a photoluminescence peak was detected at about 410nm ( FIG. 79 ), and in sharp contrast to this, the poly( ⁇ LH 2 ) sample did not have such luminescence. The pattern imprinting experiments shown in Figure 80 demonstrate the ease of this optical modification.
  • the present invention covers the light-responsive film (the film contains poly( ⁇ LH 2 ), p-trifluoromethylthiophenol, and benzoin dimethyl ether) with a mask with a hollow “CO 2 ” pattern in the middle, and performs UV light overnight. After being illuminated, a "CO 2 " fluorescent pattern appeared on the photoresponsive film, while the area covered by the mask was not emitting light ( Fig. 81 ). This demonstrates that the generation of this fluorescence is due to a successful thiol-alkene click chemistry reaction.
  • this post-modification is also a means to easily change the hydrophilic and hydrophobic properties of polymers.
  • the contact angle between ultrapure water and glass substrate is 55.7° ( Figure 82 ), while the contact angle between poly( ⁇ LH 2 ) and ultrapure water is 72.8 ⁇ 0.08° ( Figure 83 ).
  • the contact angle between poly( ⁇ LH 2 -SAr) containing fluorine atoms and ultrapure water reaches 93.0 ⁇ 0.99° ( Fig. 84 ). It may be that the post-modified poly( ⁇ LH 2 -SAr) has significantly more hydrophobic material properties due to the grafting of trifluoromethyl groups onto the polymer side chains.
  • Embodiment 93 HL monomer synthesizes polyurethane by one-pot two-step method
  • the preparation method of the carbon dioxide-based polyester polymer of the present invention can use cheap bulk materials as raw materials, effectively utilize carbon dioxide, and alleviate the greenhouse effect.
  • the polyester polymer is a chemically recyclable polymer, Has excellent physical and chemical properties.
  • the method of the present invention utilizes cheap and easy-to-obtain carbon dioxide and 1,3-butadiene to synthesize a saturated lactone and (HL) a double-substituted lactone ( ⁇ LH 2 ), and for the first time synthesizes a new Carbon dioxide based recyclable polymer material (CO 2 based recyclable polyester material).
  • the obtained material polyHL has good mechanical properties, is colorless and transparent, and can be used as a pressure-sensitive adhesive; the obtained material poly( ⁇ LH 2 ) also has certain physical properties, and has chemically adjustable properties, and has many applications in development potential of the scene. Both polymers can be chemically recycled back to the monomer under certain conditions, which can establish a closed-loop circular material economy. This method not only avoids the damage of white pollution to the environment, but also provides a new solution for the reformation and reuse of carbon dioxide, and at the same time meets the urgent needs of carbon-neutral production of new polymers and circular material economy.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial application value.

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Abstract

本发明属于聚合物合成技术领域，涉及一种聚酯高分子化合物及其合成方法，所述方法以式1杂环内酯为原料，在有机碱催化下进行开环聚合反应，得到所述式2和/或式3所述聚酯高分子化合物。本发明还公开了δLH 2及其制备方法。本发明所述方法首次实现该聚酯高分子化合物的制备。本发明方法采用的原料来源广泛，所采用的催化剂制备简单，成本低廉，活性良好，本发明能有效缓解温室效应带来的危害。本发明还公开了所述聚酯高分子化合物的应用，所制备的聚合物薄膜呈无色、透明状，且具有良好的柔性和粘弹性等性能。所述聚酯高分子化合物具有良好的物理化学特性和可回收性，具有广泛应用前景。

Description

一种聚酯高分子化合物及其制备方法和应用 技术领域
本发明属于聚合物合成技术领域，涉及一种聚酯高分子化合物及其制备方法和应用，特别涉及一种基于CO 2、H 2和1，3-丁二烯的化学可回收高分子(CO 2-based chemical recyclable polymer)及其制备方法和应用。
背景技术
合成高分子作为一种常见材料，已经深入人类衣食住行的方方面面。根据预测，从1950年至2050年的一百年中，全球的高分子产量累积将达到340亿吨，其中绝大多数的高分子由于其含有稳定的碳碳键骨架，难以降解。不可降解高分子的大量使用，使其呈现出一种“原料-单体-高分子-材料-垃圾”的不合理的线性使用模式，正是这种模式直接导致了如今十分严峻的塑料垃圾污染以及不计其数的材料价值损失。
化学回收是减少高分子材料对于环境和经济的影响和考量的具有前景的策略。化学回收可以通过“合成、利用、回收”的策略实现一个材料经济的闭环。这一循环经济模式是十分有前景的解决白色污染的手段。与此同时，通过廉价易得的大宗化学品，例如CO 2和烯烃来合成化学可回收高分子，能够降低材料成本并且推动其走向工业大规模生产。因此，发展二氧化碳高效转化和利用对于工业生产和可持续发展具有十分重要的意义。
CO 2作为一种廉价易得且可再生的C1源，十分适用于合成多种高分子材料，包括聚碳酸酯、聚氨酯、聚脲和聚酯等。通过CO 2和廉价大宗的化学药品合成新型高分子，尤其是乙烯和1,3-丁二烯等，从上世纪七十年代以来就是一个十分有前景的方向。经过Inoue、Behr、Beller的研究，CO 2和1,3-丁二烯实现通过Pd催化的偶联反应，生成含有两个碳碳双键的六元环内酯中间体3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one(δ-L)。基于此，Nozaki于2014年报道了δ-L的自由基聚合，并且可以得到具有三种不同拓扑结构的侧链含有酯键官能团的聚烯烃。紧接着，林柏霖报道了该单体可以在仅有空气引发、无溶剂且无添加剂的条件下直接进行自由基聚合，并且在拓扑结构的研究过程中发现了第四个结构(δ结构)。后来又报道，CO 2和1,3-丁二烯合成的二乙基取代的六元环内酯即3,6-二乙基四氢-2h-吡喃-2-酮(HL)，但是以HL为代表的二取代己内酯在传统意义上被认为是不可聚合的单体。
为了实现CO 2基高分子的大规模生产，需至少满足以下几个条件：1.为了满足大规模生产的经济性要求，与CO 2共聚的原料应是廉价的大宗化学原料；2.生产获得的聚合物应可以 方便地被加工成为人们想要的性状，并且具有可商业化的性能指标；3.为了解决日益严重的塑料污染问题，该新型聚合物必须可以被降解。目前市场上采用CO 2合成的商品化CO 2-基高分子材料，主要为聚碳酸酯和聚多元醇，无法同时满足材料在成本、材料性能和可降解能力三方面的要求，且其中CO 2的使用量并不大，并不能满足对CO 2的减排需求。为了建立CO 2基聚合物在成本、材料性能和闭环循环经济(closed-loop circular economy)的优势，并实现有力减排的效果，亟需设计、合成一种结构新颖、成本低廉、具有工业化潜力的全新的CO 2基聚合物。
发明内容
鉴于以上所述现有技术的缺点，本发明首次提出一种聚酯高分子化合物及其合成方法，该方法通过以杂环内酯进行开环聚合(ROP)制备得到所述聚酯高分子化合物，如该方法通过将CO 2、H 2和1,3-丁二烯衍生而来的二乙基取代的六元环内酯即3,6-二乙基四氢-2h-吡喃-2-酮(HL)进行开环聚合(ROP)制备得到polyHL，用于解决现有技术中制备步骤复杂、产率低、成本高，制备的聚酯分子量低，相关聚酯产品性能不高，如透明度低、稳定性低等问题；再如以杂环内酯为原料，通过阴离子开环聚合合成该环状聚合物，其可以在特定条件下降解回到内酯单体HL(图15～16)。本发明还提出了由该方法获得的聚酯高分子化合物，以及所述聚酯高分子化合物的用途。
为实现上述目的及其他相关目的，本发明提供一种聚酯高分子化合物，所述聚酯高分子化合物包含如下式4所示的重复单元：
Figure PCTCN2022134072-appb-000001
R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基(线性烷基、支链烷基、环烷基)、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香 基包括苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同，且必须同时存在；
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
X选自杂原子。
所述式4所示的重复单元的个数为n，所述n为大于等于1的正整数。
在一优选实施方式中，所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)，所述二氧化碳基聚酯poly(δLH 2)包含如下式6所示的重复单元：
Figure PCTCN2022134072-appb-000002
其中，n为大于等于1的正整数。
本发明中所述聚酯高分子化合物包括线性、环状、星形等拓扑结构。
在一优选实施方式中，所述聚酯高分子化合物结构为线性结构时，其结构如式2所示：
Figure PCTCN2022134072-appb-000003
R 1、R 2、X、n、m定义如上式4化合物中所述。
R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个。
在进一步优选实施方式中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述二氧化碳基聚酯poly(δLH 2)结构如式7所示：
Figure PCTCN2022134072-appb-000004
其中，R 14选自C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
n为大于等于1的正整数；
m为大于等于1的正整数。
在一优选实施方式中，所述聚酯高分子化合物结构为环状结构时，其结构如式3所示：
Figure PCTCN2022134072-appb-000005
本发明另一方面是提供所述聚酯化合物在制备聚氨酯、聚合物薄膜、压敏胶黏剂、胶带、热塑性弹性体中的一种或几种的应用。
在一优选实施方式中，所述聚酯高分子化合物结构为线性结构时，所述聚酯化合物在制备聚氨酯或压敏胶黏剂中的应用。
在一优选实施方式中，所述聚酯高分子化合物结构为环状结构时，所述聚酯化合物在制备聚合物薄膜、压敏胶黏剂、热塑性弹性体中的应用。在一具体实施方式中，所述聚酯高分子化合物结构为聚合物薄膜。在一具体实施方式中，所述聚酯高分子化合物结构为胶带。
本发明另一方面是提供一种聚酯高分子化合物的合成方法，选自以下方法中任一种或两种：
A)当所述聚酯高分子化合物结构为线性结构时，所述方法包括：式1所示的杂环内酯，在有机碱为催化剂，能够提供活性质子的试剂R(OH) m为引发剂的条件下，合成得到式 2所示的聚酯高分子化合物；反应过程如反应式I所示：
Figure PCTCN2022134072-appb-000006
B)当所述聚酯高分子化合物结构为环性结构时，所述方法包括：式1所示的杂环内酯，在有机碱催化下，合成得到式3所示的聚酯高分子化合物；反应过程如反应式Ⅱ所示：
Figure PCTCN2022134072-appb-000007
在A)和/或B)中，R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基(线性烷基、支链烷基、环烷基)、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基包括苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同，且必须同时存在；
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、 亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
X选自杂原子；
n为大于等于1的正整数；
所述有机碱包括磷腈、含有胍基基团的化合物、含脒基基团的化合物；
在B)中，R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
m为大于等于1的正整数。
在一优选实施方式中，在A)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述方法包括：式8所示的δLH 2，在有机碱作为催化剂，提供活性质子的试剂R 14(OH)m和/或(MO) mR 14作为引发剂的条件下，合成得到式7所示的二氧化碳基聚酯poly(δLH 2)；反应过程如反应式Ⅲ所示：
Figure PCTCN2022134072-appb-000008
其中，R 14选自C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
M为K，Na，Li，Rb或Cs；
n为大于等于1的正整数；
m为大于等于1的正整数；
所述有机碱选自磷腈、含有胍基基团的化合物、含脒基基团的化合物中的一种或几种。
在一优选实施方式中，所述磷腈为含有(R 2N) 2-P＝N结构的强Lewis碱；优选地，所述磷腈结构如式5所示：
Figure PCTCN2022134072-appb-000009
式5中，R 3-R 10分别独立地选自C1-C10烷基；y为大于等于1的正整数。
在一优选实施方式中，所述磷腈选自 tBu-P 1、 tBu-P 2、 tBu-P 4，结构分别以下所示：
Figure PCTCN2022134072-appb-000010
本发明另一方面是提供一种聚酯高分子化合物，所述聚酯高分子化合物由如上所述的方法合成得到。
本发明另一方面是提供有机碱在催化如上所述式1化合物合成式2和/或式3所示的聚酯高分子化合物中的用途，所述有机碱包括磷腈、含有胍基基团的化合物、含脒基基团的化合物；其中，式1所示的杂环内酯、式2和/或式3所示的聚酯高分子化合物结构分别如下：
Figure PCTCN2022134072-appb-000011
Figure PCTCN2022134072-appb-000012
作为优选，本发明提供有机碱在催化式8所示的δLH 2合成式7所示的二氧化碳基聚酯poly(δLH 2)中的用途，式8所示的δLH 2、式7所示的二氧化碳基聚酯poly(δLH 2)结构分别如下：
Figure PCTCN2022134072-appb-000013
作为优选，所述有机碱为磷腈，所述磷腈的结构如下式5所示：
Figure PCTCN2022134072-appb-000014
式5中，R 3-R 10分别独立地选自C1-C10烷基；
y为1，2或3。
本发明另一方面是提供一种催化如上所述式2/或式3所示的聚酯高分子化合物回收杂环 单体的方法，所述方法选自以下任一种或两种：
a)如催化式2所示的方法包括催化法和热解法；
b)如催化式3所示的方法包括无机盐热解催化法和La[N(SiMe 3) 2] 3温和催化法；
a)中，所述催化法包括：采用无机盐、金属有机化合物、有机化合物催化剂中的至少一种化合物降解所述式2聚酯高分子化合物，回收得到式1所示的杂环单体或其寡聚物或其衍生物；
所述热解法包括：对所述式2聚酯高分子化合物进行加热裂解，回收得到式1所示的杂环单体或其寡聚物或其衍生物；
b)中，所述无机盐热解催化法包括：采用无机盐催化降解如式3所示的聚酯高分子化合物，得到式1所示的杂环化合物或其寡聚物或式1相应的衍生物；
所述La[N(SiMe 3) 2] 3温和催化法包括：在温和条件下对式3所示的聚酯高分子化合物采用La[N(SiMe 3) 2] 3进行催化裂解，得到式1所示的杂环化合物或其寡聚物亦或是式1相应的衍生物。
作为优选，在a)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，
所述催化法包括：采用无机盐、金属有机化合物或有机化合物催化剂中的至少一种化合物降解所述式8所示的二氧化碳基聚酯poly(δLH 2)，回收得到式7所示的δLH 2或其寡聚物或其衍生物；
所述热解法包括：对所述式8所示的二氧化碳基聚酯poly(δLH 2)进行加热裂解，回收得到式7所示的δLH 2或其寡聚物或其衍生物。
本发明另一方面是在所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，提供一种二取代α,β-饱和六元环内酯的制备方法，所述方法以式9所示的二取代α,β-不饱和六元环内酯为原料，以Stryker试剂或者能够原位生成Stryker试剂的混合试剂为催化剂，有机硅烷为氢源，通过共轭烯烃的选择性还原反应制备得到式10所示的二取代α,β-饱和六元环内酯；所述选择性还原反应如反应式A所示：
Figure PCTCN2022134072-appb-000015
其中，R 1、R 2分别独立地选自氢、卤素、C1-C20烷基、取代的C1-C20烷基、C2-C20 烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同。
本发明的另一目的是提供一种如上所述的δLH 2的制备方法在制备式8所示的二氧化碳基聚酯poly(δLH 2)或聚氨酯或压敏胶黏剂中的应用，式10所示的二取代α,β-饱和六元环内酯结构如下：
Figure PCTCN2022134072-appb-000016
如上所述，本发明的二氧化碳基聚酯高分子化合物及其制备方法和应用，具有以下有益效果：
本发明提供的二氧化碳基聚酯高分子化合物的制备方法，该方法以式1杂环单体为原料，采用两种引发模式：1.有机碱为催化剂，能够提供活性质子的试剂如R(OH)m为引发剂；2.单独使用醇盐作为引发剂，在例如-100～200℃条件下进行开环聚合反应，一步法得到聚合物分子可控的聚酯高分子化合物。该方法简单，原料易得，原材料来自于廉价的二氧化碳气体，能够有效缓解温室效应，通过调整原料的配比，反应温度和反应时间等条件，可以控制聚酯高分子化合物的分子量。本发明方法通过开环聚合得到具有良好物理化学特性的(如力学性能)和可回收性的高分子，增加其应用潜力。
本发明方法采用的原料杂环内酯来源广泛，制备简单；当杂环内酯为HL时，所述HL可以通过CO 2和1，3-丁二烯制备获得，进而可以缓解CO 2引起的温室效应带来的危害。本发明方法所采用的催化剂催化活性良好，制备方法简单，成本低廉。
本发明方法能够合成获得超高分子量和中等分子量分布的环状聚合物，在一些实施方式中，所述环状聚合物的分子量可达613.8kg mol-1，分子量分布
Figure PCTCN2022134072-appb-000017
为1.45。所述环状聚合物可以用于制备多种聚合物产品，例如是聚合物薄膜，胶带等；所制备的聚合物薄膜呈无色、透明状，且具有良好的柔性和粘弹性等性能。
本发明提供的方法，底物广谱性强，能够有效回收各种环状聚合物包括但不限于本发明所述方法制备的环状聚合物中的单体，具有广泛应用前景。
本发明提供的二氧化碳基聚酯poly(δLH 2)的制备方法，以式1所示的δLH 2为原料，采 用两种引发模式：1.有机碱为催化剂，能够提供活性质子的试剂如R(OH)m为引发剂；2.单独使用醇盐作为引发剂，进行开环聚合反应，一步法得到聚合物分子可控的聚酯高分子化合物。所述poly(δLH 2)的制备方法步骤简单，产率高，可控性强；采用的催化剂制备简单，成本低廉，活性良好。
本发明通过调整原料的种类，各试剂的用量，反应温度和反应时间等条件，可以控制聚酯化合物poly(δLH 2)的分子量大小和分子量分布。制备得到的poly(δLH 2)是一种柔性材料，其可以完全被降解成为单体，且该聚酯材料具有良好的物理化学特性，如具有透明性高、分子量高、热稳定性强、延展性好等特点。
本发明提供的方法，可以采用廉价易得的C1源二氧化碳和大宗化学产品1,3-丁二烯为原料，先合成六元环内酯δLH 2，然后经开环聚合反应合成所述poly(δLH 2)，能够有效缓解温室效应。通过对poly(δLH 2)进行化学回收，以得到单体δLH 2，实现闭环绿色循环。
本发明制备的聚酯材料具有优异的聚合后修饰和改性的能力，通过后修饰改性方法对poly(δLH 2)进行聚合后修饰，如通过光致引发的硫醇-烯烃点击反应可以对poly(δLH 2)烯烃侧链进行接枝，从而对聚合物性质进行调控。
本发明提供的二取代α,β-饱和六元环内酯如δLH 2的制备方法，以二取代α,β-不饱和六元环内酯如δ-L为原料，以Stryker试剂或者能够原位生成Stryker试剂的混合试剂为催化剂，有机硅烷为氢源，通过共轭烯烃的选择性还原反应制备得到。所述δLH 2的制备方法产率高，步骤简单，成本低。
本发明所述的制备poly(δLH 2)的方法和制备δLH 2的方法具有在材料领域尤其是高分子材料领域具有较大应用前景。
附图说明
图1显示 tBu-P 4/BnOH催化HL的开环聚合过程中可能的链引发机制(当量实验的 1H NMR谱图)。a.磷腈 tBu-P 4；b.BnOH；c.[ tBu-P 4]/[BnOH]＝1/1。
图2显示实施例18产物的MALDI-TOF表征图。
图3显示实施例19产物的MALDI-TOF表征图。
图4显示实施例20由 tBu-P 4/BnOH催化的HL-ROP活性聚合分析。a.HL转化率随时间变化曲线；b.ln([M]/[M] 0)；c.polyHL的分子量和分子量分布随着HL单体转化率的变化曲线；d.不同聚合时间下得到的polyHL的GPC曲线叠加图。
图5显示实施例21线性polyHL聚合物的MALDI-TOF表征，证实是BnOH封端产物。
图6显示实施例21线性polyHL聚合物的 1H NMR表征。
图7显示实施例21线性polyHL聚合物的 13C NMR表征。
图8显示实施例21中1,4-BDM作为引发剂制备的线性polyHL二元醇的MALDI-TOF表征。
图9显示实施例23线性polyHL的TGA和DTG曲线图。
图10显示实施例23线性polyHL的DSC曲线图。
图11显示实施例24不同温度条件下，HL单体浓度随着时间的变化曲线图。
图12显示实施例24中HL的Van’t Hoff分析曲线。
图13显示实施例25线性polyHL化学回收的 1H NMR图。底部：线性polyHL的核磁谱图(合成条件：[HL]/[ tBuP 4]/[BnOH]＝50/0.1/1；反应温度：-25℃；溶剂：THF，M n＝9.2kg mol -1,
Figure PCTCN2022134072-appb-000018
)；中部：化学回收之后的无色油状产物除去溶剂后的谱图；顶部：用于ROP的干净的起始单体HL。
图14显示实施例26通过热解方法回收聚合物单体的结果图。
图15为由CO2和丁二烯为原料制备环状聚合物以及环状聚合物的化学回收路线图。
图16为由HL开环聚合物合成环状聚合物的机制原理示意图。
图17为tBu-P4催化的HL开环聚合动力学数据。a.转化率随时间的变化曲线；b.ln([M]0/[M])随反应时间的变化曲线；c.数均分子量和分子量分布随转化率的变化曲线；d.不同实施例的GPC曲线叠加图。
图18为实施例44制备的环状PolyHL产物的MALDI-TOF表征数据。
图19为环状polyHL聚合物的1H NMR谱图(实施例29)。
图20为环状polyHL聚合物的13C NMR谱图(实施例29)。
图21为体系未严格除水时的polyHL产物MALDI-TOF表征。
图22为不同比例下的HL和 tBu-P 4混合实验( 31P NMR谱图)。
图23为不同比例下的HL和 tBu-P 4混合实验( 1H NMR谱图，局部放大)。
图24为不同比例下的HL和 tBu-P 4混合实验( 1H NMR谱图，总览)。
图25为tBu-P4对于BnOH、HL和水脱质子的自由能计算数据。
图26为环状polyHL产物的TGA和DTG曲线。
图27为环状polyHL产物的DSC曲线。
图28为环状polyHL样品压敏胶性能测定。a.180°剥离测定示意图；b.环状polyHL薄膜的截面SEM图(实施例29)；c.环状polyHL样品和三种商品化胶带的180°剥离性能测定结果(数据见表29)；d.polyHL薄膜无色和光透过性的样品展示(实施例29)。
图29为实施例30制备的polyHL聚合物的核磁氢谱图。
图30为实施例31制备的polyHL聚合物的核磁氢谱图。
图31为实施例32制备的polyHL聚合物的核磁氢谱图。
图32为实施例50降解后的产物的核磁氢谱图。
图33为实施例51降解后的产物的核磁氢谱图。
图34为实施例52降解后的产物的核磁氢谱图。
图35为实施例53降解后的产物的核磁氢谱图。
图36为实施例54降解后的产物的核磁氢谱图。
图37为实施例55降解后的产物的核磁氢谱图。
图38为实施例56降解后的产物的核磁氢谱图。
图39为实施例57降解后的产物的核磁氢谱图。
图40为实施例58降解后的产物的核磁氢谱图。
图41为实施例59降解后的产物的核磁氢谱图。
图42为实施例60降解后的产物的核磁氢谱图。
图43为实施例61降解后的产物的核磁氢谱图。
图44为实施例62降解后的产物的核磁氢谱图。
图45为实施例63降解后的产物的核磁氢谱图。
图46为实施例64降解后的产物的核磁氢谱图。
图47为实施例65降解后的产物的核磁氢谱图。
图48为实施例66降解后的产物的核磁氢谱图。
图49为实施例67降解后的产物的核磁氢谱图。
图50为实施例68降解后的产物的核磁氢谱图。
图51为实施例69降解后的产物的核磁氢谱图。
图52为实施例70降解后的产物的核磁氢谱图。
图53为实施例71降解后的产物的核磁氢谱图。
图54为实施例72降解后的产物的核磁氢谱图。
图55为实施例73起始原料、聚合物和降解产物的叠加核磁氢谱图。
图56为实施例49制备的polyHL_160的GPC原始数据。
图57为实施例49制备的polyHL_319的GPC原始数据。
图58为实施例49制备的polyHL_562的GPC原始数据。
图59为poly(δLH 2)合成现状和技术路线。
图60为实施例74中制备的δLH 2的核磁共振氢谱图。
图61为实施例74中制备的δLH 2的核磁共振碳谱图。
图62为实施例81制备的poly(δLH 2)的核磁氢谱图。
图63为实施例82制备的poly(δLH 2)的GPC曲线图。
图64为实施例83、86～89制备的poly(δLH 2)的GPC曲线叠加图；其中的KOMe对应实施例83，NaOMe对应实施例86，KO tBu对应实施例87，NaO tBu对应实施例88，LiO tBu对应实施例89。
图65为实施例83制备的poly(δLH 2)的核磁氢谱图。
图66为实施例83制备的poly(δLH 2)的核磁碳谱图。
图67为实施例83制备的poly(δLH 2)的核磁碳氢HSQC图。
图68为实施例83～85制备的poly(δLH 2)的GPC图。
图69为对应实施例79制备的poly(δLH 2)的TGA曲线图。
图70为对应实施例82制备的poly(δLH 2)的TGA曲线图。
图71为对应实施例83制备的poly(δLH 2)的TGA曲线图。
图72为对应实施例84制备的poly(δLH 2)的TGA曲线图。
图73为对应实施例79制备的poly(δLH 2)的DSC曲线图。
图74为对应实施例84制备的poly(δLH 2)的DSC曲线图。
图75为应用例1中，采用的实施例85制备的poly(δLH 2)的外观和光透过性结果图。
图76为实施例91中，采用的实施例81制备的poly(δLH 2)的降解结果。
图77为应用例3/实施例92聚合后修饰实验中，采用的实施例81制备的poly(δLH 2)的后修饰样品前后GPC曲线的变化图。
图78为应用例3/实施例92聚合后修饰实验中，纯化后的poly(δLH 2-SAr)的核磁共振氢谱图。
图79为应用例3/实施例92聚合后修饰实验中，采用的实施例81制备的poly(δLH 2)后修饰前后的样品荧光发射光谱图。
图80为应用例3/实施例92聚合后修饰实验中，图案印刻实验示意图及掩板实物图。
图81为应用例3/实施例92聚合后修饰实验中，图案印刻实验。
图82为应用例3/实施例92聚合后修饰实验中，水与玻璃基板的接触角(55.7°)(左上角比例尺大小为1mm；标注的角度数值分别为55.7°(左)，55.5°(右)。
图83为应用例3/实施例92聚合后修饰实验中，其中一个poly(δLH 2)样品的亲疏水性质测试图(三个poly(δLH 2)样品与水的接触角为72.8±0.08°)，左上角比例尺大小为0.5mm，标注的角度数值分别为72.8°(左)，73.3°(右)。
图84为应用例3/实施例92聚合后修饰实验中，其中一个poly(δLH 2-SAr)样品的亲疏水性质测试图(三个poly(δLH 2-SAr)样品与水的接触角为93.0±0.99°)，左上角比例尺大小为1mm，标注的角度数值分别为94.4°(左)，94.6°(右)。
图85为实施例93制备的以HL为单体一锅两步法合成的聚氨酯的核磁氢谱图。
图86为实施例93制备的以HL为单体一锅两步法合成的聚氨酯的GPC原始数据。
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
本发明突破了现有技术的技术瓶颈，首次报道了一种化学可回收聚合物及其合成方法，所述聚合物可以是单羟基封端或双羟基封端结构，分子量可以根据聚合度进行调控，二氧化碳含量可以为28wt％。本发明方法能够实现杂环内酯如六元内酯3,6-二乙基四氢-2h-吡喃-2-酮(HL)的活性聚合。当原料为HL时，所述HL可以使用二氧化碳和廉价的大宗化学品作为起始原料制备获得，如反应路线1所示，采用钯催化两步法由CO 2、H 2和1,3-丁二烯合成HL；所述HL再经有机碱(如 tBu-P 4)催化阴离子开环聚合(AROP)得到聚酯高分子化合物。本发明还开发了一系列的催化方法来化学降解聚酯高分子化合物如polyHL，从而回收杂环内酯单体如HL单体。
Figure PCTCN2022134072-appb-000019
反应路线1线性polyHL的合成路径
具体来说，本发明还首次提出一种十分高效的多步反应策略，从而实现以CO 2和丁二烯为原料合成化学可回收高分子二氧化碳基聚酯poly(δLH 2)。本发明以CO 2和丁二烯为原料合成δ-L，通过对δ-L进行共轭烯烃的选择性还原制备得到侧链含有端烯烃基团的六元环内酯——3-ethyl-6-vinyltetrahydro-2H-pyran-2-one(δLH 2)，并且通过对δLH 2这样一个不同寻常的 具有双基团取代的六元环内酯的开环聚合，首次实现了二氧化碳基聚酯poly(δLH 2)的合成。该聚酯具有高CO 2含量(如优选地，可达到29wt％)、透明性好、分子量高、热稳定性高等特点。该聚酯能够在催化剂的参与下被完全降解回到单体，并且由于该聚酯重复单元中存在端烯烃侧链，因此本发明可以十分容易地对聚合物poly(δLH 2)进行聚合后修饰；如本发明通过光致引发的硫醇-烯烃点击反应可以对poly(δLH 2)烯烃侧链进行接枝，从而对聚合物性质进行调控。本发明二氧化碳基聚酯poly(δLH 2)的合成路径如反应路线2所示；二氧化碳基聚酯poly(δLH 2)合成现状和本发明的技术路线见图59。
Figure PCTCN2022134072-appb-000020
反应路线2二氧化碳基聚酯poly(δLH 2)的合成路径
同时，本发明旨在首次提出一种单体可回收的环状聚合物及其合成方法，以杂环内酯为原料，通过该杂环内酯阴离子开环聚合制备环状聚合物。所述合成方法可以根据聚合度调控环状聚合物的聚合度，进而调控聚合物的Mn(数均分子量)和
Figure PCTCN2022134072-appb-000021
(分子量分布)。本发明还提供了一系列的方法来回收环状聚合物单体。本发明所述合成方法可以采用简单易得的原料制备环状聚合物；例如，当原料杂环内酯为3,6-diethyltetrahydro-2H-pyran-2-one(HL)时，所述HL可以使用CO 2、H 2和廉价的大宗化学品1,3-丁二烯通过钯催化两步法制备获得，即通过CO 2和1,3-丁二烯合成侧链含有两个C-C双键的不饱和内酯δ-lactone，δ-lactone在过渡金属催化剂的参与下与氢气反应得到HL，如反应路线3所示；制得的HL再经有机碱(如 tBu-P 4)催化阴离子开环聚合(AROP)得到环状聚合物polyHL，polyHL经本发明的催化方法可以进一步裂解，得到单体HL。
Figure PCTCN2022134072-appb-000022
反应路线3环状聚合物polyHL的合成路径
本发明提供了一种聚酯高分子化合物，所述聚酯高分子化合物包含如下式4所示的重复单元：
Figure PCTCN2022134072-appb-000023
其中，R 1、R 2可相同或不同，并且R 1、R 2两个基团必须满足同时存在于六元杂环上，取代的位点为四个亚甲基碳中的任意两个，即必须同时存在。
R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；
所述卤素选自氟、氯、溴、碘。
所述烷基为线性烷基、支链烷基、环烷基；进一步地，所述烷基可以是C1-C20的烷基；也可以是C1-C10的烷基，包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，为乙基。
所述取代的烷基为取代的线性烷基、支链烷基、环烷基。
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。进一步地，所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、羟基、硝基、卤素、羧基、C1-C10烷基、烷氧基、胺基、环烷氧基、环胺基、C2-C12烯基、C2-C12炔基、C3-C12环烷基、苄基、烷基羰基、C2-C12烯基羰基、C3-C12环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜 基、砜基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
优选地，R 1为C1-C20的烷基，R 2选自C1-C20的烷基；更进一步优选地，R 1为C1-C10的烷基，R 2选自C1-C10的烷基，R 1和R 2可以分别为C1、C2、C3、C4、C5、C6、C7、C8、C9、C10烷基。进一步优选地，R 1和R 2分别为乙基。
X选自杂原子，包括O、S、N、P等在内的杂原子；优选地，X为O。
n为大于等于1的正整数，n为大于等于1的正整数；例如，n可以是1-100、100-1000、1000-5000、5000-10000、10000-15000、15000-20000、20000-30000、30000-40000、40000-50000、50000-100000、100000-200000等。
作为优选，所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)，所述二氧化碳基聚酯poly(δLH 2)包含如下式6所示的重复单元：
Figure PCTCN2022134072-appb-000024
其中，n为大于等于1的正整数。
所述聚酯高分子化合物包括线性、环状、星形拓扑结构。
作为优选，所述聚酯高分子化合物结构为线性结构时，其结构如式2所示：
Figure PCTCN2022134072-appb-000025
R 1、R 2、X、n、m定义如上式4化合物中所述。
R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个。
作为优选，R可代表芳香性基团，包含苯基、萘基、蒽基、菲基、芘基、苯并芘及其衍生物等；具体地，R可选自苯基、苄基、均三苄基、邻二苄基、间二苄基、对二苄基、1,2,3-三苄基、1,2,4-三苄基、1,2,3,4-四苄基、1,2,3,5-四苄基、1,2,4,5-四苄基、五苄基、六苄 基、苯乙基、均三乙基苯基、邻二乙基苯基、间二乙基苯基、对二乙基苯基、1,2,3-三乙基苯基、1,2,4-三乙基苯基、1,2,3,4-四乙基苯基、1,2,3,5-四乙基苯基、1,2,4,5-四乙基苯基、五乙基苯基、六乙基苯基、苯丙基、均三正丙基苯基、邻二正丙基苯基、间二正丙基苯基、对二正丙基苯基、1,2,3-三正丙基苯基、1,2,4-三正丙基苯基、1,2,3,4-四正丙基苯基、1,2,3,5-四正丙基苯基、1,2,4,5-四正丙基苯基、五正丙基苯基、六正丙基苯基、异丙基苯基、均三异丙基苯基、邻二异丙基苯基、间二异丙基苯基、对二异丙基苯基、1,2,3-三异丙基苯基、1,2,4-三异丙基苯基、1,2,3,4-四异丙基苯基、1,2,3,5-四异丙基苯基、1,2,4,5-四异丙基苯基、五异丙基苯基、六异丙基苯基、正丁基苯基、异丁基苯基、叔丁基苯基、邻二正丁基苯基、间二正丁基苯基、对二正丁基苯基、邻二异丁基苯基、间二异丁基苯基、对二异丁基苯基、邻二叔丁基苯基、间二叔丁基苯基、对二叔丁基苯基中的至少一个。
作为优选，R还可以是直链或支链烷烃；更优选地，R可以是碳原子数在10以内的线性或支链烷烃以及含有个别不饱和键的烷基取代基(不饱和键指的是发生SP2杂化的碳碳双键和SP杂化的碳碳叁键)。
作为优选，R还可以是分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团。
进一步优选地，R为苄基、对二苄基、(CH2)3、(CH2)4。
进一步优选地，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述二氧化碳基聚酯poly(δLH 2)结构如式7所示：
Figure PCTCN2022134072-appb-000026
其中，R 14选自C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
n为大于等于1的正整数；
m为大于等于1的正整数。
具体来说，R 14可代表芳香性基团，包含苯基、萘基、蒽基、菲基、芘基、苯并芘及其衍生物等；具体地，R 14可选自苯基、苄基、均三苄基、邻二苄基、间二苄基、对二苄基、 1,2,3-三苄基、1,2,4-三苄基、1,2,3,4-四苄基、1,2,3,5-四苄基、1,2,4,5-四苄基、五苄基、六苄基、苯乙基、均三乙基苯基、邻二乙基苯基、间二乙基苯基、对二乙基苯基、1,2,3-三乙基苯基、1,2,4-三乙基苯基、1,2,3,4-四乙基苯基、1,2,3,5-四乙基苯基、1,2,4,5-四乙基苯基、五乙基苯基、六乙基苯基、苯丙基、均三正丙基苯基、邻二正丙基苯基、间二正丙基苯基、对二正丙基苯基、1,2,3-三正丙基苯基、1,2,4-三正丙基苯基、1,2,3,4-四正丙基苯基、1,2,3,5-四正丙基苯基、1,2,4,5-四正丙基苯基、五正丙基苯基、六正丙基苯基、异丙基苯基、均三异丙基苯基、邻二异丙基苯基、间二异丙基苯基、对二异丙基苯基、1,2,3-三异丙基苯基、1,2,4-三异丙基苯基、1,2,3,4-四异丙基苯基、1,2,3,5-四异丙基苯基、1,2,4,5-四异丙基苯基、五异丙基苯基、六异丙基苯基、正丁基苯基、异丁基苯基、叔丁基苯基、邻二正丁基苯基、间二正丁基苯基、对二正丁基苯基、邻二异丁基苯基、间二异丁基苯基、对二异丁基苯基、邻二叔丁基苯基、间二叔丁基苯基、对二叔丁基苯基中的至少一个。
具体来说，R 14还可以是直链或支链烷烃；更优选地，R 14可以是碳原子数在10以内的线性或支链烷烃以及含有个别不饱和键的烷基取代基(不饱和键指的是发生SP 2杂化的碳碳双键和SP杂化的碳碳叁键)。
具体来说，R 14还可以是分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团。
更进一步优选地，R 14为苄基、对二苄基、(CH 2) 3、(CH 2) 4。
具体来说，n值代表重复单元个数，n为大于等于1的正整数；例如，n可以是1-100、100-1000、1000-5000、5000-10000、10000-15000、15000-20000、20000-30000、30000-40000、40000-50000、50000-100000、100000-200000等。
具体来说，m为支化度，m为大于等于1的正整数。例如，1≤m≤10，10≤m≤20；优选地，1≤m≤10(m同时也可以代表引发剂R 14(OH)m和/或(MO) mR 14的官能度)。
作为优选，所述聚酯高分子化合物结构为环状结构时，其结构如式3所示：
Figure PCTCN2022134072-appb-000027
Figure PCTCN2022134072-appb-000028
R 1、R 2、X、n定义如上式4化合物中所述。
本发明提供了一种聚酯高分子化合物的合成方法，选自以下方法中任一种或两种：
A)当所述聚酯高分子化合物结构为线性结构时，所述方法包括：式1所示的杂环内酯，在有机碱为催化剂，能够提供活性质子的试剂R(OH) m为引发剂的条件下，合成得到式2所示的聚酯高分子化合物；反应过程如反应式I所示：
Figure PCTCN2022134072-appb-000029
B)当所述聚酯高分子化合物结构为环性结构时，所述方法包括：式1所示的杂环内酯，在有机碱催化下，合成得到式3所示的聚酯高分子化合物；反应过程如反应式Ⅱ所示：
Figure PCTCN2022134072-appb-000030
在A)和/或B)中，R 1、R 2可相同或不同，并且R 1、R 2两个基团必须满足同时存在于六元杂环上，取代的位点为四个亚甲基碳中的任意两个，即必须同时存在。
在A)和/或B)中，R 1、R 2分别独立地选自氢、卤素、烷基(线性烷基、支链烷基、环烷基)、取代的烷基(线性烷基、支链烷基、环烷基)、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、 取代的多杂环芳香基中的任意一个；所述单环芳香基包括苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；
所述卤素选自氟、氯、溴、碘。
所述烷基为线性烷基、支链烷基、环烷基；进一步地，所述烷基可以是C1-C20的烷基；也可以是C1-C10的烷基，包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，为乙基。
所述取代的烷基为取代的线性烷基、支链烷基、环烷基。
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。进一步地，所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、羟基、硝基、卤素、羧基、C1-C10烷基、烷氧基、胺基、环烷氧基、环胺基、C2-C12烯基、C2-C12炔基、C3-C12环烷基、苄基、烷基羰基、C2-C12烯基羰基、C3-C12环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、砜基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
优选地，R 1为C1-C20的烷基，R 2选自C1-C20的烷基；更进一步优选地，R 1为C1-C10的烷基，R 2选自C1-C10的烷基，R 1和R 2可以分别为C1、C2、C3、C4、C5、C6、C7、C8、C9、C10烷基。进一步优选地，R 1和R 2分别为乙基。
反应式I或Ⅱ中，X选自杂原子，包括O、S、N、P等在内的杂原子；优选地，X为O。
反应式I或Ⅱ中，n值代表重复单元个数，n为大于等于1的正整数；例如，n可以是1-100、100-1000、1000-5000、5000-10000、10000-15000、15000-20000、20000-30000、30000-40000、40000-50000、50000-100000、100000-200000等。
反应式I中，m为支化度，m为大于等于1的正整数。例如，1≤m≤10，10≤m≤20；优选地，1≤m≤10(m同时也可以代表引发剂ROH的官能度)。
反应式I或Ⅱ中，所述有机碱可以为大位阻或非亲核性碱。
在A)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述方法包括： 式8所示的δLH 2，在有机碱作为催化剂，提供活性质子的试剂R 14(OH)m和/或(MO) mR 14作为引发剂的条件下，合成得到式7所示的二氧化碳基聚酯poly(δLH 2)；反应过程如反应式Ⅲ所示：
Figure PCTCN2022134072-appb-000031
其中，R 14定义同上文所述。
在有机碱作为催化剂和/或提供活性质子的试剂作为引发剂是指，本发明所述方法可以是在催化剂和引发剂同时存在的条件下进行合成，也可以仅在引发剂条件下进行。
作为优选，所述有机碱为胺类化合物或含氮杂环化合物；所述胺类化合物具有下式：
Figure PCTCN2022134072-appb-000032
并且所述铵盐具有式R 11R 12R 13N +H，其中R 11、R 12和R 13各自分别代表氢(H)、C1-C20烷基、C5-C20环烷基或C7-C20烷芳基基团，所述基团各自可选包含一个或多个杂原子(例如氧、磷或硫原子)和/或取代基，并且R 11和R 12之间、R 12和R 13之间、和/或R 11和R 13之间可以存在环，所述环可以包含杂原子。
作为优选，所述有机碱选自磷腈、含有胍基基团的化合物、含脒基基团的化合物中的一种或几种。在一些实施方式中，所述有机碱选自 tBu-P 1、 tBu-P 2、 tBu-P 4、1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)、1,8-二氮杂二环十一碳-7-烯(DBU)、二乙胺、二甲胺、三乙胺、N,N‐二异丙基乙胺、N‐甲基吗啉、正辛胺、三正丁胺、月桂胺、硬脂胺、四丙基氢氧化铵(TPAOH)、四丁基氢氧化铵(TBAOH)、C1～C5的醇钠或醇钾、三乙醇胺、胆碱、N-甲基吗啉、吡啶、二甲氨基吡啶、N，N’-二羟乙基乙二胺、β-羟乙基乙二胺、N-(2-羟乙基)乙二胺、N，N，N’，N’-四羟乙基乙二胺、N-羟乙基丙二胺、三甲基羟乙基丙二胺、N，N’-二(2-羟乙基)-1，3-丙二胺等中的一种或几种。
优选地，所述催化剂为磷腈、TBD中的一种或几种。进一步优选地，所述磷腈为含有(R 2N) 2-P＝N结构的强Lewis碱。更进一步优选地，所述磷腈结构如式5所示：
Figure PCTCN2022134072-appb-000033
式5中，R 3-R 10分别独立地选自烷基，优选为C1-C10烷基，例如C1(甲基)、C2(乙基)、C3(丙基、异丙基)、C4(丁基、叔丁基)、C5、C6、C7、C8、C9、C10烷基。
y为大于等于1的正整数。优选地，1≤y≤3。
优选地，所述磷腈选自 tBu-P 1、 tBu-P 2、 tBu-P 4，结构分别以下所示：
Figure PCTCN2022134072-appb-000034
反应式I中，所述引发剂为能够提供活性质子的试剂，具体为醇类；优选地，所述引发剂为醇盐。
所述醇盐为R(OH)m，其中R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个。m同时也可以代表引发剂的官能度，m为大于等于1的正整数；例如，1≤m≤10，10≤m≤20；优选地，1≤m≤10。
当仅采用引发剂不加入催化剂时，优选地，如反应式Ⅲ中，引发剂为(MO) mR 14、或R 14(OH)m和(MO) mR 14的混合物，所述混合物中包含一种或几种R 14(OH)m以及一种或几种(MO) mR 14；在一些优选实施方式中，混合物中包含一种R 14(OH)m和一种(MO) mR 14。例如，二氧化碳基聚酯poly(δLH 2)，还可以仅在有机碱催化剂条件下，不加入引发剂合成得到。具体来说，反应式Ⅲ中，所述引发剂为能够提供活性质子的试剂R 14(OH)m和/或(MO) mR 14，其中R 14选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂 环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个。
作为优选，R可代表芳香性基团，包含苯基、萘基、蒽基、菲基、芘基、苯并芘及其衍生物等；具体地，R可选自苯基、苄基、均三苄基、邻二苄基、间二苄基、对二苄基、1,2,3-三苄基、1,2,4-三苄基、1,2,3,4-四苄基、1,2,3,5-四苄基、1,2,4,5-四苄基、五苄基、六苄基、苯乙基、均三乙基苯基、邻二乙基苯基、间二乙基苯基、对二乙基苯基、1,2,3-三乙基苯基、1,2,4-三乙基苯基、1,2,3,4-四乙基苯基、1,2,3,5-四乙基苯基、1,2,4,5-四乙基苯基、五乙基苯基、六乙基苯基、苯丙基、均三正丙基苯基、邻二正丙基苯基、间二正丙基苯基、对二正丙基苯基、1,2,3-三正丙基苯基、1,2,4-三正丙基苯基、1,2,3,4-四正丙基苯基、1,2,3,5-四正丙基苯基、1,2,4,5-四正丙基苯基、五正丙基苯基、六正丙基苯基、异丙基苯基、均三异丙基苯基、邻二异丙基苯基、间二异丙基苯基、对二异丙基苯基、1,2,3-三异丙基苯基、1,2,4-三异丙基苯基、1,2,3,4-四异丙基苯基、1,2,3,5-四异丙基苯基、1,2,4,5-四异丙基苯基、五异丙基苯基、六异丙基苯基、正丁基苯基、异丁基苯基、叔丁基苯基、邻二正丁基苯基、间二正丁基苯基、对二正丁基苯基、邻二异丁基苯基、间二异丁基苯基、对二异丁基苯基、邻二叔丁基苯基、间二叔丁基苯基、对二叔丁基苯基中的至少一个。
作为优选，R还可以是直链或支链烷烃；更优选地，R可以是碳原子数在10以内的线性或支链烷烃以及含有个别不饱和键的烷基取代基(不饱和键指的是发生SP2杂化的碳碳双键和SP杂化的碳碳叁键)。
作为优选，R还可以是分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团。
进一步优选地，R为苄基、对二苄基、(CH2)3、(CH2)4，即所述引发剂选自苯甲醇(BnOH)、1,4-苯二甲醇(1,4-BDM)、1,3-丙二醇、1,4-丁二醇。
作为优选，R 14可代表碳原子数在10以内的线性或支链烷烃以及含有个别不饱和键的烷基取代基(不饱和键指的是发生SP 2杂化的碳碳双键和SP杂化的碳碳叁键)，芳香性基团。
作为进一步优选，R 14可代表C1-C10烷基；芳香性基团，包含苯基、萘基、蒽基、菲基、芘基、苯并芘及其衍生物等；具体地，R可选自甲基、乙基、丙基、异丙基、苯基、苄基、均三苄基、邻二苄基、间二苄基、对二苄基、1,2,3-三苄基、1,2,4-三苄基、1,2,3,4-四苄基、1,2,3,5-四苄基、1,2,4,5-四苄基、五苄基、六苄基、苯乙基、均三乙基苯基、邻二乙基苯基、间二乙基苯基、对二乙基苯基、1,2,3-三乙基苯基、1,2,4-三乙基苯基、1,2,3,4-四乙基苯基、1,2,3,5-四乙基苯基、1,2,4,5-四乙基苯基、五乙基苯基、六乙基苯基、苯丙基、均三 正丙基苯基、邻二正丙基苯基、间二正丙基苯基、对二正丙基苯基、1,2,3-三正丙基苯基、1,2,4-三正丙基苯基、1,2,3,4-四正丙基苯基、1,2,3,5-四正丙基苯基、1,2,4,5-四正丙基苯基、五正丙基苯基、六正丙基苯基、异丙基苯基、均三异丙基苯基、邻二异丙基苯基、间二异丙基苯基、对二异丙基苯基、1,2,3-三异丙基苯基、1,2,4-三异丙基苯基、1,2,3,4-四异丙基苯基、1,2,3,5-四异丙基苯基、1,2,4,5-四异丙基苯基、五异丙基苯基、六异丙基苯基、正丁基苯基、异丁基苯基、叔丁基苯基、邻二正丁基苯基、间二正丁基苯基、对二正丁基苯基、邻二异丁基苯基、间二异丁基苯基、对二异丁基苯基、邻二叔丁基苯基、间二叔丁基苯基、对二叔丁基苯基中的至少一个。
进一步优选地，R 14为苄基、甲基。
进一步优选地，M为K，Na，Li，Rb或H。
进一步优选地，所述引发剂选自苯甲醇(BnOH)、甲醇钾(KOMe)、甲醇钠(NaOMe)、叔丁醇钾(KO tBu)、叔丁醇钠(NaO tBu)、叔丁醇锂(LiO tBu)。
反应式Ⅲ中，n值代表重复单元个数，n为大于等于1的正整数；例如，n可以是1-100、100-1000、1000-5000、5000-10000、10000-15000、15000-20000、20000-30000、30000-40000、40000-50000、50000-100000、100000-200000等。
反应式Ⅲ中，m为支化度，m为大于等于1的正整数。例如，1≤m≤10，10≤m≤20；优选地，1≤m≤10(m同时也可以代表引发剂R 14(OH)m和/或(MO) mR 14的官能度)。
本发明所述方法中，反应式I中，所述式1、催化剂、引发剂的摩尔用量比值为(5-200):(0.01-5):1；优选地，为(25-100):(0.1-1):1，例如可以是(25-30):(0.1-1):1、(35-40):(0.1-1):1、(45-50):(0.1-1):1、(55-60):(0.1-1):1、(65-70):(0.1-1):1、(75-80):(0.1-1):1、(85-90):(0.1-1):1、(95-100):(0.1-1):1、(25-100):(0.1-0.2):1；(25-100):(0.2-0.3):1；(25-100):(0.3-0.4):1；(25-100):(0.4-0.5):1；(25-100):(0.5-0.6):1；(25-100):(0.6-0.7):1；(25-100):(0.7-0.8):1；(25-100):(0.8-0.9):1；(25-100):(0.9-1):1；进一步优选地，为40:0.5:1、50:0.5:1、50:1:1、50:0.25:1、50:0.2:1、50:0.1:1、25:0.1:1、100:0.2:1；更进一步优选地，为50:0.5:1、50:1:1、50:0.25:1、50:0.2:1、50:0.1:1、25:0.1:1或100:0.2:1。
作为优选，如反应式Ⅲ中，所述式8、催化剂、引发剂的摩尔用量比值为(5-200):(0-5):(0-1)；催化剂、引发剂不同时为0。优选地，为(25-200):(0-1):(0-1)；进一步优选地，为(50-200):(0-1):(0-1)，例如可以是(50-55):(0-1):(0-1)、(55-60):(0-1):(0-1)、(65-70):(0-1):(0-1)、(75-80):(0-1):(0-1)、(85-90):(0-1):(0-1)、(95-100):(0-0.1):(0-1)、(100-110):(0.1-0.2):(0-1)、(110-120):(0.2-0.3):(0-1)、(120-130):(0.3-0.4):(0-1)、(130-140):(0.4-0.5):(0-1)、(140- 150):(0.5-0.6):(0-1)、(150-160):(0.6-0.7):(0-1)、(160-170):(0.7-0.8):(0-1)、(170-180):(0.8-0.9):(0-1)、(180-190):(0.9-1):(0-1)、(190-200):(0.9-1):(0-1)；更进一步优选地，为50:0.1:0、50:0.1:1、50:0.2:1、50:0.5:1、50:1:1、50:0:1、100:0:1、200:0:1。
本发明所述方法中，反应式Ⅱ中，所述式1、催化剂的摩尔用量比值为(10-500):(0.01-5)；优选地，为(20-40):(0.1-4)，进一步优选地，为(30-350):(0.3-3)，更进一步优选地，为(40-300):(0.8-1.5)，更进一步优选地，为(50-260):1；例如可以是50:1、60:1、70:1、80:1、90:1、100:1、110:1、120:1、130:1、140:1、150:1、160:1、170:1、180:1、190:1、200:1、210:1、220:1、230:1、240:1、250:1、260:1。
反应式I、Ⅱ或Ⅲ中，本发明所述方法可以在无溶剂条件(即本体条件)和溶剂条件下进行。
当在溶剂条件下进行时，所述反应的溶剂选自：四氢呋喃(THF)、TBD、苯、甲苯、二甲苯、二氯苯、均三甲苯、二氯甲烷、氯仿、1,2-二氯乙烷、四氢吡咯、四氢吡喃、六氢吡啶、乙酸乙酯、乙醚、二甲醚、甲乙醚、正己烷、环己烷、环戊烷、乙腈、二氧六环、N,N-二甲基甲酰胺、二甲基亚砜等中的一种或几种；优选地，反应的溶剂为四氢呋喃(THF)和/或TBD。更进一步优选地，所述溶剂为THF。
本发明所述方法中，对式1所示的聚酯高分子化合物的初始浓度[M] 0不作特别的限制，只要能实现所述聚酯高分子化合物的制备即可。
在一些实施方式中，如反应式I中，式1所示的聚酯高分子化合物的初始浓度[M] 0为1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20mol L -1；优选地，[M] 0为3.0-10.0mol L -1；进一步优选地，为4.0-8.0mol L -1；更进一步优选地，为5.0-6.3mol L -1；更进一步优选地，为5.0、5.3或6.3mol L -1。
在一些实施方式中，如反应式Ⅱ中，式1所示的杂环内酯的初始浓度[M] 0为0.1-20mol L -1，例如可以是1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20mol L -1。优选地，为0.4-16mol L -1；更优选地，为0.6-12mol L -1；更进一步优选地，为1.2-8mol L -1，例如可以是1.2、1.4、1.6、1.8、2.0、2.2、2.4、2.6、2.8、3.0、3.2、3.4、3.6、3.8、4.0、4.2、4.4、4.6、4.8、5.0、5.2、5.4、5.6、5.8、6.0、6.2、6.4、6.6、6.8、7.0、7.2、7.4、7.6、7.8、8.0mol L -1。在一些优选实施方式中，所述杂环内酯的初始浓度[M] 0为3-6mol L -1。在另一些优选实施方式中，所述杂环内酯的初始浓度[M] 0为4-5mol L - 1。在另一些优选实施方式中，所述杂环内酯的初始浓度[M] 0为4.0mol L -1。
在一些实施方式中，如反应式Ⅲ中，所述式8在所述反应的溶剂的初始浓度[δLH 2] 0为 1-7M；优选地，为3-7M；进一步优选地，为5-6M；更进一步优选地，为5.5-6M；更进一步优选地，为5.62或5.82M。
本发明所述方法中，对反应的温度不作特别的限制，只要能实现所述聚酯高分子化合物的制备即可。
在一些实施方式中，如反应式I或Ⅲ中，所述反应温度为-100～200℃，可以是-100～180、-80～200、-100～150、-100～130、-100～120、-100～100℃、-80～80、-70～70、-60～60、-50～50、-50～60、-40～40、-30～30、-20～20、-10～10℃。优选地，为-50～60℃。进一步优选地，为-25～45℃，例如可以是-25、-24、-23、-22、-21、-20、-19、-18、-17、-16、-15、-14、-13、-12、-11、-10、-9、-8、-7、-6、-5、-4、-3、-2、-1、0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45℃。更进一步优选地，为-25～-9℃。更进一步优选地，为-25℃。
在一些实施方式中，如反应式Ⅱ中，所述反应温度为-100～220℃，可以是-100～180、-80～200、-100～150、-100～130、-100～120、-100～100℃、-80～80、-70～70、-60～60、-50～50、-50～60、-40～40、-30～30、-20～20、-10～10℃。优选地，为-80～80℃。更优选地，为-50～60℃。更进一步优选地，为-50～30℃，例如可以是-50、-49、-48、-47、-46、-45、-44、-43、-42、-41、-40、-39、-38、-37、36、-35、-34、-33、-32、-31、-30、-29、-28、-27、-26、-25、-24、-23、-22、-21、-20、-19、-18、-17、-16、-15、-14、-13、-12、-11、-10、-9、-8、-7、-6、-5、-4、-3、-2、-1、0、1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30℃。在一些优选实施方式中，所述反应的温度为-30～-10℃。在一些优选实施方式中，所述反应的温度为-25℃。
本发明所述方法中，对反应的时间不作特别的限制，只要能实现所述聚酯高分子化合物的制备即可。
在一些实施方式中，如反应式I中，所述反应时间为10s-360h；可以是10s-360h、20s-340h、30s-320h、40s-300h、1min-280h、1min-260h、1min-240h、1min-220h、1min-200h、1min-180h、1min-160h、1min-140h、1min-120h、2min-260h、3min-240h、4min-220h、5min-200h、10min-180h、30min s-160h、1-150h、1h-140h、5h-120h、10h-100h。优选地，所述反应时间为1-150h。更优选地，为8-120h，例如可以是8、10、12、14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48、 50、60、70、72、80、90、96、100、110、120h。更进一步优选地，为8-12h。
在一些实施方式中，如反应式Ⅲ中，所述反应时间为10s-360h；可以是10s-360h、20s-340h、30s-320h、40s-300h、1min-280h、1min-260h、1min-240h、1min-220h、1min-200h、1min-180h、1min-160h、1min-140h、1min-120h、2min-260h、3min-240h、4min-220h、5min-200h、10min-180h、30min s-160h、1-150h、1h-140h、5h-120h、10h-100h。优选地，所述反应时间为1-150h。更优选地，为8-120h，例如可以是8、10、12、14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48、50、60、70、72、80、90、96、100、110、120h。更进一步优选地，为12-48h。
在一些实施方式中，如反应式Ⅱ中，所述反应时间为5s-400h；可以是10s-380h、20s-36e40h、40s-320h、1min-300h、1min-280h、1min-260h、1min-240h、1min-220h、1min-200h、1min-180h、1min-160h、1min-140h、1min-120h、1min-100h、1min-80h、1min-60h、1min-40h、5min-40h、11min-40h、16min-40h、1min-40h、1min-40h、1min-40h、1min-40h、1min-40h、5min-100h、2min-260h、3min-240h、4min-220h、5min-200h、10min-180h、30min-160h、1h-150h、1h-120h、1h-100h、1h-80h、1h-60h、1h-40h、1h-20h、1h-10h、1h-5h、5h-100h、5h-80h、5h-60h、5h-40h、5h-20h、5h-10h、10h-100h、10h-80h、10h-60h、10h-40h、10h-20h、20h-60h、20h-40h、10h-30h、10h-20h。优选地，所述反应时间为10min-20h，例如是10min、11min、12min、13min、14min、15min、16min、17min、18min、19min、20min、30min、1h、2h、3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h、20h。在一些优选实施方式中，所述反应时间为11min；在另一些优选实施方式中，所述反应时间为16min；在另一些优选实施方式中，所述反应时间为0.5h；在另一些优选实施方式中，所述反应时间为2h；在另一些优选实施方式中，所述反应时间为2.5h；在另一些优选实施方式中，所述反应时间为3h；在另一些优选实施方式中，所述反应时间为4h；在另一些优选实施方式中，所述反应时间为6-8h；在另一些优选实施方式中，所述反应时间为7h；在另一些优选实施方式中，所述反应时间为10h；在另一些优选实施方式中，所述反应时间为12h。
本发明所述方法中，当R 1为乙基，R 2为乙基，即式1为HL，催化剂为 tBu-P 4，引发剂为BnOH，反应过程如下反应式Ⅲ所示：
Figure PCTCN2022134072-appb-000035
本发明所述方法中，当R 1为乙基，R 2为乙基，即式1为HL，引发剂为R 1OH时，生成单羟基封端聚酯高分子化合物；当R 1为乙基，R 2为乙基，即式1为HL，引发剂为HO-R 2-OH时，生成双羟基封端聚酯高分子化合物；反应式如下所示：
Figure PCTCN2022134072-appb-000036
本发明 tBu-P 4/BnOH催化HL的开环聚合过程中可能的链引发机制如图1所示。通过 1H NMR监测 tBu-P 4与BnOH在室温下的化学计量反应，发现配合物[ tBu-P 4H+…OBn]的形成。本发明观察到δ0.92ppm羟基H的消失以及tBu-P4和BnOH的其他信号化学位移的变化。
用于佐证机理的当量实验步骤：如图1，取等当量(0.05mmol)的BnOH和 tBu-P 4混合后溶解于0.6mL氘代甲苯中，将二者装入核磁管中并且充分震荡，进行核磁测试。
本发明所述方法中，当引发剂R 14(OH)m和/或(MO) mR 14，且m为1时，生成单羟基封端二氧化碳基聚酯poly(δLH 2)；当引发剂为R 14(OH)m和/或(MO) mR 14且m为大于1的整数时，生成多羟基封端二氧化碳基聚酯poly(δLH 2)；反应式如式Ⅲ所示。
本发明所述方法中，当R 1为乙基，R 2为乙基，即式1为HL，催化剂为 tBu-P 4，反应过程如下反应式Ⅴ所示：
Figure PCTCN2022134072-appb-000037
n的定义如上文所述。
本发明[ tBu-P 4H] +催化HL的开环聚合过程中可能的链引发机制如图22-24所示。将HL和 tBu-P 4分别以不同的摩尔比例在室温下混合，并通过相应的1H和31P NMR光谱对反应中的[ tBu-P 4H] +的特征信号和 tBu-P 4的特征信号进行监测， tBu-P 4只能将很小一部分的HL单体进行脱质子化反应。
本发明还提供了由上述方法制备得到的环状的聚酯高分子化合物。所述方法可以根据聚合度调控环状聚合物的聚合度，进而调控聚合物的Mn(数均分子量)和
Figure PCTCN2022134072-appb-000038
(分子量分布)。在一些实施方式中，所述环状聚合物的M n在30-2000kg mol -1之间。在一些实施方式中，所述环状聚合物的M n在30-100kg mol -1之间。在一些实施方式中，所述环状聚合物的M n在100-200kg mol -1之间。在一些实施方式中，所述环状聚合物的M n在200-400kg mol -1之间。在另一些优选实施方式中，环状聚合物的M n在500-600kg mol -1之间。在另一些优选实施方式中，环状聚合物的M n在500-800kg mol -1之间。在另一些优选实施方式中，环状聚合物的M n在400-1500kg mol -1之间。在另一些优选实施方式中，环状聚合物的M n在300-2000kg mol -1之间。
本发明还提供了式3所示的环状的聚酯高分子化合物或由上述方法制备的环状的聚酯高分子化合物在制备聚合物薄膜、压敏胶黏剂(如胶带)、热塑性弹性体中的任意一种或几种的应用；其中，所述压敏胶黏剂可以进一步用于制备胶带等产品。在一些实施方式中，所述聚合物薄膜为无色、透明且具有良好的柔性和粘弹性。在一些实施方式中，所述胶带为无色、透明且具有良好的柔性和粘弹性。
本发明还提供了由上述方法制备得到的聚酯高分子化合物。
本发明还提供了由上述方法制备得到的二氧化碳基聚酯poly(δLH 2)。
本发明还提供了所述聚酯高分子化合物或由上述方法制备的聚酯高分子化合物在制备聚氨酯、聚合物薄膜、压敏胶黏剂、胶带、热塑性弹性体中的一种或几种的应用。
本发明所述poly(δLH 2)为柔性材料，具有多种优异的物理化学特性，包括透明性高、分子量高、热稳定性强、延展性好等。基于此，本发明还提供了所述二氧化碳基聚酯poly(δLH 2)或由上述方法制备的二氧化碳基聚酯poly(δLH 2)在应用于聚氨酯、压敏胶黏剂领域中的应用。
聚氨酯领域：聚氨酯全称为聚氨基甲酸酯，是一种高分子化合物，主要有聚酯型和聚醚型两种。聚氨酯主要是通过聚酯多元醇或聚醚多元醇与多官能度的异氰酸酯(如二苯甲烷二异氰酸酯MDI、甲苯二异氰酸酯TDI等)进行反应，从而共聚得到的，因而不同分子量的聚酯多元醇或聚醚多元醇是聚氨酯合成领域不可或缺的原料。
聚氨酯根据其材料性质的不同分为硬泡、软泡、聚氨酯弹性体、热塑性塑料、聚氨酯胶黏剂、聚氨酯涂料、油漆，被广泛地应用于汽车制造业、家具、建筑、保温材料、以及鞋类制造业等诸多领域，具有十分重要的应用价值。
聚酯多元醇和聚醚多元醇是工业上用于合成聚氨酯材料的重要前体，并且基于聚酯多元醇的聚氨酯材料往往比聚醚多元醇聚氨酯有着更好的力学性能。然而，由于聚酯多元醇的生产成本要远高于聚醚多元醇，因此限制了聚酯多元醇的大规模应用。因此，本发明制备的polyHL，一种廉价易得、且具有全新化学结构的聚酯材料以及相对应的聚酯多元醇对于聚氨酯领域以至化工领域都具有十分重大且深远的意义。
压敏胶黏剂，全称为压力敏感性胶黏剂，俗称不干胶，简称压敏胶，是高分子工业中不可或缺的一种功能性材料。从化学结构上讲，目前市场上主要的压敏胶都是以聚烯烃为主，那么聚烯烃无法做到使用后降解，而polyHL经过本发明初步的实验结果证实了其具有相对较好的压敏胶性能，并且由于polyHL可以实现单体的化学回收，因此有潜力成为市面上第一种可以实现单体回收的压敏胶黏剂，具有光明的产业化前景。
胶带可以是透明胶带、不透明胶带、单面胶带、双面胶带、保护胶带、隔热胶带、高温胶带、美纹胶带、电工胶带、电镀胶带、包装胶带、布基胶带、纤维胶带、PE泡棉胶带、牛皮纸胶带、保护膜胶带、特种胶带等。另一些优选实施方式中，所述胶带为透明胶带。在另一些优选实施方式中，所述胶带为3M商业化透明胶带。
聚合物薄膜呈无色透明状，具有良好的柔性和粘弹性(剥离强度)。
本发明还提供了有机碱如磷腈在催化如上所述式1化合物合成式2和/或式3所示的聚酯 高分子化合物中的应用。所述有机碱可以为大位阻或非亲核性碱。
作为优选，所述有机碱为胺类化合物或含氮杂环化合物；所述胺类化合物具有下式：
Figure PCTCN2022134072-appb-000039
并且所述铵盐具有式R 11R 12R 13N +H，其中R 11、R 12和R 13各自分别代表氢(H)、C1-C20烷基、C5-C20环烷基或C7-C20烷芳基基团，所述基团各自可选包含一个或多个杂原子(例如氧、磷或硫原子)和/或取代基，并且R 11和R 12之间、R 12和R 13之间、和/或R 11和R 13之间可以存在环，所述环可以包含杂原子。
作为优选，所述有机碱选自磷腈、含有胍基基团的化合物、含脒基基团的化合物中的一种或几种。在一些实施方式中，所述有机碱选自 tBu-P 4、1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)、1,8-二氮杂二环十一碳-7-烯(DBU)、二乙胺、二甲胺、三乙胺、N,N‐二异丙基乙胺、N‐甲基吗啉、正辛胺、三正丁胺、月桂胺、硬脂胺、四丙基氢氧化铵(TPAOH)、四丁基氢氧化铵(TBAOH)、C1～C5的醇钠或醇钾、三乙醇胺、胆碱、N-甲基吗啉、吡啶、二甲氨基吡啶、N，N’-二羟乙基乙二胺、β-羟乙基乙二胺、N-(2-羟乙基)乙二胺、N，N，N’，N’-四羟乙基乙二胺、N-羟乙基丙二胺、三甲基羟乙基丙二胺、N，N’-二(2-羟乙基)-1，3-丙二胺等中的一种或几种。
优选地，所述有机碱为磷腈、TBD中的一种或几种。进一步优选地，所述磷腈为含有(R 2N) 2-P＝N结构的强Lewis碱。更进一步优选地，所述磷腈结构如式5所示：
Figure PCTCN2022134072-appb-000040
式5中，R 3-R 10分别独立地选自烷基，优选为C1-C10烷基，例如C1(甲基)、C2(乙基)、C3(丙基、异丙基)、C4(丁基、叔丁基)、C5、C6、C7、C8、C9、C10烷基。
y为大于等于1的正整数。例如，1≤y≤10，10≤y≤20；优选地，1≤y≤3。
进一步优选地，所述磷腈选自 tBu-P 1、 tBu-P 2、 tBu-P 4，结构分别以下所示：
Figure PCTCN2022134072-appb-000041
本发明还提供了催化聚合物回收单体的方法，所述方法选自以下任一种或两种：
a)如催化式2所示的方法包括催化法和热解法(thermolysis)；
b)如催化式3所示的方法包括无机盐热解催化法和La[N(SiMe 3) 2] 3温和催化法。
本发明中，a)中，所述催化法包括：采用无机盐、金属有机化合物、有机化合物催化剂降解所述式2聚酯高分子化合物，回收得到式1所示的杂环单体或其寡聚物或其衍生物；
具体来说，在a)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，由聚合物Poly(δLH 2)回收δLH 2单体，反应过程如下反应式Ⅵ所示：
Figure PCTCN2022134072-appb-000042
所述催化法包括：采用无机盐、金属有机化合物或有机化合物催化剂中的至少一种化合物降解所述式8所示的二氧化碳基聚酯poly(δLH 2)，回收得到式7所示的δLH 2或其寡聚物或其衍生物；
a)中，所述热解法包括：对所述式2聚酯高分子化合物进行加热裂解，回收得到式1所示的杂环单体或其寡聚物或其衍生物；所述催化法包括：在溶剂中，采用无机盐、金属有机化合物、有机化合物等催化剂降解如式2所示的聚酯高分子化合物，得到式1所示的杂环化合物或其寡聚物或式1相应的衍生物。
具体来说，在a)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述热解法包括：对所述式8所示的二氧化碳基聚酯poly(δLH 2)进行加热裂解，回收得到式7所示的δLH 2或其寡聚物或其衍生物。
a)中，所述溶剂选自苯、氯苯、溴苯、二氯苯、二溴苯、邻二氯苯、邻二溴苯、间二氯苯、间二溴苯、对二氯苯、对二溴苯甲苯、间二甲苯、对二甲苯、邻二甲苯、均三甲苯、 二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等中的一种或几种；优选地，为甲苯或邻二氯苯；更优选地，为邻二氯苯。当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述溶剂更优选为甲苯。
a)中，所述盐为无机盐，所述无机盐选自氯化锌、氯化锡、氯化铜、氯化镍、氯化亚铜、氯化钯、氯化铂、氯化钇、氯化铁、氯化亚铁、三氯化钛、氯化锆、三氯化镧、氧化铝镧、氟化镧、硼化镧、硫酸镧、氢氧化镧、碳酸镧、草酸镧、乙酸镧、溴化镧、硝酸镧等中的一种或几种；优选地，为氯化锌。
a)中，所述金属有机化合物选自辛酸亚锡、异辛酸亚锡、二月桂酸二丁基锡、双[双(三甲基甲硅烷基)氨基]锡、三异丙基氧镧、三[N,N-双(三甲基硅烷)胺]镧、三氟甲磺酸镧、三氟甲磺酸银、三氟甲磺酸铜、三氟甲磺酸铁、三氟甲磺酸钪、三氟甲磺酸钇等中的一种或几种；优选地，为辛酸亚锡、三[N,N-双(三甲基硅烷)胺]镧。
a)中，所述有机化合物选自1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、1 5 7-三叠氮双环(4.4.0)癸-5-烯(TBD)、1,3-二均三甲苯基咪唑-2-叉(IMes)、 tBu-P 1、 tBu-P 2、 tBu-P 4等中的一种或几种；优选地，为DBU。
当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述催化剂为无机盐；更进一步优选地，为镧盐；更进一步优选地，为La[N(SiMe 3) 2] 3。
a)中，所述降解的条件为油浴或沙浴等热浴方法，所述的温度范围为100-300℃；优选为120-300℃；更优选为160℃。当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述的温度范围优选为120-180℃；更优选为120℃。
a)中，所述降解的时间为8-24h；优选为12h。当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述降解的时间为0.5-24h；优选为0.5-8h；优选为1-5h；优选为2h。
本发明中，a)中，所述热解法包括：对如上所述的聚酯高分子化合物进行加热裂解，得到式1所示的杂环化合物或其寡聚物亦或是式1相应的衍生物。
作为优选，所述加热裂解优选在氮气氛围中进行。
作为优选，所述加热裂解在密封条件下进行。
作为优选，所述加热裂解在真空条件下进行。
其中，所述加热裂解优选在沙浴中进行。本发明对所述加热的温度不作限制，只要能够实现所述加热裂解的目的，以回收聚酯高分子化合物的单体即可。在一些实施方式中，所述加热的温度大于100℃。在另一些实施方式中，所述加热的温度为100-1000℃；可以是100- 200、200-300、150-300、300-400、400-500、500-600、600-700、700-800、800-900、900-1000℃。优选地，所述加热的温度为150-300℃。进一步优选地，为150-260℃。更进一步优选地，为180-230℃。更进一步优选地，为200-230℃。更进一步优选地，为220℃。
其中，本发明对所述加热的时间不作限制，只要能够实现所述加热裂解的目的，以回收聚酯高分子化合物的单体即可。在一些实施方式中，所述加热的时间大于0.5h。在另一些实施方式中，所述加热的时间为1-50h；可以是1-5、5-10、10-15、15-20、1-20、20-25、25-30、30-35、35-40、40-45、45-50h。优选地，所述加热的时间为1-20h。进一步优选地，为1-10h。更进一步优选地，为1-5h。更进一步优选地，为3h。
在一优选实施方式中，当采用催化法催化二氧化碳基聚酯poly(δLH 2)以回收单体δLH 2的步骤包括：在甲苯中，在120℃条件下，对式8所示的二氧化碳基聚酯poly(δLH 2)采用La[N(SiMe 3) 2] 3进行催化裂解2h，得到式7所示的δLH 2或其寡聚物亦或是式7相应的衍生物。
b)中，所述无机盐热解催化法包括：采用无机盐催化降解如式3所示的聚酯高分子化合物，得到式1所示的杂环化合物或其寡聚物或式1相应的衍生物；
b)中，所述La[N(SiMe 3) 2] 3温和催化法包括：在温和条件下对式3所示的聚酯高分子化合物采用La[N(SiMe 3) 2] 3进行催化裂解，得到式1所示的杂环化合物或其寡聚物亦或是式1相应的衍生物。
所述热解催化法可以在溶剂或无溶剂条件下进行。
b)中，当在溶剂中进行降解时，所述溶剂可以选自甲苯、苯、氯苯、溴苯、二氯苯、二溴苯、邻二氯苯、邻二溴苯、间二氯苯、间二溴苯、对二氯苯、对二溴苯甲苯、间二甲苯、对二甲苯、邻二甲苯、均三甲苯、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等中的一种或几种。在一些优选实施方式中，所述溶剂为甲苯。在另一些优选实施方式中，所述溶剂为均三甲苯。在另一些优选实施方式中，所述溶剂为邻二氯苯。
其中，所述热解催化法对式(2)环状聚合物初始浓度[M] 0不作特别的限制，只要能实现所述环状聚合物的制备即可。在一些实施方式中，式(2)环状聚合物的初始浓度[M] 0为1-50mol L -1，例如可以是2、4、6、8、10、12、14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48、50mol L -1。优选地，为2-40mol L -1；更优选地，为3-30mol L -1；更进一步优选地，为4-20mol L -1。在一些优选实施方式中，所述环状聚合物的初始浓度[M] 0为3-6mol L -1。在另一些优选实施方式中，所述杂环内酯的初始浓度[M] 0为4.0mol L -1。
其中，所述热解催化的条件为油浴或沙浴等热浴方法，所述的温度范围为100-350℃。优选地，为110-300℃；更优选地，为120-240℃；可以是120、30、140、150、160、170、180、190、200、210、220、230、240℃。在一些优选实施方式中，所述热解催化的温度为120℃。在一些优选实施方式中，所述热解催化的温度为130℃。在一些优选实施方式中，所述热解催化的温度为140℃。在一些优选实施方式中，所述热解催化的温度为150℃。在一些优选实施方式中，所述热解催化的温度为160℃。在一些优选实施方式中，所述热解催化的温度为180℃。
其中，所述热解催化的时间为6-45h；优选地，为8-36h，可以是8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36h。在一些优选实施方式中，所述热解催化的时间为10h。在一些优选实施方式中，所述热解催化的时间为12h。在一些优选实施方式中，所述热解催化的时间为16h。在一些优选实施方式中，所述热解催化的时间为24h。
本发明所述无机盐催化裂解法适用的环状聚合物的物理化学特性没有特别的限定，只要是按照本发明上述方法或其他方法获得的环状聚合物均可以采用本发明的裂解法回收单体。在一些优选实施方式中，本发明所述无机盐催化裂解法适用于M n在300-2000kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述无机盐催化裂解法适用于M n在400-1500kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述无机盐催化裂解法适用于M n在500-800kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述无机盐催化裂解法适用于M n在500-600kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述无机盐催化裂解法适用于本发明实施例1～17制备的环状聚合物。
可选地，所述热解催化在氮气氛围中进行。
可选地，所述热解催化在密封条件下进行。
可选地，所述热解催化在真空条件下进行。
本发明中，所述La[N(SiMe 3) 2] 3温和催化法包括：在温和条件下对如上所述的环状聚合物采用La[N(SiMe 3) 2] 3进行催化裂解，得到式1所示的杂环化合物或其寡聚物亦或是式1相应的衍生物。
其中，所述La[N(SiMe 3) 2] 3温和催化法可以在溶剂或无溶剂条件下进行。
当在溶剂中进行降解时，所述溶剂可以选自甲苯、苯、氯苯、溴苯、二氯苯、二溴苯、邻二氯苯、邻二溴苯、间二氯苯、间二溴苯、对二氯苯、对二溴苯甲苯、间二甲苯、对二甲苯、邻二甲苯、均三甲苯、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等中的一种 或几种。在一些优选实施方式中，所述溶剂为甲苯。在另一些优选实施方式中，所述溶剂为均三甲苯。
其中，所述温和催化法对式(2)环状聚合物初始浓度[M] 0不作特别的限制，只要能实现所述环状聚合物的制备即可。在一些实施方式中，式(2)环状聚合物的初始浓度[M] 0为1-50mol L -1，例如可以是2、4、6、8、10、12、14、16、18、20、22、24、26、28、30、32、34、36、38、40、42、44、46、48、50mol L -1。优选地，为2-40mol L -1；更优选地，为3-30mol L -1；更进一步优选地，为4-20mol L -1。在一些优选实施方式中，所述环状聚合物的初始浓度[M] 0为3-6mol L -1。在另一些优选实施方式中，所述杂环内酯的初始浓度[M] 0为4.0mol L -1。
其中，所述温和催化的条件为油浴或沙浴等热浴方法，所述的温度范围为40-90℃；优选地，为50-80℃，可以是50、55、60、65、70、75、80℃。在一些优选实施方式中，所述降解的温度为50℃。在一些优选实施方式中，所述降解的温度为60℃。在一些优选实施方式中，所述降解的温度为70℃。在一些优选实施方式中，所述降解的温度为80℃。
其中，所述温和催化的时间为1-45h，可以是1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45h。在一些优选实施方式中，所述降解的时间为3h。在一些优选实施方式中，所述降解的时间为6h。在一些优选实施方式中，所述降解的时间为9h。在一些优选实施方式中，所述降解的时间为12h。在一些优选实施方式中，所述降解的时间为15h。在一些优选实施方式中，所述降解的时间为18h。在一些优选实施方式中，所述降解的时间为21h。在一些优选实施方式中，所述降解的时间为24h。
本发明所述温和催化法适用的环状聚合物的物理化学特性没有特别的限定，只要是按照本发明上述方法或其他方法获得的环状聚合物均可以采用本发明的温和催化法回收单体。在一些优选实施方式中，本发明所述温和催化法适用于M n在300-2000kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述温和催化法适用于M n在400-1500kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述温和催化法适用于M n在500-800kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述温和催化法适用于M n在500-600kg mol -1范围的环状聚合物。在一些优选实施方式中，本发明所述温和催化法适用于本发明实施例1～17制备的环状聚合物。
可选地，所述温和催化在氮气氛围中进行。
可选地，所述温和催化在密封条件下进行。
可选地，所述温和催化在真空条件下进行。
本发明所述方法中，当催化聚合物PolyHL回收Poly单体时，反应过程选自如下反应式Ⅶ或反应式Ⅷ中任一种或两种：
Figure PCTCN2022134072-appb-000043
当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，本发明对以下实施例中使用的δ-L原料不加限制，可以是商购获得，或通过如下方法制备得到：CO 2和1,4-丁二烯在Pd催化条件下合成δ-L，δ-L在Stryker试剂催化和三乙氧基硅烷(HSi(OEt)3)作为氢源条件下合成δ-L，反应过程如下反应路线4所示。
Figure PCTCN2022134072-appb-000044
当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，本发明提供了一种二取代α,β-饱和六元环内酯，其结构如下式10所示：
Figure PCTCN2022134072-appb-000045
R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同。
所述卤素选自氟、氯、溴、碘。
所述烷基为线性烷基、支链烷基、环烷基；进一步地，所述烷基可以是C1-C20的烷基；也可以是C1-C10的烷基，包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，为乙基。
所述取代的烷基为取代的线性烷基、支链烷基、环烷基。
所述烯基为线性烷基、支链烷基、环烷基；进一步地，所述烯基可以是C2-C20的烯基；也可以是C2-C10的烯基，包括乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基；优选地，为乙烯基。
所述取代的烯基为取代的线性烯基、支链烯基、环烯基。
所述炔基为线性炔基、支链炔基、环炔基；进一步地，所述炔基可以是C2-C20的炔基；也可以是C2-C10的炔基，包括乙炔基、丙炔基、丁炔基、戊炔基、己炔基、庚炔基、辛炔基、壬炔基、癸炔基；优选地，为乙炔基。
所述取代的炔基为取代的线性炔基、支链炔基、环炔基。
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。进一步地，所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的 一个或多个：氢、杂原子、氨基、氰基、羟基、硝基、卤素、羧基、C1-C10烷基、烷氧基、胺基、环烷氧基、环胺基、C2-C12烯基、C2-C12炔基、C3-C12环烷基、苄基、烷基羰基、C2-C12烯基羰基、C3-C12环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、砜基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
优选地，R 1为C1-C20的烷基，R 2选自C2-C20的烯基；更进一步优选地，R 1为C1-C10的烷基(可以为C1、C2、C3、C4、C5、C6、C7、C8、C9、C10烷基)，R 2选自C1-C10的烯基(可以C2、C3、C4、C5、C6、C7、C8、C9、C10烯基)。进一步优选地，R 1为甲基，R 2为乙烯基。
当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，本发明还提供了如式10所示的二取代α,β-饱和六元环内酯的制备方法，所述方法以式9所示的二取代α,β-不饱和六元环内酯为原料，以Stryker试剂或者能够原位生成Stryker试剂的混合试剂为催化剂，有机硅烷为氢源，通过共轭烯烃的选择性还原反应制备得到式10所示的二取代α,β-饱和六元环内酯；所述选择性还原反应如反应式A所示，
R 1、R 2定义同上文式10中所述。
所述二取代α,β-饱和六元环内酯为具有双基团取代的六元环内酯。
在一些实施方式中，所述二取代α,β-饱和六元环内酯为非对映异构体混合物。
所述Stryker试剂的化学式为[(Ph 3P)CuH] 6。
所述能够原位生成Stryker试剂的混合试剂包括CuXp和膦配体；其中，p＝0，1，2，X指代卤原子、阴离子物种或配体化合物中的任一种；优选地，X指代卤原子如F，Cl，Br，I，或是阴离子物种如硫酸根、亚硫酸根、亚硫酸氢根、硝酸根、醋酸根等，亦或是配体化合物如乙酰丙酮负离子、双二亚苄基丙酮、三苯基膦、三乙基膦、三乙氧基膦、BINAP等。
所述有机硅烷为含有硅氢键的化合物；优选地，所述有机硅烷为SiH q(R 0) t，其中q和t为0～5以内的整数，且q+t＝4，R 0基团可代表卤原子如氟、氯、溴和碘，也可以指代不同的取代基如烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的一种或多种。其中，所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团。
所述卤素选自氟、氯、溴、碘。
所述烷基为线性烷基、支链烷基、环烷基；进一步地，所述烷基可以是C1-C20的烷 基；也可以是C1-C10的烷基，包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基；优选地，为乙基。
所述取代的烷基为取代的线性烷基、支链烷基、环烷基。
所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。进一步地，所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、羟基、硝基、卤素、羧基、C1-C10烷基、烷氧基、胺基、环烷氧基、环胺基、C2-C12烯基、C2-C12炔基、C3-C12环烷基、苄基、烷基羰基、C2-C12烯基羰基、C3-C12环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、砜基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
进一步优选地，R 0为C1-C20的烷基，更进一步优选地，R 0为C1-C10的烷基，可以为C1、C2、C3、C4、C5、C6、C7、C8、C9、C10烷基。
本发明所述二取代α,β-饱和六元环内酯的制备方法中，所述Stryker试剂可以由CuXp和膦配体原位生成；其中，p＝0，1，2，X指代卤原子如F，Cl，Br，I，或是阴离子物种如硫酸根、亚硫酸根、亚硫酸氢根、硝酸根、醋酸根等，亦或是配体化合物如乙酰丙酮负离子、双二亚苄基丙酮、三苯基膦、三乙基膦、三乙氧基膦、BINAP等。如式10所示的二取代α,β-饱和六元环内酯的制备方法如下反应式A-1所示：
Figure PCTCN2022134072-appb-000046
所述二取代α,β-不饱和六元环内酯、Stryker试剂、有机硅烷的质量比为(0.5-30):(0.05-5):(3-40)；优选地，为(2-15):(0.06-1):(6-20)，例如可以是(2-5):(0.06-1):(6-20)、(5-8):(0.06-1):(6-20)、(8-10):(0.06-1):(6-20)、(10-15):(0.06-1):(6-20)、(2-15):(0.08-0.1):(6-20)、(2-15):(0.1-0.3):(6-20)、(2-15):(0.3-0.5):(6-20)、(2-15):(0.5-0.8):(6-20)、(2-15):(0.8-1):(6-20)、(2- 15):(0.06-1):(6-8)、(2-15):(0.06-1):(8-10)、(2-15):(0.06-1):(10-12)、(2-15):(0.06-1):(12-15)、(2-15):(0.06-1):(15-20)；进一步优选地，为(3-10):(0.08-0.3):(8-15)；更进一步优选地，为5:0.11:11.9。
所述选择性还原反应的温度不作特别的限制，只要能实现所述二取代α,β-饱和六元环内酯的制备即可。在一些实施方式中，所述反应的温度为0～50℃，可以是0～10、10～20、20～30、30～40、40～50℃。优选地，为10～40℃。进一步优选地，为15～35℃，例如可以是15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35℃。更进一步优选地，为常温25±5℃。更进一步优选地，为25℃。
所述选择性还原反应的时间不作特别的限制，只要能实现所述二取代α,β-饱和六元环内酯的制备即可。在一些实施方式中，所述反应的时间为30s-160h；可以是30s-10min、10min-30min、30min-1h、1h-3h、3h-6h、6h-10h、10h-30h、30h-60h、60h-90h、90h-120h、120h-160h。优选地，所述反应时间为1h-10h。更优选地，为2-8h。更进一步优选地，为6h。
所述选择性还原反应的溶剂选自甲苯、二甲苯、二氯苯、均三甲苯、二氯甲烷、氯仿、四氢呋喃(THF)、TBD、苯、1,2-二氯乙烷、四氢吡咯、四氢吡喃、六氢吡啶、乙酸乙酯、乙醚、二甲醚、甲乙醚、正己烷、环己烷、环戊烷、乙腈、二氧六环、N,N-二甲基甲酰胺、二甲基亚砜等中的一种或几种。优选地，为甲苯。
作为优选，本发明制备二取代α,β-饱和六元环内酯的过程在搅拌条件下进行。
作为优选，本发明制备二取代α,β-饱和六元环内酯的过程具体包括，先将Stryker试剂和有机硅烷在溶剂中溶解，然后向混合物中逐滴滴加δ-L进行反应。
在一具体实施方式中，当反应式A中R 1为甲基，R 2为乙烯基时，如式6二取代α,β-饱和六元环内酯为δLH 2，其制备方法如下反应式A-2所示：
Figure PCTCN2022134072-appb-000047
在另一具体实施方式中，当反应式A中R 1为甲基，R 2为乙烯基时，如式6二取代α,β-饱和六元环内酯为δLH 2，其制备方法如下反应式A-3所示：
Figure PCTCN2022134072-appb-000048
须知，下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。此外应理解，本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤，除非另有说明。在进一步描述本发明具体实施方式之前，应理解，本发明的保护范围不局限于下述特定的具体实施方案；还应当理解，本发明实施例中使用的术语是为了描述特定的具体实施方案，而不是为了限制本发明的保护范围；在本发明说明书和权利要求书中，除非文中另外明确指出，单数形式“一个”、“一”和“这个”包括复数形式。
当实施例给出数值范围时，应理解，除非本发明另有说明，每个数值范围的两个端点以及两个端点之间任何一个数值均可选用。除非另外定义，本发明中使用的所有技术和科学术语与本技术领域技术人员通常理解的意义相同。除实施例中使用的具体方法、设备、材料外，根据本技术领域的技术人员对现有技术的掌握及本发明的记载，还可以使用与本发明实施例中所述的方法、设备、材料相似或等同的现有技术的任何方法、设备和材料来实现本发明。
本发明对以下实施例中使用的HL原料不加限制，可以是商购获得，或通过如下方法制备得到：CO 2和1,4-丁二烯在Pd催化条件下合成δ-L，δ-L和H2在Pd/C催化条件下合成六元内酯3,6-二乙基四氢-2h-吡喃-2-酮(HL)，反应过程如下反应路线2所示。
Figure PCTCN2022134072-appb-000049
以下实施例中，原料为HL，由HL和BnOH开环聚合制备化合物polyHL，反应式如下
Figure PCTCN2022134072-appb-000050
以下实施例中，原料为HL，由HL在有机碱的催化下开环聚合制备环状化合物polyHL，反应式如下
Figure PCTCN2022134072-appb-000051
聚合物数均分子量Mn和分子量分布
Figure PCTCN2022134072-appb-000052
测定方法：从反应体系中取出200μL反应液，将溶剂旋蒸除去，通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得产物的Mn(数均分子量)和
Figure PCTCN2022134072-appb-000053
(分子量分布)。
实施例1～2
实施例1 TBD、DBU催化HL的ROP反应
具体合成步骤包括：
为了使HL开环聚合(ring-opening polymerization,ROP)生成polyHL，本发明最初尝试了配合插入机制的催化剂，包括锡(II)2-乙基己酸酯[Sn(Oct) 2]和二月桂酸二丁基锡(DBTDL)等，但没有得到聚合物。本发明还使用了有机酸磷酸二苯(DPP)，也没有得到聚合物。然后有机碱如1、8-Diazabicyclo[5.4.0]undec-7-ene(DBU)和1,5,7-triazabicyclo[4.4.0]dec-5-ene(TBD)测试表明只有TBD/BnOH可以促进中等程度的单体转化，导致液体polyHL分子量较低(表1，run 9:M n＝6.0kg mol -1，
Figure PCTCN2022134072-appb-000054
表1，run 10:M n＝5.6kg mol -1，
Figure PCTCN2022134072-appb-000055
)。
Figure PCTCN2022134072-appb-000056
反应路线1线性polyHL的合成路径
表1.初始的HL的ROP尝试
Figure PCTCN2022134072-appb-000057
实施例1本体代表无溶剂条件；[M] 0(mol/L)为HL单体在体系中的初始浓度，指的是反应投料时单体在体系中的浓度。
实施例2
在氮气氛围的手套箱内，取0.0158mmol的TBD催化剂和0.0158mmol的BnOH加入至一个火焰干燥过的10mL Schlenk管中，之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的30℃油浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌96h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的polyHL样品。M n(数均分子量)和
Figure PCTCN2022134072-appb-000058
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例2
制备步骤如实施例1，不同的是，在氮气氛围的手套箱内，取0.0158mmol的TBD催化剂和0.0158mmol的BnOH加入至一个火焰干燥过的10mL Schlenk管中，需要再加入0.02mL的四氢呋喃THF将其溶解。其它条件参照表1。
实施例3～17研究三种磷腈与BnOH结合后在HL的ROP中的催化活性
当[HL]/[BnOH]＝50/1时，1mol％的 tBu-P 1或 tBu-P 2-25℃的THF溶液中([M] 0＝5.3M)，72h后， tBu-P 1催化下没有聚合物的生成72h后； tBu-P 2在进行为期五天的反应之后，单体转化率达到了41％。令人鼓舞的是， tBu-P 4大大促进了聚合物的生成，12h后转化率为87％，得到了M n＝19.9kg mol -1和略宽的分子量分布
Figure PCTCN2022134072-appb-000059
的PolyHL。 tBu-P 1、 tBu-P 2和 tBu-P 4在乙腈中的pKa分别为26.9、33.5和42.7，这可能是三种磷腈之间存在较大碱性差异导致的。接下来，逐渐降低 tBu-P 4的载量，从2mol％降低到0.2mol％，可以使聚合更加可控。特别是，当 tBu-P 4的载量降低到0.2mol％时，获得了M n＝9.2kg mol -1的polyHL，具有很低的分散度
Figure PCTCN2022134072-appb-000060
(表2，run 7)，表明了HL的活性开环聚合(living ROP)。然而，当体系的初始单体浓度在THF中逐渐稀释到2.0、1.6和1.3M时，HL的ROP变得不那么受控:转化率显著降低，M n随着分散性的扩大(表2，run 8-10)。将反应温度从-25℃提高到41℃也会导致聚合更加不可控。本发明还设计了[HL]/[BnOH]比例为25/1和100/1的两组实验，两个聚合条件均能达到最高单体转化率88％，并且所得聚合物的M n随[HL]/[BnOH]比值的增加而线性增加，聚合物的分散性始终维持较低。
表2.磷腈/BnOH催化的HL的ROP反应结果
Figure PCTCN2022134072-appb-000061
[M] 0是指HL单体在体系中初始浓度，指的是反应投料时单体在整个体系中的浓度。
实施例3
在氮气氛围的手套箱内，取0.0063mmol的 tBu-P 1催化剂和0.0126mmol的BnOH加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌72h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。
实施例4
在氮气氛围的手套箱内，取0.0063mmol的 tBu-P 2催化剂和0.0126mmol的BnOH加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌120h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为最终产物。M n(数均分子量)和
Figure PCTCN2022134072-appb-000062
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例5-9
制备步骤如实施例4，不同之处在于在0.0126～0.126mmol范围调整催化剂的摩尔浓度，其它条件参照表2。其中，实施例9获得的聚合物样品的表征参见实施例19。
实施例10-12
制备步骤如实施例9，不同之处在于将HL在体系中的初始摩尔浓度从5.3M逐渐降低至1.3M，其它条件参照表2。
实施例13-15
制备步骤如实施例9，不同之处在于将反应温度从-25℃分别升高至-9℃、28℃、41℃，其它条件参照表2。
实施例16-17
制备步骤如实施例9，不同之处在于将HL、 tBu-P 4、BnOH三者的投料比分别调整为25/0.1/1和100/0.2/1，其它条件参照表2。其中，实施例16获得的聚合物样品的表征参见实施例19。
实施例18：以1,3-丙二醇作为引发剂的聚酯二元醇的合成
Figure PCTCN2022134072-appb-000063
上式中，j和k为大于1的正整数，j和k可以相同或不同。
具体实施方法：在氮气氛围的手套箱内，取0.0063mmol的 tBu-P 4催化剂和0.042mmol的1,3-丙二醇加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌48h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为最终产物。图2为产物的MALDI-TOF表征图。
实施例19：以1,4-丁二醇作为引发剂的聚酯二元醇的合成
Figure PCTCN2022134072-appb-000064
上式中，t和r为大于1的正整数，t和r可以相同或不同。
具体实施方法：在氮气氛围的手套箱内，取0.0063mmol的 tBu-P 4催化剂和0.042mmol的1,4-丁二醇加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌48h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为最终产物。图3为产物的MALDI-TOF表征图。
实施例20对实施例9的开环聚合ROP反应特性研究
用于开环聚合反应特性研究的反应体系、反应条件、反应步骤等参见实施例9，仅改变反应时间，进行了多次平行聚合反应，来研究转化率随着时间的变化；在预定的反应时间后淬灭反应，以避免不断从同一个反应体系中取样测试引起转化率的系统误差。
图4a和4b中的数据来源于 1H NMR表征的转化率数据，图4c和4d中的数据来源于GPC分析。聚合动力学数据支持该条件下的聚合为是活性聚合：单体转化率随反应时间线性增长(图4a)。ln[M] 0/[M]的时间相关曲线展现出十分明确的一级动力学特征(图4b)。polyHL的M n与单体转化率呈线性相关，在链增长阶段，所得polyHL的分散度始终很低(
Figure PCTCN2022134072-appb-000065
～1.1)(图4c)。图4d给出的单峰分布的GPC曲线同样证实了这一结论。
实施例21对实施例9和16获得的聚合物分子进行表征
采用基质辅助激光解吸附电离飞行时间质谱仪(MALDI-TOF MS)对合成的聚酯(polyHL)链端基保真度进行了研究。polyHL的MS信号显示只有一组分子离子峰，与本发明所期望的由BnOH引发的线性polyHL的结构相符合(图5)。通过NMR光谱对tBu-P4/BnOH体系催化得到的polyHL的结构进行进一步表征，可以观察到1H NMR波谱中(图6)BnO -上的亚甲基上的质子信号(δ5.12ppm)和与羟基端基相连的次甲基上的质子信号(δ3.49ppm)，并在 13C NMR谱图中也能观察到相应的信号(图7)。
MALDI-TOF实验过程：所选样品为实施例9中纯化后的聚合物样品。实验通过一台Bruker Autoflex Speed MALDI-TOF质谱分析仪进行测试，测试模式为正离子、反射模式。首 先在不锈钢靶板上面滴加一滴1％的NaI溶液，之后将1μL的基质和聚合物样品的混合液滴上去(DHB是基质，DHB为2,5-二羟基苯甲酸的缩写，基质浓度为20mg mL -1，溶剂为THF)。MALDI-TOF对仪器分子量的外部校正通过在靶板上的样品孔位旁边另外加一个多肽校正标准样品来进行校正。原始数据的处理是在FlexAnalysis软件中进行，采集到的原始数据被用于上述谱图5的绘制，绘制均由Origin Pro 2019b进行。
图6和图7核磁测试所用样品为实施例16所得，由于BnOH引发的聚合物属于同一物质(化学结构完全相同)，分子量的差异对于核磁谱图中的化学位移和特征峰无影响，只有聚合物端基的积分面积大小的差异，因此在此以实施例中优选条件得到的聚合物的特征谱图作为代表进行说明。
以 tBu-P 4和1,4-苯二甲醇(1,4-BDM)为催化剂，在[HL]/[ tBu-P 4]/[1,4-BDM]＝15/0.15/1的条件下，合成了具有良好的链端保真度的遥爪聚合物polyHL(双羟基封端的polyHL)。MALDI-TOF MS信号显示M n＝n×156.1+161.1的一组信号峰，与预期的二醇封端的端基结构相匹配(图8)。
实施例22以1,4-苯二甲醇作为线性polyHL二元醇样品的制备方法
Figure PCTCN2022134072-appb-000066
上式中，p和q为大于1的正整数，p和q可以相同或不同。
在氮气氛围的手套箱内，取0.0063mmol的 tBu-P 4催化剂和0.042mmol的1,4-BDM加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌48h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为最终产物。
实施例23 polyHL物理性能测定
本发明通过热重分析(TGA)和差示扫描量热(DSC)分析了实施例17 tBu-P 4/BnOH体系制备的polyHL的热稳定性。
线性polyHL表现出优秀的热稳定性：其TGA和DTG曲线显示，其T d,5％＝326.0℃,T max＝335.3℃(图9)；线性polyHL样品的第二次加热扫描曲线(5℃ min -1)的DSC曲线显示出其玻璃化转变温度(Tg)为-30.6℃，并且没有观察到结晶峰(图10)。结果表明，polyHL是一种具有良好热稳定性的非晶态聚合物材料。
实施例24 PolyHL在溶剂中的化学可回收性测定
热力学实验样品制备：所用的PolyHL样品实验条件均参照实施例9，不同之处在于将反应温度改变为-26℃、-16℃、-9℃、28℃和41℃，并且相应地改变反应时间来获取不同时间下的转化率信息。图11显示不同温度条件下，HL单体浓度随着时间的变化曲线图。图12显示HL的Van’t Hoff分析曲线。
本发明通过不同温度(-25、-16、-9、28、41℃)下，进一步考察 tBu-P 4/BnOH催化HL的ROP反应，从而计算其聚合热力学参数(图11和12)。根据Dainton方程，计算得到THF在[HL] 0＝1.0mol L -1时的焓变(ΔH o p)和熵变(ΔS o p)分别为-13.12kJ mol -1和-49.09J mol -1K -1，进一步得到T c为-6℃。与其它单取代和无取代的六元环内酯相比，该T c明显更低。因此，在δ-VL的α-和δ-位置引入取代基是一种能够提高单体的化学可回收能力的有效策略。
实施例25 PolyHL在溶剂中的化学可回收性测定
化学回收实验步骤：在氮气氛围的手套箱内，取200mg的polyHL样品(实施例9)和5mol％的氯化锌于10mL Schlenk管中，再加入2.6mL的邻二氯苯(o-DCB)将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的160℃油浴中加热搅拌12h之后，除去体系中的溶剂，并且取出10mg降解后的液体产物用于 1H NMR分析HL产率。
回收结果如图13所示，由图可知，HL的回收率可达到100％，说明采用ZnCl 2作为催化剂进行催化反应，对化学回收线性polyHL是有效的。
实施例26 PolyHL通过热解(thermolysis)方法在无溶剂条件下的化学可回收性测定
在氮气氛围的手套箱内，取200mg的polyHL样品(实施例9)于10mL Schlenk管 中，并且将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的220℃沙浴中加热搅拌3h，并且同时用旋片式真空泵不断抽真空。3h之后，体系内的生成无色的油状液体，取出10mg该液体用于 1H NMR分析HL产率。
回收结果如图14所示，HL的回收率可达到100％，说明在无溶剂条件下，通过热解的方法，可以对PolyHL进行有效回收。
实施例27～32：tBu-P4催化的HL开环聚合
本发明选用三种常用的磷腈碱： tBu-P 1、 tBu-P 2、 tBu-P 4作为催化剂，控制[HL]/[磷腈碱]摩尔比＝50/1，在四氢呋喃(THF)中，于-25℃下反应12h，结果如表1所示。其中，tBu-P1和tBu-P2在反应了12h后均未生成聚合物(实施例27、实施例28)，但令人惊讶的是，tBu-P4在12h后最大转化率达到88％(表1)，并获得了超高分子量Mn＝613.8kg mol-1和中等分子量分布
Figure PCTCN2022134072-appb-000067
的polyHL样品(实施例29)。并且本发明发现，改变tBu-P4的在体系中的浓度，对Mn和由此生成的polyHL的分子量M n和分子量分布
Figure PCTCN2022134072-appb-000068
仅有很小的影响(实施例30-32)。
为了测定 tBu-P 4单独催化HL的ROP的可控性，在-25℃的THF溶液中([HL]/[ tBu-P 4]摩尔比＝50/1，[M] 0＝4.0M)进行了动力学实验(图17和表4)。ln[M] 0/[M]随时间的变化曲线显示，初始转化率在4h内达到63％，之后聚合速率趋于放缓，在接下来的6-8h内转化率达到84％(图17a)。ln[M] 0/[M]的时间相关曲线展现出十分明确的一级动力学特征(图17b)。有趣的是，polyHL的M n与单体转化率呈明显的线性相关，但在单体转化率达到50％后分散度明显变宽(图17c)。随着反应时间的增加，GPC曲线也逐渐呈现双峰分布，可能是由于在高单体转化率下发生了严重的酯交换反应(图17d)。这些数据表明，如果在反应前4小时内淬灭反应，就可以以相对可控的ROP方式来生产高分子量聚合物。
表3.磷腈碱催化剂对HL单体开环聚合的实验结果
Figure PCTCN2022134072-appb-000069
表4.磷腈碱催化开环聚合的动力学实验数据
Figure PCTCN2022134072-appb-000070
实施例27
在氮气氛围的手套箱内，取0.0126mmol的 tBu-P 1催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.025mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌12h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。测定结果如表3所示。
实施例28
制备步骤如实施例27，不同的是，将催化剂替换为等当量的 tBu-P 2。
实施例29
制备步骤如实施例27，不同的是，将催化剂替换为等当量的 tBu-P 4。具体步骤包括：
在氮气氛围的手套箱内，取0.0126mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.025mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温 度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌12h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。
为了提纯出polyHL产物，将淬灭后的反应液逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，将最后一次得到的沉淀物，放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的polyHL样品。同时测定产物的M n(数均分子量)和
Figure PCTCN2022134072-appb-000071
(分子量分布)。
实施例30～32
制备步骤如实施例29，不同的是，将催化剂当量从2mol％调整为1mol％(实施例30)、0.67mol％(实施例31，其中HL/催化剂为150/1)、0.5mol％(实施例32)，详见表3。
实施例33～43：tBu-P4催化HL的开环聚合动力学研究
实施例33的聚合物制备方法
在氮气氛围的手套箱内，取0.0126mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.058mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌11min之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。同时测定产物的M n(数均分子量)和
Figure PCTCN2022134072-appb-000072
(分子量分布)。
实施例34-43的聚合物制备方法
制备步骤如实施例33，不同的是，将搅拌反应的时间从11min调整为约0.267h(即16min)(实施例34)、0.5h(实施例35)、1h(实施例36)、2h(实施例37)、2.5h(实施例38)、3h(实施例39)、4h(实施例40)、7h(实施例41)、10h(实施例42)、12h(实施例43)。
实施例44HL严格去除残留水时，合成的环状聚合物的MALDI-TOF谱图特征
(1.1)测定样品制备
在氮气氛围的手套箱内，取0.0126mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.058mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温 度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌3-5min之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应。淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为待测样品。
(1.2)MALDI-TOF谱图表征
将本实施例步骤(1.1)制备的待测样品放入真空干燥箱中干燥至恒重，取出少量进行MALDI-TOF测定，测定结果如图18所示，结果只显示一组可归属到环状polyHL质量峰的信号。
(1.3) 1H和 13C NMR谱图表征
测定实施例29制备的环状聚合物样品的 1H和 13C NMR谱图，结果可以看出，谱图中未观察到链末端信号，进一步支持该聚合物结构为环状结构(图19、图20)。
实施例45 HL未严格去除残留水时，合成的环状聚合物的MALDI-TOF谱图特征
(1.1)测定样品制备
制备方法同实施例44中的(1.1)，不同之处在于，所用HL单体未经过严格除水，经Karl Fischer水分仪检测，该HL单体的水含量约为100ppm。
(1.2)MALDI-TOF谱图表征
将待测样品放入真空干燥箱中干燥至恒重，取出少量进行MALDI-TOF测定，测定结果如图21所示。由图可以看出，只有在没有严格去除HL单体中或制备体系中的残留水的情况下，才有可能检测到水引发的线性质量峰。
实施例46  tBu-P 4单独催化HL的ROP从而形成环状polyHL产物的可能链引发机制
通过 1H NMR谱图检测，催化剂 tBu-P 4从HL中提取酸性H的能力得到了验证。将HL和 tBu-P 4分别以1/1、2/1、4/1、8/1的摩尔比例在室温下混合，并通过相应的 1H和 31P NMR光谱对其反应进行监测。
结果如图22-24所示，由图可知，[ tBu-P 4H] +的特征信号为： 1H NMR中，δ7.92-8.07ppm；31P NMR中，δ分别为12.48ppm和-23.64ppm；然而，随着HL/ tBu-P 4比值的增加，[ tBu-P 4H]+信号强度仅略有所增强。 tBu-P 4的特征信号为：1H NMR中，δ1.72,2.70和2.72ppm；31P NMRδ4.96和-25.31ppm。这些数据清楚地表明， tBu-P 4只能将很小一部分的HL单体进行脱质子化反应，这可能可以解释 tBu-P 4浓度与本发明所述制备体系合成的环状polyHL的M n之间缺乏直接相关性的原因(见上文所述)。
(1)不同比例下的HL和 tBu-P 4混合实验( 31P NMR谱图)
图22实验方法：在氮气氛围的手套箱中，称取如图22中当量的 tBu-P 4催化剂，并且加入0.6mL的干燥氘代甲苯将其溶解。再向该溶液中加入确定当量的HL单体，稍加搅拌后将溶液转移至一根火焰干燥过的J-Young核磁管，并且即刻进行核磁共振谱图表征，结果如图22所示。
(2)不同比例下的HL和 tBu-P 4混合实验( 1H NMR谱图)
图23-24实验方法：在氮气氛围的手套箱中，称取如图23-24中当量的 tBu-P 4催化剂，并且加入0.6mL的干燥氘代甲苯将其溶解。再向该溶液中加入确定当量的HL单体，搅拌如图中所示的时间后，将溶液转移如一根火焰干燥过的J-Young核磁管，并且即刻进行核磁共振谱图表征，结果如图23-24所示。
实施例47  tBu-P 4从BnOH、HL和H 2O中攫取质子的吉布斯自由能差异
本发明通过量子力学计算，以评估 tBu-P 4从HL单体中攫取质子从而生成环状高分子的吉布斯自由能，与 tBu-P 4从BnOH和水分子中攫取质子的吉布斯自由能的差异大小，从而通过计算来验证经由脱质子生成环状polyHL过程的可行性。反应过程及自由能数据如图25所示。脱质子反应的吉布斯自由能顺序为BnOH(3.9kcal mol-1)<HL(5.7kcal mol-1)<H 2O(9.3kcal mol -1)，说明BnO -是最容易产生引发活性种的引发剂，而HL产生引发活性种的能量仅仅比BnOH高出了1.8kcal mol -1，说明HL在 tBu-P 4催化下通过脱质子机理能够生成环状polyHL。
实施例48环状polyHL的物理性能
(1)测定样品制备
在氮气氛围的手套箱内，取0.063mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.058mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌30min之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应。为了提纯出polyHL产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的polyHL样品。同时测定产物的M n(数均分子量)和
Figure PCTCN2022134072-appb-000073
(分子量分布)，结 果为M n＝21.7kg/mol，
Figure PCTCN2022134072-appb-000074
(2)通过热重分析(TGA)、微商热重法(DTG)和差示扫描量热(DSC)分析 tBu-P 4体系制备的环状polyHL的热稳定性
结果如图26-27所示。由图26可知，环状polyHL表现出了优秀的热稳定性(Td,5％>325℃)。该产物的TGA和DTG曲线显示，其T d,5％＝332.3℃，Tmax＝367.3℃；由图27可知，环状polyHL样品的第二次加热扫描曲线(5℃ min -1)的DSC曲线显示出其玻璃化转变温度(T g)为-29.7℃，并且没有观察到结晶峰。
结果表明，polyHL是一种具有良好热稳定性的非晶态聚合物材料。
实施例49不同分子量的polyHL聚合物剥离性能测定
(1)环状聚合物样品制备
tBu-P 4单独催化下的HL的开环聚合可以得到很高分子量的polyHL，这一点为获得具有潜在应用价值的压敏胶粘剂提供了一条十分有前景的途径。本实施例采用简单的180°剥离实验测定不同分子量的polyHL的剥离强度，制备过程分别如下：
polyHL_160(分子量M n分别为160)环状聚合物样品制备：在氮气氛围的手套箱内，取0.025mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.025mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将1.26mmol的HL快速注入Schlenk管中，并且搅拌60min之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应。
为了提纯出polyHL产物，将淬灭后的反应液逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为polyHL。重复上述提纯步骤3-5次，将最后一次得到的沉淀物，放入真空干燥箱中干燥至恒重，所得即为polyHL_160样品，其GPC原始数据见图56所示，同时测定polyHL_160的M n和
Figure PCTCN2022134072-appb-000075
。
polyHL_319(分子量M n分别为319)环状聚合物样品制备：制备步骤如实施例polyHL_160，不同的是，将催化剂当量改为0.013mmol，反应时间改为4h，得到polyHL_319样品，其GPC原始数据见图57所示，同时测定polyHL_319的M n和
Figure PCTCN2022134072-appb-000076
。
polyHL_562(分子量M n分别为562)环状聚合物样品制备：制备步骤如实施例polyHL_160，不同的是，将催化剂当量改为0.0063mmol，反应时间改为6h，得到polyHL_562样品，其GPC原始数据见图57所示，同时测定polyHL_562的M n和
Figure PCTCN2022134072-appb-000077
。
(2)聚合物剥离性能测定
以载玻片作为硬质基板，以A4纸(15×2.6cm)作为表面基材(图28a)，并且用涂层刀片将polyHL样品均匀地涂在载玻片上(以3M 665、3M810、3M1600为对照)。横断面扫描电镜(SEM)显示薄膜厚度均匀，为36.9±1.2μm(图28b)。实验在25℃条件下，在Instron5966万用力学测试仪上进行，剥离角为180°，剥离速度为10mm min -1。令我们高兴的是，polyHL_319,562和160(数字是指polyHL的分子量M n分别为319、562和160kg mol -1的样品)的粘附力分别为3.8±0.12，3.5±0.20和1.5±0.65N cm -1(图28c和表5)。在相同测定条件下，polyHL_319和polyHL_562的剥离强度高于
Figure PCTCN2022134072-appb-000078
商业化透明胶带(
Figure PCTCN2022134072-appb-000079
为2.4±0.40N cm -1；
Figure PCTCN2022134072-appb-000080
为1.9±0.31N cm -1)和乙烯基电气胶带(
Figure PCTCN2022134072-appb-000081
为0.8±0.17N cm - 1)。PolyHL_160的剥离强度为1.5±0.65N cm -1，与
Figure PCTCN2022134072-appb-000082
商业化透明胶胶带
Figure PCTCN2022134072-appb-000083
相当。
(3)透光率、柔性和粘弹性测定
为了显示polyHL的透光率和颜色，高MW聚合物样品(M n＝613.8kg mol -1
Figure PCTCN2022134072-appb-000084
实施例29)通过溶液浇铸法在PTFE模具上形成透明、无色聚合物薄膜，且该薄膜具有良好的柔性和粘弹性(图28d)。
表5.环状polyHL样品和三种商品化胶带的180°剥离性能测定数据(相同样品重复测定三次)
Figure PCTCN2022134072-appb-000085
实施例50-64：环状polyHL聚合物在高温条件下的化学回收实验
采用实施例30制备的polyHL样品，测定其化学可回收性，其M n在500-600kg mol - 1范围内，为571.5kg mol -1。
首先，使用几种三氟甲磺酸金属盐，包括AgCF3SO3、Cu(CF3SO3)2、Fe(CF3SO3)3、Sc(CF3SO3)3和Y(CF3SO3)3，在封闭的反应管中催化polyHL(甲苯溶液，HL的初始浓度[M] 0＝0.5M)中在120℃下解聚24h(实施例50-54)。然而，只有Fe(CF3SO3)3和Sc(CF3SO3)3能回收得到HL单体，回收率分别为53％和27％(实施例52、53)。
然后在实施例50的基础上，改变催化剂，溶剂和反应温度，进行回收实验，实验条件具体见表6。结果表明，只有FeCl2能回收得到HL单体，回收率为21％(实施例55)；Sn(Oct)2回收率仅为5％；而Fe(acac)2、DBTDL和 tBu-P 4即使在150°高温下加热12小时也没有明显的反应活性(实施例55-59)。
接着，分别在130℃、140℃和150℃下以ZnCl 2为催化剂，在甲苯中反应12h，观察到随着温度的升高，单体回收率逐渐增加(实施例60-62；31％、39％和54％)。有趣的是，当在150℃和160℃使用更高极性的溶剂邻二氯苯时，单体回收率分别显著提高到91％和100％(实施例63-64)，实现了ZnCl 2催化剂的100％化学回收过程。
表6.环状polyHL样品的化学回收实验
Figure PCTCN2022134072-appb-000086
实施例50
在氮气氛围的手套箱内，取200mg的环状polyHL样品(实施例40制备)和5mol％的AgCF 3SO 3于25mL Schlenk管中，再加入2.6mL甲苯将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的120℃油浴中加热搅拌24h之后，除去体系中的溶剂，并且取出10mg降解后的产物用于 1H NMR分析HL产率。
实施例51-54
实验条件参照实施例50，不同的是，将AgCF 3SO 3替换为Cu(CF 3SO 3) 2(实施例51)、Fe(CF 3SO 3) 3(实施例52)、Sc(CF 3SO 3) 3(实施例53)、Y(CF 3SO 3) 3(实施例54)。
实施例55-59
实验条件参照实施例50，不同的是，改变了催化剂种类，并且将反应温度升高至150℃、反应时间缩短至12h、将溶剂替换为均三甲苯。催化剂种类分别为：FeCl 2(实施例55)、Fe(acac) 2(实施例56)、Sn(Oct) 2(实施例57)、DBTDL(实施例58)、 tBu-P 4(实施例59)。
实施例60
在氮气氛围的手套箱内，取200mg的环状polyHL样品(实施例40制备)和5mol％的ZnCl 2于25mL Schlenk管中，再加入2.6mL甲苯将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的130℃油浴中加热搅拌12h之后，除去体系中的溶剂，并且取出10mg降解后的产物用于 1H NMR分析HL产率。
实施例61-62
实验条件参照实施例60，不同的是，升高反应温度至140℃(实施例61)、150℃(实施例62)。
实施例63-64
实验条件参照实施例60，不同的是，改变了反应温度和溶剂；150℃、邻二氯苯(实施例63)，160℃、邻二氯苯(实施例64)。
实施例65-73：环状polyHL聚合物在温和条件下的化学回收实验
为了进一步降低化学循环过程中的能量输入，本发明还对IMes、DBU、TBD和La(La[N(SiMe 3) 2] 3)的催化活性进行了测定。在50℃下，(甲苯作溶剂，[HL] 0＝0.5M)，只有La[N(SiMe 3) 2] 3展现出很好的HL回收率：3h达到47％，12h达到了81％，并在24小时达到了88％(实施例65-67)。
当将上述体系中的[HL] 0稀释至0.1M后，并没有观察到回收率的显著提高(实施例68-69)。为了实现HL单体的完全回收，本发明在[HL] 0＝0.5M的甲苯溶液中将反应温度升高到80℃，此时HL单体的回收率在3h内达到85％，在12h内保持不变(实施例70-71)，这表明解聚过程比50℃更加快速。然后在80℃下将体系稀释到0.1M，3h内HL单体回收率达到93％(实施例72)，最终在12h内回收率达到100％(实施例73)。结果见表7。
表7.环状polyHL的温和条件降解实验
Figure PCTCN2022134072-appb-000087
实施例65
在氮气氛围的手套箱内，取200mg的环状polyHL样品(实施例40制备)和3mol％的La[N(SiMe 3) 2] 3于25mL Schlenk管中，再加入2.6mL甲苯将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的50℃油浴中加热搅拌3h之后，除去体系中的溶剂，并且取出10mg降解后的产物用于 1H NMR分析HL产率。
实施例66-69
实验条件参照实施例65，不同的是，改变反应溶剂的加入量和/或反应时间：2.6mL甲苯、12h(实施例66)；2.6mL甲苯、24h(实施例67)；12.8mL甲苯、3h(实施例68)；12.8mL甲苯、24h(实施例69)。
实施例70
在氮气氛围的手套箱内，取200mg的环状polyHL样品(实施例40制备)和3mol％的La[N(SiMe 3) 2] 3于25mL Schlenk管中，再加入2.6mL甲苯将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的80℃油浴中加热搅拌3h之后，除去体系中的溶剂，并且取出10mg降解后的产物用于 1H NMR分析HL产率。
实施例71-73
实验条件参照实施例70，不同的是，改变了反应溶剂的加入量和/或反应时间：2.6mL甲苯、12h(实施例71)；12.8mL甲苯、3h(实施例72)；12.8mL甲苯、12h(实施例73)。
为了制备得到目标单体δLH 2，本发明以δ-L为原料，通过使用Stryker试剂([(Ph 3P)CuH] 6)作为催化剂，三乙氧基硅烷(His(OEt) 3)作为氢源，在常温条件下，在甲苯溶液中搅拌6h，首次成功实现了δLH 2单体的制备。
实施例74：δLH 2单体的制备
在氮气氛围的手套箱内，取109.7mg(0.17mol％)Stryker试剂和11.9g(2.2equiv)的三乙氧基硅烷于一个茄形烧瓶中，并且加入250ml甲苯将其溶解，室温下搅拌0.5h。接下来，取约5.0g的δ-L并且逐滴加入至上述烧瓶中，滴加完毕后继续在室温下反应6h。反应结束后，将烧瓶取出手套箱，向其中加入大量的饱和碳酸氢钠溶液淬灭反应，并且通过氯仿和碳酸氢钠溶液萃取三次，将有机层合并后通过无水硫酸钠干燥，过滤后旋蒸除去溶剂，得到粗产物。粗产物再通过色谱柱层析进行分离(石油醚/乙酸乙酯＝8/1)，所得纯品为无色油状液体。其核磁共振谱氢谱图和核磁共振碳谱图如图60～61所示。本发明制备δLH 2单体的产率达到了83％，所得产物的非对映异构体比例为55/45，该产物性状为无色的油状液体。
Figure PCTCN2022134072-appb-000088
实施例75～81： tBu-P 4催化的δLH 2开环聚合
本发明使用 tBu-P 4磷腈催化剂作为δLH 2阴离子开环聚合的催化剂尝试聚合反应。在[δLH 2]/[ tBu-P 4]摩尔比＝500/1的投料比之下，在-25℃的THF溶液中搅拌反应24h([δLH 2] 0＝5.82M)，δLH 2的转化率为84％，所得聚合物poly(δLH 2)具有高分子量M n＝246.0kg mol -1和较宽的分子量分布
Figure PCTCN2022134072-appb-000089
( 实施例75)。若是使用苯甲醇(BnOH)作为外加的醇引发剂，以[δLH 2]/[BnOH]摩尔比＝50/1的投料比进行聚合反应。当磷腈催化剂的加入当量不断减少时(从2、1、0.4至0.2mol％)，所得聚合物的分子量和分子量分布都有减小的趋势，即分子量趋近投料比计算的分子量( 实施例76～79)。同样地，若将苯甲醇引发剂更换成为二苯甲醇，也会观察到相似的分子量及分子量分布趋势( 实施例80～81，其中实施例81制备的poly(δLH 2)的核磁氢谱图如图62所示)。
实施例75
在氮气氛围的手套箱内，取0.00134mmol的 tBu-P 4催化剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.016mL的THF将催化剂溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.67mmol的δLH 2快速注入Schlenk管中，并且搅拌24h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出poly(δLH 2)产物，淬灭后的反应液被逐滴滴加至20mL 冰甲醇中，离心后舍弃上清液，沉淀物即为poly(δLH 2)。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的poly(δLH 2)样品。M n(数均分子量)和
Figure PCTCN2022134072-appb-000090
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例76
在氮气氛围的手套箱内，取0.0134mmol的 tBu-P 4催化剂以及0.0134mmol的BnOH引发剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.016mL的THF将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.67mmol的δLH 2快速注入Schlenk管中，并且搅拌12h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出poly(δLH 2)产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为poly(δLH 2)。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的poly(δLH 2)样品。M n(数均分子量)和
Figure PCTCN2022134072-appb-000091
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例77～79
制备步骤如实施例76，不同的是，将 tBu-P 4催化剂的当量进行改变：实施例77(0.0067mmol)、实施例78(0.00268mmol)、实施例79(0.00134mmol)。
实施例80
制备步骤参照实施例76，不同的是，将实施例76中的BnOH引发剂替换为二苯甲醇(Ph 2CHOH)引发剂。
实施例81
制备步骤参照实施例79，不同的是，将实施例79中的BnOH引发剂替换为二苯甲醇(Ph 2CHOH)引发剂。
受到初步开环聚合结果的鼓舞，本发明接下来研究了使用几种碱金属醇盐作为ROP引发剂的可行性。起初，在THF溶液中，本发明使用KOMe(甲醇钾)和BnOH作为共引发剂，以[δLH 2]/[KOMe]/[BnOH]摩尔比＝50/0.5/1进行投料，实现了86％的δLH 2转化率。制得的poly(δLH 2)的分子量为M n＝73.4kg mol -1，分子量分布为
Figure PCTCN2022134072-appb-000092
( 实施例82)。本发明推断这种不太可控的聚合行为可能是BnOH加入后的KOMe和BnOK的竞争性双重引发 造成的( 图63)。随后，仅仅使用KOMe作为引发剂，测试了在[δLH 2]/[KOMe]＝50/1的投料比下，在-25℃下的THF中反应24h。该反应转化率可以达到94％，所得poly(δLH 2)具有非常高的分子量M n＝442.8kg mol -1和相当窄的分子量分布
Figure PCTCN2022134072-appb-000093
( 实施例83)。
实施例82～85：甲醇作为引发剂引发的δLH 2开环聚合
实施例82
在氮气氛围的手套箱内，取0.0067mmol的KOMe引发剂和0.0134mmol的BnOH引发剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的THF进行溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.67mmol的δLH 2快速注入Schlenk管中，并且搅拌24h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出poly(δLH 2)产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为poly(δLH 2)。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的poly(δLH 2)样品。M n(数均分子量)和
Figure PCTCN2022134072-appb-000094
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例83
在氮气氛围的手套箱内，取0.0134mmol的KOMe引发剂加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的THF进行溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃低温浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.67mmol的δLH 2快速注入Schlenk管中，并且搅拌24h之后，向体系中加入1mL 5％的HCl-甲醇溶液淬灭反应，并且取出50μL反应液用于 1H NMR分析单体转化率。为了提纯出poly(δLH 2)产物，淬灭后的反应液被逐滴滴加至20mL冰甲醇中，离心后舍弃上清液，沉淀物即为poly(δLH 2)。重复上述提纯步骤3-5次，最后一次得到沉淀物后，将其放入真空干燥箱中干燥至恒重，所得即为该条件下纯化后的poly(δLH 2)样品。M n(数均分子量)和
Figure PCTCN2022134072-appb-000095
(分子量分布)通过GPC方法，在40℃条件下，在四氢呋喃流动相中依据PMMA标准样品校正后测得。
实施例84
制备步骤参照实施例83，不同的是将KOMe引发剂的当量降低至0.0067mmol。
实施例85
制备步骤参照实施例83，不同的是将反应时间延长至48h，以及将KOMe引发剂的当量降低至0.00335mmol。
表8.不同体系催化δLH 2的开环聚合结果
Figure PCTCN2022134072-appb-000096
接下来，在相同的聚合条件下，本发明筛选了另外几种常见的碱金属醇盐，包括NaOMe、KO tBu、NaO tBu和LiO tBu( 图64)。如表8和表9所示，由KOMe和NaOMe引发制得的poly(δLH 2)具有很高的分子量和理想的可控性( 实施例83和图65～67，M n＝442.8kg mol -1，
Figure PCTCN2022134072-appb-000097
实施例86，M n＝534.6kg mol -1，
Figure PCTCN2022134072-appb-000098
)。至于KO tBu和NaO tBu，GPC曲线能够清楚地检测到双峰分布，大概是由于该体系中存在快速和不可控的酯交换反应( 实施例87～88)。由LiO tBu引发而制得的poly(δLH 2)表现出显着降低的分子量和窄的分子量分布，但同时单体转化率也随之降低，这表明LiO tBu是一种反应性低但可控性好的引发剂( 实施例89)。此外，在-25℃的THF中，随着KOMe的投料当量分别从2mol％降低到1.0mol％和0.5mol％，所得聚合物的M n略有增加，而分子量分布却仍然很窄( 图68， 实施 例83～85)。使用0.5mol％的KOMe( 实施例85， M n＝587.7kg mol -1，
Figure PCTCN2022134072-appb-000099
)生成具有很高分子量和很低分子量分布的poly(δLH 2)。
实施例86～89：不同碱金属醇盐引发剂参与的δLH 2开环聚合
制备步骤参考实施例83，不同的是将KOMe进行更换：实施例86(甲醇钠，NaOMe)、实施例87(叔丁醇钾，KO tBu)、实施例88(叔丁醇钠，NaO tBu)、实施例89(叔丁醇锂，LiO tBu)。
表9不同引发剂体系引发δLH 2的开环聚合结果
Figure PCTCN2022134072-appb-000100
Figure PCTCN2022134072-appb-000101
实施例90:热力学性能
不同条件下制备的poly(δLH 2)的热力学稳定性可以通过热重分析仪(TGA)和差示扫描量热仪(DSC)进行分析。
首先，采用 tBu-P 4为催化剂，BnOH为引发剂(实施例79)，和不加入催化剂，只加入引发剂KOMe(实施例 82～84)制备得到的poly(δLH 2)都具有良好的热稳定性(5％热失重温度都大于300℃)。TGA曲线揭示了不同样品的T d,5％和T max与样品的分子量有关。其T max都处于370～376℃之间( 图69～72，分别对应实施例79，82，83，84)，然而实施例79采用 tBu-P 4 tBu-P 4为催化剂，BnOH为引发剂制备的样品T d,5％比仅采用引发剂KOMe(实施例 82～84)制备的样品低20～30℃，造成这种差异的主要原因可能是这两种体系制备得到的聚合物存在较大的分子量差异造成的。
DSC曲线表明，实施例79和84制备得到的poly(δLH 2)的T g分别是-30.5和-27.0℃( 图 73～74，分别对应实施例6，11)，样品在10℃/min下的第二次升温和第一次降温曲线都仅仅只有玻璃化转变温度(T g)而无结晶和熔融吸热峰，说明这种poly(δLH 2)材料是无定型态的聚合物。
应用例1:poly(δLH 2)样品的外观和光透过性
为了验证poly(δLH 2)样品的外观和光透过性，本发明将实施例85制得的样品通过热压法制备得到了条形的材料，该材料是一种柔性且具有良好延展性的无色透明材料( 图75)。
应用例2:化学回收
接下来，本发明研究了poly(δLH 2)样品的化学可回收能力( 实施例91)。测试样品选取的是 实施例81中制备所得的poly(δLH 2)(M n＝11.7kg mol -1,
Figure PCTCN2022134072-appb-000102
)。在甲苯中，加入测试样品5mol％的La[N(SiMe 3) 2] 3作为催化剂，控制单体的初始浓度[δLH 2] 0＝0.18M，在120℃下加热2h，该聚合物样品可以完全被降解成为δLH 2单体。
实施例91：化学回收实验
在氮气氛围的手套箱内，取200mg的poly(δLH 2)样品(实施例81制得)和5mol％的La[N(SiMe 3) 2] 3于50mL Schlenk管中，再加入7.2mL甲苯将其溶解。之后将Schlenk管用橡 胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的120℃油浴中加热搅拌2h之后，除去体系中的溶剂，并且取出10mg降解后的产物用于 1H NMR分析δLH 2产率，见 图76。
应用例3:聚合后修饰
由于poly(δLH 2)的侧链存在大量的烯烃官能团，因此本发明可以通过聚合后修饰来对聚合物的性质进行调控，而光引发的硫醇-烯烃间的点击化学反应就是一个很好的聚合后修饰方法。本发明将poly(δLH 2)样品、对三氟甲基苯硫酚、安息香二甲醚配成溶液，之后将其涂成一张均匀薄膜，并且用254和365nm波长的紫外光对薄膜照射12h( 实施例92)。通过核磁，大约有87％的烯烃官能团发生了反应，并且GPC曲线也观测到了聚合物样品明显的分子量增长( 图77)。除此之外，核磁氢谱信号可以观察到poly(δLH 2-SAr)样品中烯烃信号的明显衰减，以及苯基和硫醚键特征信号的产生( 图78)。
实施例92：光引发的硫醇-烯烃点击化学反应
在空气中，取100mg的poly(δLH 2)样品(按实施例81制得)、5.0当量的对三氟甲基苯硫酚和10mol％的安息香二甲醚于10mL的样品瓶中，再加入0.5mL二氯甲烷将其溶解。搅拌约15min后，将该溶液浇铸到一个圆形的PTFE模具上面，待溶剂挥发后将形成的薄膜置于254和365nm波长的紫外光照下，照射过夜。待照射足够长时间后，用少量二氯甲烷将薄膜溶解，用正己烷多次重沉淀并干燥，所得产物即为聚合后修饰后的poly(δLH 2-SAr)。
有趣的是，本发明在进行光引发的硫醇-烯烃点击化学反应时，发现薄膜在365nm波长的紫外光照下会产生非常明显的蓝色荧光。于是，本发明利用光致发光光谱进一步表征了合成的poly(δLH 2-SAr)的光学性质。在波长为360nm的紫外光激发下，在约410nm处检测到一个光致发光峰( 图79)，而与此形成鲜明对比的是，poly(δLH 2)样品并没有这种发光。 图 80所示的图案印刻实验证明了这种光学改性的便捷性。本发明用一个中间镂空“CO 2”图案的掩板盖在光响应的薄膜上面(该薄膜包含poly(δLH 2)、对三氟甲基苯硫酚、安息香二甲醚)，并将其进行紫外光照过夜。经过光照后，在光响应薄膜上面出现了一个“CO 2”荧光的图案，而被掩板遮盖住的区域却是不发光的( 图81)。这证明了该荧光的产生归因于成功的硫醇-烯烃点击化学反应。
同样地，这种后修饰也是一种可以轻松改变聚合物亲疏水性质的手段。经过测试，超纯水与玻璃基板的接触角为55.7°( 图82)，而poly(δLH 2)与超纯水的接触角为72.8±0.08°( 图83)。然而，含有氟原子的poly(δLH 2-SAr)与超纯水的接触角更是达到了93.0±0.99°( 图84)。也许正是由于三氟甲基基团被接枝到了聚合物侧链上导致了后修饰的poly(δLH 2-SAr)具有明显更加疏水的材料性质。
实施例93：HL单体通过一锅两步法合成聚氨酯
在氮气氛围的手套箱内，取0.0063mmol的tBu-P4催化剂和0.042mmol的1,4-BDM加入至一个火焰干燥过的10mL Schlenk管中，再加入0.02mL的四氢呋喃将其溶解。之后将Schlenk管用橡胶塞密封，缠上封口膜后拿出手套箱，置于事先设置好的-25℃冰浴中直至温度达到平衡。当温度达到平衡后，使用一个注射器将0.63mmol的HL快速注入Schlenk管中，并且搅拌12h之后，向体系中加入0.0063mmol的磷酸二苯酯溶液淬灭，并将体系转移到50℃下平衡，待温度达到后保持5min。用注射器快速向体系内加入23.39mg 4,4’-亚甲基双(异氰酸苯酯),并迅速放回-25℃冰浴中继续反应24h。反应结束后用5mL四氢呋喃稀释反应体系，并逐滴加入事先降温至0℃的大量甲醇中，在10000rpm的转速下离心5min并舍去上清液保留固体，重复3次，最后取保留底部固体，在60℃下真空干燥12h，得到以HL作为单体的聚氨酯样品。进一步HL单体通过一锅两步法合成聚氨酯的NMR和GPC数据如图85、图86所示。
综上所述，本发明二氧化碳基聚酯高分子聚合物的制备方法，能够以廉价大宗材料为原料，有效利用二氧化碳，缓解温室效应，所述聚酯高分子聚合物为化学可回收高分子，具有优异的物理化学特性。本发明方法利用廉价易得的二氧化碳、1,3-丁二烯合成一种饱和内酯和(HL)一种双取代内酯(δLH 2)，并通过阴离子开环聚合的方法首次合成了全新的二氧化碳基可回收聚合物材料(CO 2基可回收聚酯材料)。得到材料polyHL力学性能较好，具有无色，透明的特点，可以用作压敏胶黏剂；得到材料poly(δLH 2)也有一定的物理性能，且具有化学可调性质，有开发多种应用场景的潜质。两种高分子都可在一定条件下被化学回收回到单体，可以建立闭环的循环材料经济。该方法既避免了白色污染对于环境的破坏，又为二氧化碳的重整与再利用提供了全新的解决方案，同时满足了新聚合物碳中和生产和循环材料经济的迫切需求。
所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (26)

  1. 聚酯高分子化合物，其特征在于，所述聚酯高分子化合物包含如下式4所示的重复单元：
    Figure PCTCN2022134072-appb-100001
    R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同，且必须同时存在；
    X选自杂原子；
    n为大于等于1的正整数。
  2. 如权利要求1所述的聚酯高分子化合物，其特征在于，所述烷基、烯基、炔基、单环芳香基、多环芳香基、多杂环芳香基上的取代基为单取代或多取代，分别独立选自下列基团中的一个或多个：氢、杂原子、氨基、氰基、苄基、烷基羰基、烯基羰基、环烷基羰基、苯基羰基、苄基羰基、烷氧羰基、酯基、亚砜基、烯基、炔基、环烷基、砜基、羟基、硝基、卤素、羧基、烷基、烷氧基、胺基、环烷氧基、环胺基、亚磺酰胺基、磺酰胺基、吗啉基、哌嗪基。
  3. 如权利要求1所述的聚酯高分子化合物，其特征在于，所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)，所述二氧化碳基聚酯poly(δLH 2)包含如下式6所示的重复单元：
    Figure PCTCN2022134072-appb-100002
    其中，n为大于等于1的正整数。
  4. 如权利要求1-3任一所述的聚酯高分子化合物，其特征在于，所述聚酯高分子化合物包 括线性、环状、星形拓扑结构。
  5. 如权利要求4所述的聚酯高分子化合物，其特征在于，所述聚酯高分子化合物结构为线性结构时，其结构如式2所示：
    Figure PCTCN2022134072-appb-100003
    R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个。
  6. 如权利要求5所述的聚酯高分子化合物，其特征在于，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述二氧化碳基聚酯poly(δLH 2)结构如式7所示：
    Figure PCTCN2022134072-appb-100004
    其中，R 14选自C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
    n为大于等于1的正整数；
    m为大于等于1的正整数。
  7. 如权利要求4所述的聚酯高分子化合物，其特征在于，所述聚酯高分子化合物结构为环状结构时，其结构如式3所示：
    Figure PCTCN2022134072-appb-100005
  8. 如权利要求1～7任一项所述的聚酯高分子化合物在制备聚氨酯、聚合物薄膜、压敏胶黏剂、胶带、热塑性弹性体中的一种或几种的应用。
  9. 一种聚酯高分子化合物产品，其特征在于，其由如权利要求1～7任一项所述的聚酯高分子化合物制备获得；优选地，所述聚酯高分子化合物产品为聚氨酯、聚合物薄膜、压敏胶黏剂或胶带。
  10. 一种聚酯高分子化合物的合成方法，其特征在于，选自以下方法中任一种或两种：
    A)当所述聚酯高分子化合物结构为线性结构时，所述方法包括：式1所示的杂环内酯，在有机碱为催化剂，能够提供活性质子的试剂R(OH) m为引发剂的条件下，合成得到式2所示的聚酯高分子化合物；反应过程如反应式I所示：
    Figure PCTCN2022134072-appb-100006
    B)当所述聚酯高分子化合物结构为环性结构时，所述方法包括：式1所示的杂环内酯，在有机碱催化下，合成得到式3所示的聚酯高分子化合物；反应过程如反应式Ⅱ所示：
    Figure PCTCN2022134072-appb-100007
    在A)和/或B)中，R 1、R 2分别独立地选自氢、卤素、烷基、取代的烷基(线性烷基、支链烷基、环烷基)、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基包括苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同，且必须同时存在；
    X选自杂原子；
    n为大于等于1的正整数；
    所述有机碱包括磷腈、含有胍基基团的化合物、含脒基基团的化合物；
    在B)中，R选自烷基、取代的烷基、烯基、取代的烯基、炔基、取代的炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
    m为大于等于1的正整数。
  11. 如权利要求10所述的合成方法，其特征在于，在A)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述方法包括：式8所示的δLH 2，在有机碱作为催化剂，提供活性质子的试剂R 14(OH)m和/或(MO) mR 14作为引发剂的条件下，合成得到式7所示的二氧化碳基聚酯poly(δLH 2)；反应过程如反应式Ⅲ所示：
    Figure PCTCN2022134072-appb-100008
    Figure PCTCN2022134072-appb-100009
    其中，R 14选自C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基、分子量在100000g/mol及以下的含有聚乙烯醇、聚乙二醇重复单元结构的高分子基团中的任意一个；
    M为K，Na，Li，Rb或Cs；
    n为大于等于1的正整数；
    m为大于等于1的正整数；
    所述有机碱选自磷腈、含有胍基基团的化合物、含脒基基团的化合物中的一种或几种。
  12. 如权利要求10或11任一所述的合成方法，其特征在于，所述磷腈为含有(R 2N) 2-P＝N结构的强Lewis碱；优选地，所述磷腈结构如式5所示：
    Figure PCTCN2022134072-appb-100010
    式5中，R 3-R 10分别独立地选自C1-C10烷基；y为大于等于1的正整数。
  13. 如权利要求10或11任一所述的合成方法，其特征在于，所述磷腈选自 tBu-P 1、 tBu-P 2、 tBu-P 4，结构分别以下所示：
    Figure PCTCN2022134072-appb-100011
  14. 如权利要求10所述的合成方法，其特征在于，所述方法包括如下特征1)～11)之任一项或几项：
    1)所述R 1为C1-C10的烷基；
    2)所述R 2选自C1-C10的烷基；
    3)所述X为O、S、N或P；
    4)在A)中，所述1≤m≤10；
    5)在A)中，所述式1、有机碱、引发剂的摩尔用量比值为(5-200):(0.01-5):1；
    6)在B)中，所述式1、有机碱的摩尔比为(10-500):(0.01-5)；
    7)所述反应在无溶剂条件下或溶剂条件下进行；
    当所述方法在溶剂条件下进行时，所述反应的溶剂选自四氢呋喃THF、苯、甲苯、二甲苯、二氯苯、均三甲苯、二氯甲烷、氯仿、1,2-二氯乙烷、四氢吡咯、四氢吡喃、六氢吡啶、乙酸乙酯、乙醚、二甲醚、甲乙醚、正己烷、环己烷、环戊烷、乙腈、二氧六环、N,N-二甲基甲酰胺、二甲基亚砜中的一种或几种；
    8)在A)中，所述反应温度为-100～200℃；
    9)在A)中，所述反应时间为10s-360h
    10)在B)中，所述反应温度为-120～220℃；
    11)在B)中，所述反应时间为5s-400h。
  15. 如权利要求10所述的合成方法，其特征在于，所述方法包括如下特征i)～ⅹ)之任一项或几项：
    i)所述R 1为乙基，R 2为乙基，即式1为HL；
    ii)所述磷腈为 tBu-P 4；
    iii)在A)中，所述引发剂为醇类；优选地，所述引发剂为醇盐；更优选地，所述引发剂为苯甲醇(BnOH)、1,4-苯二甲醇(1,4-BDM)、1,3-丙二醇、1,4-丁二醇、甲醇钾(KOMe)、甲醇钠(NaOMe)、叔丁醇钾(KO tBu)、叔丁醇钠(NaO tBu)、叔丁醇锂(LiO tBu)中的一种或几种；
    iv)在A)中，所述式1、有机碱、引发剂的摩尔用量比值为(25-100):(0.1-1):1；
    v)在B)中，所述式1、有机碱的摩尔比为(20-400):(0.1-4)；
    vi)所述反应溶剂为THF；
    vii)在A)中，所述反应温度为-80～200℃；
    ⅷ)在A)中，所述反应时间为1min-120h；
    ⅸ)在B)中，所述反应温度为-80～160℃；
    ⅹ)在B)中，所述反应时间为5min-80h。
  16. 如权利要求11所述的合成方法，其特征在于，所述方法包括如下特征a1)～a2)之任一项或几项：
    a1)所述引发剂为苯甲醇(BnOH)、甲醇钾(KOMe)、甲醇钠(NaOMe)、叔丁醇钾(KO tBu)、叔 丁醇钠(NaO tBu)、叔丁醇锂(LiO tBu)中的一种或几种；
    a2)所述式1、有机碱、引发剂的摩尔用量比值为(5-200):(0-5):(0-1)，且有机碱、引发剂的用量均不为0；优选地，所述式1、有机碱、引发剂的摩尔用量比值为(25-200):(0-1):(0-1)；且有机碱、引发剂的用量均不为0。
  17. 一种聚酯高分子化合物，其特征在于，所述聚酯高分子化合物由如权利要求10～16之任一项所述的方法合成得到。
  18. 有机碱在催化式1所示的杂环内酯合成式2和/或式3所示的聚酯高分子化合物中的用途，其特征在于，所述有机碱包括磷腈、含有胍基基团的化合物、含脒基基团的化合物；其中，式1所示的杂环内酯、式2和/或式3所示的聚酯高分子化合物结构分别如下：
    Figure PCTCN2022134072-appb-100012
  19. 如权利要求18所述的用途，其特征在于，有机碱在催化式8所示的δLH 2合成式7所示的二氧化碳基聚酯poly(δLH 2)中的用途，式8所示的δLH 2、式7所示的二氧化碳基聚酯 poly(δLH 2)结构分别如下：
    Figure PCTCN2022134072-appb-100013
  20. 如权利要求19或20任一所述的用途，其特征在于，所述有机碱为磷腈，所述磷腈的结构如下式5所示：
    Figure PCTCN2022134072-appb-100014
    式5中，R 3-R 10分别独立地选自C1-C10烷基；
    y为1，2或3。
  21. 一种催化式2和/或式3所示的聚酯高分子化合物回收杂环单体的方法，其特征在于，所述方法选自以下任一种或两种：
    a)如催化式2所示的方法包括催化法和热解法；
    Figure PCTCN2022134072-appb-100015
    b)如催化式3所示的方法包括无机盐热解催化法和La[N(SiMe 3) 2] 3温和催化法；
    Figure PCTCN2022134072-appb-100016
    a)中，所述催化法包括：采用无机盐、金属有机化合物、有机化合物催化剂中的至少一种化合物降解所述式2聚酯高分子化合物，回收得到式1所示的杂环单体或其寡聚物或其衍生物；
    所述热解法包括：对所述式2聚酯高分子化合物进行加热裂解，回收得到式1所示的杂环单体或其寡聚物或其衍生物；
    b)中，所述无机盐热解催化法包括：采用无机盐催化降解如式3所示的聚酯高分子化合物，得到式1所示的杂环化合物或其寡聚物或式1相应的衍生物；
    所述La[N(SiMe 3) 2] 3温和催化法包括：在温和条件下对式3所示的聚酯高分子化合物采用La[N(SiMe 3) 2] 3进行催化裂解，得到式1所示的杂环化合物或其寡聚物亦或是式1相应的衍生物。
  22. 如权利要求21所述的方法，其特征在于，在a)中，当所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，
    所述催化法包括：采用无机盐、金属有机化合物或有机化合物催化剂中的至少一种化合物降解所述式8所示的二氧化碳基聚酯poly(δLH 2)，回收得到式7所示的δLH 2或其寡聚物或其衍生物；
    所述热解法包括：对所述式8所示的二氧化碳基聚酯poly(δLH 2)进行加热裂解，回收得到式7所示的δLH 2或其寡聚物或其衍生物。
  23. 一种二取代α,β-饱和六元环内酯的制备方法，其特征在于，在所述聚酯高分子化合物为二氧化碳基聚酯poly(δLH 2)时，所述方法以式9所示的二取代α,β-不饱和六元环内酯为原料，以Stryker试剂或者能够原位生成Stryker试剂的混合试剂为催化剂，有机硅烷为氢源，通过共轭烯烃的选择性还原反应制备得到式10所示的二取代α,β-饱和六元环内酯；所述选 择性还原反应如反应式A所示：
    Figure PCTCN2022134072-appb-100017
    其中，R 1、R 2分别独立地选自氢、卤素、C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同。
  24. 如权利要求23所述的二取代α,β-饱和六元环内酯的制备方法，其特征在于，所述方法包括如下至少任一项：
    b1)所述Stryker试剂为[(Ph 3P)CuH] 6；
    b2)所述能够原位生成Stryker试剂的混合试剂包括CuXp和膦配体；其中，p＝0，1，2，X指代卤原子、阴离子物种或配体化合物中的任一种；
    b3)所述有机硅烷为含有硅氢键的化合物；优选地，所述有机硅烷为SiHq(R 0)t，其中q和t为0～5以内的整数，且q+t＝4，R 0基团代表卤原子、C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的一种或多种；
    b4)所述二取代α,β-不饱和六元环内酯、Stryker试剂、有机硅烷的质量比为(0.5-30):(0.05-5):(3-40)；
    b5)所述选择性还原反应的温度为0～50℃；
    b6)所述选择性还原反应的时间为30s-160h；
    b7)所述选择性还原反应的溶剂选自甲苯、二甲苯、二氯苯、均三甲苯、二氯甲烷、氯仿、四氢呋喃(THF)、TBD、苯、1,2-二氯乙烷、四氢吡咯、四氢吡喃、六氢吡啶、乙酸乙酯、乙醚、二甲醚、甲乙醚、正己烷、环己烷、环戊烷、乙腈、二氧六环、N,N-二甲基甲酰胺、二甲基亚砜中的一种或几种。
  25. 如权利要求23所述的二取代α,β-饱和六元环内酯的制备方法，其特征在于，所述方法包 括如下至少任一项：
    c1)所述有机硅烷为三乙氧基硅烷；
    c2)所述二取代α,β-饱和六元环内酯、Stryker试剂、有机硅烷的质量比为(2-15):(0.06-1):(6-20)；
    c3)所述选择性还原反应的温度为10～40℃；
    c4)所述选择性还原反应的时间为1h-10h；
    c5)所述选择性还原反应的溶剂为甲苯。
  26. 一种二取代α,β-饱和六元环内酯，其特征在于，其结构如式10所示：
    Figure PCTCN2022134072-appb-100018
    R 1、R 2分别独立地选自氢、卤素、C1-C20烷基、取代的C1-C20烷基、C2-C20烯基、取代的C2-C20烯基、C2-C20炔基、取代的C2-C20炔基、单环芳香基、取代的单环芳香基、多环芳香基、取代的多环芳香基、多杂环芳香基、取代的多杂环芳香基中的任意一个；所述单环芳香基选自苯基，氮杂芳香基、疏杂芳香基、氧杂芳香基；所述多环芳香基和多杂环芳香基是指包含两个及两个以上的单环芳香基的基团；R 1、R 2可相同或不同。
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