Polyester high molecular compound, its preparation method and application

Abstract

The application belongs to the technical field of polymer synthesis, and relates to a polyester macromolecular compound and a synthesis method thereof. The method uses a heterocyclic lactone of formula 1 as raw material, uses an organic base as a catalyst, and performs ring-opening polymerization under the condition of an initiator to obtain the polyester macromolecular compound. The application first realizes the preparation of the polyester macromolecular compound. The raw material heterocyclic lactone used in the method has a simple preparation method, is widely sourced, the catalyst used has a simple preparation method, is low in cost and good in activity, and the application can effectively alleviate the harm caused by the greenhouse effect. The application also discloses application of the polyester macromolecular compound. The polyester macromolecular compound has good physical and chemical properties and recyclability, and has a wide application prospect.

Description

[0001] The present application claims priority to the patent application with the application number of 2021114161422 and the title of "Polyester macromolecular compound and its preparation method and application" filed on November 25, 2021. TECHNICAL FIELD

[0002] The present application belongs to the technical field of polymer synthesis, and relates to a polyester macromolecular compound and its preparation method and application, in particular to a chemical recyclable macromolecule based on CO2, H2 and 1,3-butadiene and its preparation method and application. BACKGROUND

[0003] Synthetic macromolecules, mainly carbon-based solid macromolecular materials, have a global annual output of hundreds of millions of tons. Using carbon dioxide CO2 as the main raw material to synthesize commercial solid macromolecular materials has great prospects for CO2 emission reduction. Currently, the commercial CO2-based macromolecular materials synthesized by using CO2 on the market are mainly polycarbonates and polyols, but the use amount of CO2 is not large, which cannot meet the demand for CO2 emission reduction. Therefore, it is still a major challenge in the field of CO2 energy saving and emission reduction to develop new types of CO2-based macromolecular materials that can be produced on a large scale.

[0004] To realize large-scale research and production of CO2-based macromolecules, at least the following requirements should be met, for example: in order to meet the economic requirements of large-scale production, the raw material copolymerized with CO2 should be a cheap bulk chemical raw material; the obtained polymer should be easily processed into the desired properties and have commercial performance indicators; in order to solve the increasingly serious problem of plastic pollution, the new type of polymer must be degradable. Unfortunately, there is currently no report of a CO2-based macromolecular material that can simultaneously meet the above multiple requirements and can fix a large amount of CO2 in it for a long time.

[0005] High molecular weight polymers containing heteroatoms in the backbone, especially polyester materials, are one of the ideal materials for polymer recycling approaches due to the nature of the ester bond in the backbone that can be easily broken. Therefore, the preparation of novel polyester high molecular weight materials from CO2 and cheap bulk chemical feedstocks, especially using ethylene and butadiene which are abundant and can be derived from biomass as raw materials, has been an important challenge that has not been solved in the field for decades. Although solid-state polyolefin materials containing ester groups derived from CO2 and 1,3-butadiene have been proven to be obtained by a multi-step process, due to their lack of processability, commerciality and recyclability, their potential for large-scale use is limited. The prior art reports that CO2 and 1,4-butadiene are synthesized into diethyl-substituted six-membered lactone, i.e. 3,6-diethyltetrahydro-2h-pyran-2-one (HL), but di-substituted lactone represented by HL is considered to be one of the non-polymerizable monomers. Therefore, it is urgent to develop a polymer material that can be synthesized from CO2 and cheap bulk chemical feedstocks, and has the properties of degradability, recyclability and applicability. SUMMARY

[0006] In view of the above-mentioned disadvantages of the prior art, the present application first proposes a polyester high molecular weight compound and a synthesis method thereof, which is prepared by ring-opening polymerization (ROP) of a heterocyclic lactone to obtain the polyester high molecular weight compound, such as polyHL prepared by ring-opening polymerization (ROP) of diethyl-substituted six-membered lactone derived from CO2, H2 and 1,3-butadiene, i.e. 3,6-diethyltetrahydro-2h-pyran-2-one (HL). The present application also proposes a polyester high molecular weight compound obtained by the method, and the use of the polyester high molecular weight compound.

[0007] To achieve the above-mentioned objects and other related objects, the present application provides a polyester high molecular weight compound, which comprises a repeating unit as shown in the following formula 4:

[0008]

[0009] R1, R2 are independently selected from any one of hydrogen, halogen, alkyl, substituted alkyl (linear alkyl, branched alkyl, cyclic alkyl), alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic group, substituted monocyclic aromatic group, polycyclic aromatic group, substituted polycyclic aromatic group, polyheterocyclic aromatic group, substituted polyheterocyclic aromatic group; the monocyclic aromatic group includes phenyl, nitrogen heteroaromatic group, heteroaromatic group, oxygen heteroaromatic group; the polycyclic aromatic group and polyheterocyclic aromatic group refer to a group containing two or more monocyclic aromatic groups; R1 and R2 can be the same or different;

[0010] The substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, benzyl, alkyl carbonyl, alkenyl carbonyl, cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, alkenyl, alkynyl, cycloalkyl, sulfone, hydroxyl, nitro, halogen, carboxyl, alkyl, alkoxy, amino, cycloalkoxy, cycloamino, sulfinamide, sulfonamide, morpholino, and piperazine.

[0011] X is selected from heteroatoms.

[0012] The number of repeating units shown in Equation 4 is n, where n is a positive integer greater than or equal to 1.

[0013] In a preferred embodiment, the polyester polymer compound has the structure shown in Formula 2:

[0014]

[0015]

[0016] R1, R2, X, n, and m are defined as described in compound 4 above.

[0017] R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, substituted polyheterocyclic aromatic, or a polymeric group containing a repeating unit structure of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less.

[0018] The polyester polymer compounds described in this invention include linear, cyclic, star-shaped and other topological structures.

[0019] Another aspect of the present invention is to provide the use of the polyester compound in the preparation of polyurethane or pressure-sensitive adhesives.

[0020] Another aspect of the present invention provides a method for synthesizing a polyester polymer compound, the method comprising: a heterocyclic lactone as shown in Formula 1, in the presence of an organic base as a catalyst and a reagent R(OH) capable of providing an active proton. m Under the condition of using an initiator, the polyester polymer compound shown in Formula 2 was synthesized; the reaction process is shown in Reaction Formula I:

[0021]

[0022] In reaction formula (I), R1 and R2 are independently selected from any one of hydrogen, halogen, alkyl, substituted alkyl (linear alkyl, branched alkyl, cycloalkyl), alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, and substituted polyheterocyclic aromatic; the monocyclic aromatic includes phenyl, azirroaromatic, thioaromatic, and oxaaromatic; the polycyclic aromatic and polyheterocyclic aromatic refer to groups containing two or more monocyclic aromatic groups; R1 and R2 may be the same or different;

[0023] The substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, benzyl, alkyl carbonyl, alkenyl carbonyl, cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, alkenyl, alkynyl, cycloalkyl, sulfone, hydroxyl, nitro, halogen, carboxyl, alkyl, alkoxy, amino, cycloalkoxy, cycloamino, sulfinamide, sulfonamide, morpholino, and piperazine.

[0024] R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, substituted polyheterocyclic aromatic, and polymeric groups containing polyvinyl alcohol or polyethylene glycol repeating unit structures with a molecular weight of 100,000 g / mol or less.

[0025] X is selected from heteroatoms;

[0026] n is a positive integer greater than or equal to 1;

[0027] m is a positive integer greater than or equal to 1;

[0028] The organic base includes phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups.

[0029] The phosphazene is a strong Lewis base containing a (R₂N)₂-P=N structure; preferably, the phosphazene structure is as shown in Formula 3:

[0030]

[0031] In Equation 3, R3-R 10 Each alkyl group is independently selected from C1-C10 alkyl groups; y is a positive integer greater than or equal to 1.

[0032] Preferably, the phosphazene is selected from... t Bu-P1、 t Bu-P2, tThe structures of Bu-P4 are shown below:

[0033]

[0034] Another aspect of the present invention is to provide a polyester polymer compound, which is synthesized by the method described above.

[0035] Another aspect of the present invention is to provide the use of an organic base in catalyzing the synthesis of a polyester polymer compound of formula 2 from a compound of formula 1 as described above, said organic base including phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups.

[0036] Preferably, the organic base is a phosphazene, and the structure of the phosphazene is shown in Formula 3 below:

[0037]

[0038] In Equation 3, R3-R 10 Each is independently selected from C1-C10 alkyl groups;

[0039] y is 1, 2, or 3.

[0040] Another aspect of the present invention is a method for catalytically recovering heterocyclic monomers from a polyester polymer compound of Formula 2 as described above, the method comprising: a catalytic method and a pyrolysis method;

[0041] The catalytic method includes: using inorganic salts, organometallic compounds, or organic compound catalysts to degrade the polyester polymer compound of Formula 2, and recovering the heterocyclic monomer or its oligomer or its derivative shown in Formula 1.

[0042] The pyrolysis method includes: heating and cracking the polyester polymer compound of Formula 2 to recover the heterocyclic monomer or its oligomer or its derivative shown in Formula 1.

[0043] As described above, the carbon dioxide-based polyester polymer compound, its preparation method, and its application of the present invention have the following beneficial effects:

[0044] This invention provides a method for preparing carbon dioxide-based polyester polymers. The method uses a heterocyclic monomer of Formula 1 as a raw material, an organic base as a catalyst, and a reagent providing active protons, such as R(OH)m, as an initiator. A ring-opening polymerization reaction is carried out under conditions such as -100 to 200°C, resulting in a one-step polyester polymer with controllable molecular weight. This method is simple, uses readily available raw materials (derived from inexpensive carbon dioxide gas), effectively mitigating the greenhouse effect. By adjusting the ratio of raw materials, reaction temperature, and reaction time, the molecular weight of the polyester polymer can be controlled. This invention's method yields polymers with good physicochemical properties (such as mechanical properties) and recyclability through ring-opening polymerization, increasing their application potential. Attached Figure Description

[0045] Figure 1 show t Possible chain initiation mechanisms in the ring-opening polymerization of HL catalyzed by Bu-P4 / BnOH (equivalent experimental methods) 1 (HNMR spectrum). a. Phosphazene t Bu-P4; b.BnOH; c.[ t Bu-P4] / [BnOH]=1 / 1.

[0046] Figure 2 The MALDI-TOF characterization diagram of the product of Example 18 is shown.

[0047] Figure 3 The MALDI-TOF characterization diagram of the product of Example 19 is shown.

[0048] Figure 4 Example 20 is shown by t Analysis of the living polymerization of HL-ROP catalyzed by Bu-P4 / BnOH. a. HL conversion rate versus time curve; b. ln([M] / [M]0); c. Molecular weight and molecular weight distribution of polyHL as a function of HL monomer conversion rate; d. GPC curve overlay of polyHL obtained at different polymerization times.

[0049] Figure 5 The MALDI-TOF characterization of the linear polyHL polymer of Example 21 confirms that it is a BnOH-terminated product.

[0050] Figure 6 The linear polyHL polymer shown in Example 21 1 H NMR characterization.

[0051] Figure 7 The linear polyHL polymer shown in Example 21 13 C NMR characterization.

[0052] Figure 8 MALDI-TOF characterization of the linear polyHL diol prepared by using 1,4-BDM as an initiator in Example 21 is shown.

[0053] Figure 9 The TGA and DTG curves of the linear polyHL in Example 23 are shown.

[0054] Figure 10 The DSC curve of the linear polyHL in Example 23 is shown.

[0055] Figure 11This shows the curves of HL monomer concentration changing over time under different temperature conditions in Example 24.

[0056] Figure 12 The Van't Hoff analysis curve of HL in Example 24 is shown.

[0057] Figure 13 This demonstrates the linear polyHL chemical recovery shown in Example 25. 1 1H NMR spectrum. Bottom: NMR spectrum of linear polyHL (synthesis conditions: [HL] / [ t BuP4] / [BnOH] = 50 / 0.1 / 1; Reaction temperature: -25℃; Solvent: THF, M n = 9.2 kgmol -1 (D=1.08); Middle: Spectrum of the colorless oily product after chemical recovery and solvent removal; Top: Clean starting monomer HL for ROP.

[0058] Figure 14 This image shows the results of recovering polymer monomers by pyrolysis in Example 26. Detailed Implementation

[0059] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0060] This invention overcomes the technical bottlenecks of existing technologies and reports for the first time a chemically recyclable polymer and its synthesis method. The polymer can be monohydroxy-terminated or dihydroxy-terminated, and its molecular weight can be controlled according to the degree of polymerization. The carbon dioxide content can be 28 wt%. The method of this invention can achieve the living polymerization of heterocyclic lactones such as the hexa-membered lactone 3,6-diethyltetrahydro-2h-pyran-2-one (HL). When the starting material is HL, it can be prepared using carbon dioxide and inexpensive bulk chemicals as starting materials, as shown in reaction route 1, using a palladium-catalyzed two-step method to synthesize HL from CO2, H2, and 1,3-butadiene; the HL is then reacted with an organic base (such as...) t Bu-P4-catalyzed anionic ring-opening polymerization (AROP) yields polyester polymers. This invention also develops a series of catalytic methods for the chemical degradation of polyester polymers such as polyHL, thereby recovering heterocyclic lactone monomers such as HL monomers.

[0061]

[0062] Reaction Route 1: Linear Synthetic Pathway of PolyHL

[0063] This invention provides a polyester polymer compound comprising repeating units as shown in Formula 4:

[0064]

[0065] R1 and R2 can be the same or different, and the two groups R1 and R2 must coexist on the six-membered heterocycle, with the substitution sites being any two of the four methylene carbons.

[0066] R1 and R2 are each independently selected from any one of hydrogen, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, and substituted polyheterocyclic aromatic; the monocyclic aromatic is selected from phenyl, azirroaromatic, thioaromatic, and oxaaromatic; the polycyclic aromatic and polyheterocyclic aromatics refer to groups containing two or more monocyclic aromatics.

[0067] The halogen is selected from fluorine, chlorine, bromine, and iodine.

[0068] The alkyl group is a linear alkyl group, a branched alkyl group, or a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; or it can be a C1-C10 alkyl group, including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, it is ethyl.

[0069] The substituted alkyl group is a substituted linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0070] The substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, benzyl, alkyl carbonyl, alkenyl carbonyl, cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, alkenyl, alkynyl, cycloalkyl, sulfone, hydroxyl, nitro, halogen, carboxyl, alkyl, alkoxy, amino, cycloalkoxy, cycloamino, sulfinamide, sulfonamide, morpholino, and piperazine. Furthermore, the substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amino, cycloalkoxy, cycloamino, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkyl carbonyl, C2-C12 alkenyl carbonyl, C3-C12 cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, sulfone, sulfinamide, sulfonamide, morpholinyl, and piperazine.

[0071] Preferably, R1 is a C1-C20 alkyl group, and R2 is selected from C1-C20 alkyl groups; more preferably, R1 is a C1-C10 alkyl group, and R2 is selected from C1-C10 alkyl groups, and R1 and R2 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 alkyl groups, respectively. Even more preferably, R1 and R2 are both ethyl groups.

[0072] X is selected from heteroatoms, including heteroatoms such as O, S, N, and P; preferably, X is O.

[0073] 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.

[0074] The polyester polymer compounds include linear, cyclic, and star-shaped topologies.

[0075] Preferably, the structure of the polyester polymer compound is shown in Formula 2:

[0076]

[0077] R1, R2, X, n, and m are defined as described in compound 4 above.

[0078] R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, substituted polyheterocyclic aromatic, or a polymeric group containing a repeating unit structure of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less.

[0079] Preferably, R can represent an aromatic group, including phenyl, naphthyl, anthracene, phenanthryl, pyrene, benzo[a]pyrene and its derivatives; specifically, R can be selected from phenyl, benzyl, 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, tribenzyl 1,2,3-triethylphenyl, 1,2,4-triethylphenyl, 1,2,3,4-tetraethylphenyl, 1,2,3,5-tetraethylphenyl, 1,2,4,5-tetraethylphenyl, pentaethylphenyl, hexaethylphenyl, phenylpropyl, mesitylene-n-propylphenyl, 1,2,3,4-diethylphenyl, m-diethylphenyl, p-diethylphenyl, 1,2,3-triethylphenyl 1,2,4-Tri-n-propylphenyl, 1,2,3,4-Tetra-n-propylphenyl, 1,2,3,5-Tetra-n-propylphenyl, 1,2,4,5-Tetra-n-propylphenyl, Penta-n-propylphenyl, Hexa-n-propylphenyl, Isopropylphenyl, Mestriisopropylphenyl, o-Diisopropylphenyl, m-Diisopropylphenyl, p-Diisopropylphenyl, 1,2,3-Triisopropylphenyl, 1,2,4-Triisopropylphenyl, 1,2,3,4-Tetra-n-propylphenyl -At least one of tetraisopropylphenyl, 1,2,3,5-tetraisopropylphenyl, 1,2,4,5-tetraisopropylphenyl, pentaisopropylphenyl, hexaisopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, o-di-n-butylphenyl, m-di-n-butylphenyl, p-di-n-butylphenyl, o-diisobutylphenyl, m-diisobutylphenyl, p-diisobutylphenyl, o-di-tert-butylphenyl, m-di-tert-butylphenyl, and p-di-tert-butylphenyl.

[0080] Preferably, R can also be a straight-chain or branched alkane; more preferably, R can be a linear or branched alkane with 10 or fewer carbon atoms and an alkyl substituent containing individual unsaturated bonds (unsaturated bonds refer to carbon-carbon double bonds that undergo sp2 hybridization and carbon-carbon triple bonds that undergo sp hybridization).

[0081] Preferably, R can also be a polymeric group containing repeating units of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less.

[0082] More preferably, R is benzyl, p-dibenzyl, (CH2)3, or (CH2)4.

[0083] This invention provides a method for synthesizing a polyester polymer compound, the method comprising the steps of: a heterocyclic lactone represented by Formula 1, in which an organic base acts as a catalyst, and a reagent R(OH) provides an active proton. m Under the condition of using an initiator, the following was synthesized:

[0084] The polyester polymer compound shown in Formula 2; the reaction process is shown in Reaction Formula I.

[0085]

[0086] In reaction (I), R1 and R2 can be the same or different, and the two groups R1 and R2 must exist simultaneously on the six-membered heterocycle, with the substitution sites being any two of the four methylene carbons.

[0087] R1 and R2 are each independently selected from any one of hydrogen, halogen, alkyl (linear alkyl, branched alkyl, cycloalkyl), substituted alkyl (linear alkyl, branched alkyl, cycloalkyl), alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, and substituted polyheterocyclic aromatic; the monocyclic aromatic includes phenyl, azirroaromatic, thioaromatic, and oxaaromatic; the polycyclic aromatic and polyheterocyclic aromatic refer to groups containing two or more monocyclic aromatic groups; R1 and R2 may be the same or different;

[0088] The halogen is selected from fluorine, chlorine, bromine, and iodine.

[0089] The alkyl group is a linear alkyl group, a branched alkyl group, or a cycloalkyl group; further, the alkyl group can be a C1-C20 alkyl group; or it can be a C1-C10 alkyl group, including methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; preferably, it is ethyl.

[0090] The substituted alkyl group is a substituted linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0091] The substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, benzyl, alkyl carbonyl, alkenyl carbonyl, cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, alkenyl, alkynyl, cycloalkyl, sulfone, hydroxyl, nitro, halogen, carboxyl, alkyl, alkoxy, amino, cycloalkoxy, cycloamino, sulfinamide, sulfonamide, morpholino, and piperazine. Furthermore, the substituents on the alkyl, alkenyl, alkynyl, monocyclic aromatic, polycyclic aromatic, and polyheterocyclic aromatic groups are monosubstituted or polysubstituted, and are independently selected from one or more of the following groups: hydrogen, heteroatom, amino, cyano, hydroxyl, nitro, halogen, carboxyl, C1-C10 alkyl, alkoxy, amino, cycloalkoxy, cycloamino, C2-C12 alkenyl, C2-C12 alkynyl, C3-C12 cycloalkyl, benzyl, alkyl carbonyl, C2-C12 alkenyl carbonyl, C3-C12 cycloalkyl carbonyl, phenyl carbonyl, benzyl carbonyl, alkoxy carbonyl, ester, sulfoxide, sulfone, sulfinamide, sulfonamide, morpholinyl, and piperazine.

[0092] Preferably, R1 is a C1-C20 alkyl group, and R2 is selected from C1-C20 alkyl groups; more preferably, R1 is a C1-C10 alkyl group, and R2 is selected from C1-C10 alkyl groups, and R1 and R2 can be C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 alkyl groups, respectively. Even more preferably, R1 and R2 are both ethyl groups.

[0093] In reaction formula (I), X is selected from heteroatoms, including heteroatoms such as O, S, N, and P; preferably, X is O.

[0094] In reaction formula (I), the value of n 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.

[0095] In reaction formula (I), m is the degree of branching, and m is a positive integer greater than or equal to 1. For example, 1≤m≤10, 10≤m≤20; preferably, 1≤m≤10 (m can also represent the functionality of the initiator ROH).

[0096] The polyester polymer compounds include linear, cyclic, star-shaped and other topological structures.

[0097] In reaction formula (I), the organic base can be a sterically hindered or non-nucleophilic base.

[0098] Preferably, the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:

[0099]

[0100] And the ammonium salt has the formula R 11 R 12 R 13 N + H, where R 11 R 12 and R 13 Each of these groups represents hydrogen (H), a C1-C20 alkyl, a C5-C20 cycloalkyl, or a C7-C20 alkylaryl group, and each group may optionally contain one or more heteroatoms (e.g., oxygen, phosphorus, or sulfur atoms) and / or substituents, and R 11 and R 12 Between, R 12 and R 13 Between, and / or R 11 and R 13 Rings may exist between them, and the rings may contain heteroatoms.

[0101] Preferably, the organic base is selected from one or more of phosphazenes, compounds containing a guanidine group, and compounds containing an amidine group. In some embodiments, the organic base is selected from... t Bu-P1、 t Bu-P2, t Bu-P4, 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 alkoxides of C1-C5, triethanolamine, choline, N-methylmorpholine, pyridine, dimethylaminopyridine, N,N'-dihydroxyethylethylenediamine, β-hydroxyethylethylenediamine, N-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrahydroxyethylethylenediamine, N-hydroxyethylpropanediamine, trimethylhydroxyethylpropanediamine, N,N'-di(2-hydroxyethyl)-1,3-propanediamine, etc.

[0102] Preferably, the catalyst is one or more of phosphazene and TBD. More preferably, the phosphazene is a strong Lewis base containing a (R₂N)₂-P=N structure. Even more preferably, the phosphazene has the structure shown in Formula 3:

[0103]

[0104] In Equation 3, R3-R 10 Each alkyl group is 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, and C10 alkyl groups.

[0105] y is a positive integer greater than or equal to 1. Preferably, 1 ≤ y ≤ 3.

[0106] Preferably, the phosphazene is selected from... t Bu-P1、 t Bu-P2, t The structures of Bu-P4 are shown below:

[0107]

[0108] In reaction formula (I), the initiator is a reagent that can provide active protons; it is generally an alcohol.

[0109] The alcohol is R(OH)m, where R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyhexyl aromatic, substituted polyhexyl aromatic, or a polymeric group containing repeating units of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less. m can also represent the functionality of the initiator, where m is a positive integer greater than or equal to 1; for example, 1 ≤ m ≤ 10, 10 ≤ m ≤ 20; preferably, 1 ≤ m ≤ 10.

[0110] Preferably, R can represent an aromatic group, including phenyl, naphthyl, anthracene, phenanthryl, pyrene, benzo[a]pyrene and its derivatives; specifically, R can be selected from phenyl, benzyl, 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, tribenzyl 1,2,3-triethylphenyl, 1,2,4-triethylphenyl, 1,2,3,4-tetraethylphenyl, 1,2,3,5-tetraethylphenyl, 1,2,4,5-tetraethylphenyl, pentaethylphenyl, hexaethylphenyl, phenylpropyl, mesitylene-n-propylphenyl, 1,2,3,4-diethylphenyl, m-diethylphenyl, p-diethylphenyl, 1,2,3-triethylphenyl 1,2,4-Tri-n-propylphenyl, 1,2,3,4-Tetra-n-propylphenyl, 1,2,3,5-Tetra-n-propylphenyl, 1,2,4,5-Tetra-n-propylphenyl, Penta-n-propylphenyl, Hexa-n-propylphenyl, Isopropylphenyl, Mestriisopropylphenyl, o-Diisopropylphenyl, m-Diisopropylphenyl, p-Diisopropylphenyl, 1,2,3-Triisopropylphenyl, 1,2,4-Triisopropylphenyl, 1,2,3,4-Tetra-n-propylphenyl -At least one of tetraisopropylphenyl, 1,2,3,5-tetraisopropylphenyl, 1,2,4,5-tetraisopropylphenyl, pentaisopropylphenyl, hexaisopropylphenyl, n-butylphenyl, isobutylphenyl, tert-butylphenyl, o-di-n-butylphenyl, m-di-n-butylphenyl, p-di-n-butylphenyl, o-diisobutylphenyl, m-diisobutylphenyl, p-diisobutylphenyl, o-di-tert-butylphenyl, m-di-tert-butylphenyl, and p-di-tert-butylphenyl.

[0111] Preferably, R can also be a straight-chain or branched alkane; more preferably, R can be a linear or branched alkane with 10 or fewer carbon atoms and an alkyl substituent containing individual unsaturated bonds (unsaturated bonds refer to carbon-carbon double bonds that undergo sp2 hybridization and carbon-carbon triple bonds that undergo sp hybridization).

[0112] Preferably, R can also be a polymeric group containing repeating units of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less.

[0113] More preferably, R is benzyl, p-dibenzyl, (CH2)3, or (CH2)4, meaning the initiator is selected from benzyl alcohol (BnOH), 1,4-benzyldiethanol (1,4-BDM), 1,3-propanediol, or 1,4-butanediol.

[0114] In the method of this invention, the molar ratio of Formula 1, catalyst, and initiator is (5-200):(0.01-5):1; preferably, it is (25-100):(0.1-1):1, for example, it can be (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):(0.3-0.2):1. 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; More preferably, 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; more preferably, 50:0.5:1, 50:1:1, 50:0.25:1, 50:0.2:1, 50:0.1:1, 25:0.1:1 or 100:0.2:1.

[0115] The method described in this invention can be carried out under solvent-free conditions (i.e., bulk conditions) and solvent conditions.

[0116] When carried out under solvent conditions, the solvent for the reaction is selected from one or more of the following: tetrahydrofuran (THF), TBD, benzene, toluene, xylene, dichlorobenzene, mesitylene, dichloromethane, chloroform, 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.; preferably, the solvent for the reaction is tetrahydrofuran (THF) and / or TBD.

[0117] In the method described in this invention, the initial concentration [M]0 of the polyester polymer compound shown in formula (1) is not particularly limited, as long as the preparation of the polyester polymer compound can be achieved. In some embodiments, the initial concentration [M]0 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, 20 mol / L.-1 Preferably, [M]0 is 3.0-10.0 mol L. -1 More preferably, the concentration is 4.0-8.0 mol / L. -1 More preferably, it is 5.0-6.3 mol L. -1 More preferably, the concentration is 5.0, 5.3, or 6.3 mol / L. -1 .

[0118] In the method described in this invention, the reaction temperature is not particularly limited, as long as the preparation of the polyester polymer compound can be achieved. In some embodiments, the reaction temperature is -100 to 200°C, and can be -100 to 180, -80 to 200, -100 to 150, -100 to 130, -100 to 120, -100 to 100°C, -80 to 80, -70 to 70, -60 to 60, -50 to 50, -50 to 60, -40 to 40, -30 to 30, -20 to 20, or -10 to 10°C. Preferably, it is -50 to 60°C. More preferably, the temperature is -25 to 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. More preferably, the temperature is -25 to -9°C. More preferably, the temperature is -25°C.

[0119] In the method described in this invention, there is no particular limitation on the reaction time, as long as the preparation of the polyester polymer compound can be achieved. In some embodiments, 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, 30mins-160h, 1-150h, 1h-140h, 5h-120h, or 10h-100h. Preferably, the reaction time is 1-150 h. More preferably, it is 8-120 h, for example, it can be 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, or 120 h. Even more preferably, it is 8-12 h.

[0120] In the method described in this invention, when R1 is ethyl and R2 is ethyl, i.e., Formula 1 is HL, the catalyst is... t Bu-P4, with BnOH as the initiator, reacts as shown in reaction formula II below:

[0121]

[0122] In the method described in this invention, when R1 is ethyl, R2 is ethyl (i.e., Formula 1 is HL), and the initiator is R... 1 When OH is present, a monohydroxy-terminated polyester polymer is formed; when R1 is ethyl and R2 is ethyl, i.e., Formula 1 is HL, and the initiator is HO-R 2 When -OH is present, a dihydroxyl-terminated polyester polymer is formed; the reaction formula is shown below:

[0123]

[0124] This invention t Possible chain initiation mechanisms during the ring-opening polymerization of HL catalyzed by Bu-P4 / BnOH include: Figure 1 As shown. (Through) 1 HNMR monitoring t The stoichiometric reaction of Bu-P4 with BnOH at room temperature revealed the formation of a complex. tThe formation of Bu-P4H+···OBn] was observed. This invention also observed the disappearance of hydroxyl H at δ0.92 ppm and changes in other signal chemical shifts of tBu-P4 and BnOH.

[0125] Equivalent experimental procedures used to corroborate the mechanism: such as Figure 1 Take an equivalent amount (0.05 mmol) of BnOH and t Bu-P4 was mixed and dissolved in 0.6 mL of deuterated toluene. The mixture was then placed in an NMR tube and shaken thoroughly before NMR testing.

[0126] The present invention also provides polyester polymer compounds prepared by the above method.

[0127] The present invention also provides the application of the polyester polymer compound or the polyester polymer compound prepared by the above method in the fields of polyurethane and pressure-sensitive adhesives.

[0128] In the polyurethane field: Polyurethane, short for polyurethane, is a high molecular weight compound, mainly of two types: polyester and polyether. Polyurethane is primarily obtained by copolymerizing polyester polyols or polyether polyols with multifunctional isocyanates (such as diphenylmethane diisocyanate MDI, toluene diisocyanate TDI, etc.). Therefore, polyester polyols or polyether polyols of different molecular weights are indispensable raw materials in the field of polyurethane synthesis.

[0129] Polyurethane is classified into rigid foam, flexible foam, polyurethane elastomer, thermoplastic plastic, polyurethane adhesive, polyurethane coating, and paint according to its material properties. It is widely used in many fields such as automobile manufacturing, furniture, construction, insulation materials, and footwear manufacturing, and has very important application value.

[0130] Polyester polyols and polyether polyols are important precursors used industrially in the synthesis of polyurethane materials, and polyurethane materials based on polyester polyols often exhibit better mechanical properties than those based on polyether polyols. However, the production cost of polyester polyols is much higher than that of polyether polyols, thus limiting their large-scale application. Therefore, the polyHL prepared in this invention, a cheap and readily available polyester material with a novel chemical structure, and its corresponding polyester polyol, have significant and far-reaching implications for the polyurethane and even the chemical industry.

[0131] Pressure-sensitive adhesives, also known as pressure-sensitive self-adhesives or simply pressure-sensitive glues, are an indispensable functional material in the polymer industry. Chemically, most pressure-sensitive adhesives on the market are based on polyolefins. However, polyolefins cannot be degraded after use. Preliminary experimental results from this invention have demonstrated that polyHL possesses relatively better pressure-sensitive adhesive performance. Furthermore, because polyHL allows for the chemical recovery of its monomers, it has the potential to become the first pressure-sensitive adhesive on the market that enables monomer recovery, thus possessing a bright prospect for industrialization.

[0132] This invention also provides the application of organic bases, such as phosphazenes, in the catalytic synthesis of polyester polymers of Formula 2 from compounds of Formula 1 as described above. The organic base may be a sterically hindered or non-nucleophilic base.

[0133] Preferably, the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:

[0134]

[0135] And the ammonium salt has the formula R 11 R 12 R 13 N + H, where R 11 R 12 and R 13 Each of these groups represents hydrogen (H), a C1-C20 alkyl, a C5-C20 cycloalkyl, or a C7-C20 alkylaryl group, and each group may optionally contain one or more heteroatoms (e.g., oxygen, phosphorus, or sulfur atoms) and / or substituents, and R 11 and R 12 Between, R 12 and R 13 Between, and / or R 11 and R 13 Rings may exist between them, and the rings may contain heteroatoms.

[0136] Preferably, the organic base is selected from one or more of phosphazenes, compounds containing a guanidine group, and compounds containing an amidine group. In some embodiments, the organic base is selected from... tBu-P4, 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 alkoxides of C1-C5, triethanolamine, choline, N-methylmorpholine, pyridine, dimethylaminopyridine, N,N'-dihydroxyethylethylenediamine, β-hydroxyethylethylenediamine, N-(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrahydroxyethylethylenediamine, N-hydroxyethylpropanediamine, trimethylhydroxyethylpropanediamine, N,N'-di(2-hydroxyethyl)-1,3-propanediamine, etc.

[0137] Preferably, the organic base is one or more of phosphazene and TBD. More preferably, the phosphazene is a strong Lewis base containing a (R₂N)₂-P=N structure. Even more preferably, the phosphazene structure is as shown in Formula 3:

[0138]

[0139] In Equation 3, R3-R 10 Each alkyl group is 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, and C10 alkyl groups.

[0140] y is a positive integer greater than or equal to 1. For example, 1≤y≤10, 10≤y≤20; preferably, 1≤y≤3.

[0141] More preferably, the phosphazene is selected from... t Bu-P1、 t Bu-P2, t The structures of Bu-P4 are shown below:

[0142]

[0143] The present invention also provides a method for catalytically recovering monomers from polymers, the method comprising catalysis and pyrolysis.

[0144] In this invention, the catalytic method includes: in a solvent, using catalysts such as inorganic salts, organometallic compounds, and organic compounds to degrade polyester polymers as shown in Formula 2, to obtain heterocyclic compounds or oligomers of Formula 1 or corresponding derivatives of Formula 1.

[0145] The solvent is selected from one or more of benzene, chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, o-dichlorobenzene, o-dibromobenzene, m-dichlorobenzene, m-dibromobenzene, p-dichlorobenzene, p-dibromobenzenetoluene, m-xylene, p-xylene, o-xylene, mesitylene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; preferably, it is o-dichlorobenzene.

[0146] Wherein, the salt is an inorganic salt, and the inorganic salt is selected from one or more of the following: zinc chloride, tin chloride, copper 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, and lanthanum nitrate; preferably, it is zinc chloride.

[0147] The organometallic compound is selected from one or more of the following: stannous octoate, stannous isooctanoate, dibutyltin dilaurate, bis[bis(trimethylsilyl)amino]tin, triisopropyllanthanum oxide, tri[N,N-bis(trimethylsilane)amine]lanthanum, lanthanum trifluoromethanesulfonate, silver trifluoromethanesulfonate, copper trifluoromethanesulfonate, iron trifluoromethanesulfonate, scandium trifluoromethanesulfonate, and yttrium trifluoromethanesulfonate; preferably, it is stannous octoate or tri[N,N-bis(trimethylsilane)amine]lanthanum.

[0148] The organic compound is selected from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5,7-triazidobicyclo(4.4.0)dec-5-ene (TBD), 1,3-di-methylene-imidazolium-2-ide (IMes), and others. t Bu-P1、 t Bu-P2, t One or more of Bu-P4, etc.; preferably, DBU.

[0149] The degradation conditions are described as a hot bath method such as an oil bath or sand bath, with a temperature range of 120-300℃; preferably 160℃.

[0150] The degradation time is 8-24 hours; preferably 12 hours.

[0151] In this invention, the pyrolysis method includes: heating and pyrolyzing the polyester polymer compound as described above to obtain the heterocyclic compound or its oligomer or the corresponding derivative of Formula 1.

[0152] Preferably, the thermal pyrolysis is carried out in a nitrogen atmosphere.

[0153] Preferably, the thermal pyrolysis is carried out under sealed conditions.

[0154] Preferably, the thermal pyrolysis is carried out under vacuum conditions.

[0155] The thermal pyrolysis is preferably carried out in a sand bath. The present invention does not limit the heating temperature, as long as the purpose of thermal pyrolysis can be achieved to recover the monomers of the polyester polymer compound. In some embodiments, the heating temperature is greater than 100°C. In other embodiments, the heating temperature is 100-1000°C; it can be 100-200, 200-300, 150-300, 300-400, 400-500, 500-600, 600-700, 700-800, 800-900, or 900-1000°C. Preferably, the heating temperature is 150-300°C. More preferably, it is 150-260°C. Even more preferably, it is 180-230°C. Even more preferably, it is 200-230°C. Even more preferably, it is 220°C.

[0156] In this invention, the heating time is not limited, as long as the purpose of heating and pyrolysis can be achieved to recover the monomers of the polyester polymer compound. In some embodiments, the heating time is greater than 0.5 hours. In other embodiments, the heating time is 1-50 hours; it can be 1-5, 5-10, 10-15, 15-20, 1-20, 20-25, 25-30, 30-35, 35-40, 40-45, or 45-50 hours. Preferably, the heating time is 1-20 hours. More preferably, it is 1-10 hours. Even more preferably, it is 1-5 hours. Even more preferably, it is 3 hours.

[0157] In the method described in this invention, when the catalytic polymer PolyHL recovers Poly monomers, the reaction process is shown in reaction formula IV below:

[0158]

[0159] It should be noted that the process equipment or apparatus not specifically specified in the following embodiments are all conventional equipment or apparatus in the art. Furthermore, it should be understood that one or more method steps mentioned in this invention do not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, unless otherwise stated. Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific specific embodiments, and not for limiting the scope of protection of the present invention; in the specification and claims of this invention, unless otherwise expressly stated herein, the singular forms "a," "an," and "this" include the plural forms.

[0160] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0161] The present invention does not limit the HL raw materials used in the following examples. They can be commercially available or prepared by the following method: CO2 and 1,4-butadiene are synthesized into δ-L under Pd catalysis, and δ-L and H2 are synthesized into the hexa-membered lactone 3,6-diethyltetrahydro-2h-pyran-2-one (HL) under Pd / C catalysis. The reaction process is shown in the following reaction route (2).

[0162]

[0163] In the following examples, the raw material is HL, and the compound polyHL is prepared by ring-opening polymerization of HL and BnOH, as shown in the following reaction formula.

[0164]

[0165] Examples 1-2

[0166] Example 1: ROP reaction of HL catalyzed by TBD and DBU

[0167] The specific synthesis steps include:

[0168] To induce ring-opening polymerization (ROP) of HL to produce polyHL, this invention initially explored catalysts with intercalation mechanisms, including tin(II)2-ethylhexanoate [Sn(Oct)2] and dibutyltin dilaurate (DBTDL), but no polymer was obtained. The invention also used the organic acid diphenyl phosphate (DPP), but this also failed to yield a polymer. Then, tests with organic bases such as 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) showed that only TBD / BnOH could promote a moderate degree of monomer conversion, resulting in a lower molecular weight of liquid polyHL (Table 1, run 9:M). n =6.0kg mol -1 , Table 1, run 10:M n = 5.6 kg mol -1 , ).

[0169]

[0170] Reaction Route 1: Linear Synthetic Pathway of PolyHL

[0171] Table 1. Initial ROP attempts for HL

[0172]

[0173] Example 1 represents solvent-free conditions; [M]0 (mol / L) is the initial concentration of HL monomer in the system, which refers to the concentration of monomer in the system when the reaction is started.

[0174] Example 2

[0175] In a glove box under a nitrogen atmosphere, 0.0158 mmol of TBD catalyst and 0.0158 mmol of BnOH were added to a flame-dried 10 mL Schlenk tube. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was then placed in a pre-set 30°C oil bath until temperature equilibrium was reached. Once temperature equilibrium was reached, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 96 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for… 1 ¹H NMR was used to analyze the monomer conversion rate. To purify the polyHL product, the quenched reaction solution was added dropwise to 20 mL of ice-cold methanol. After centrifugation, the supernatant was discarded, and the precipitate was polyHL. The above purification steps were repeated 3-5 times. After obtaining the precipitate on the last attempt, it was placed in a vacuum drying oven and dried to constant weight. The resulting product was the polyHL sample purified under these conditions. n (number average molecular weight) and (Molecular weight distribution) was determined by GPC method at 40°C in a tetrahydrofuran mobile phase after correction based on PMMA standard sample.

[0176] Example 2

[0177] The preparation steps are the same as in Example 1, except that in a glove box under a nitrogen atmosphere, 0.0158 mmol of TBD catalyst and 0.0158 mmol of BnOH are added to a flame-dried 10 mL Schlenk tube, and then 0.02 mL of tetrahydrofuran (THF) is added to dissolve them. Other conditions are as shown in Table 1.

[0178] Examples 3-17 investigated the catalytic activity of three phosphazenes combined with BnOH in the ROP of HL.

[0179] When [HL] / [BnOH] = 50 / 1, 1 mol% t Bu-P1 or t In a Bu-P2-25℃ THF solution ([M]0=5.3M), after 72h, t No polymer was generated under Bu-P1 catalysis after 72 h; t After a five-day reaction, Bu-P2 achieved a monomer conversion rate of 41%. Encouragingly, t Bu-P4 significantly promoted polymer formation, achieving a conversion rate of 87% after 12 hours, yielding M. n =19.9kg mol -1 PolyHL with a slightly wider molecular weight distribution D = 1.90. t Bu-P1、 t Bu-P2 and t The pKa values ​​of Bu-P4 in acetonitrile were 26.9, 33.5, and 42.7, respectively, which may be due to the significant differences in basicity among the three phosphazenes. Next, the pKa values ​​were gradually decreased... t Reducing the loading of Bu-P4 from 2 mol% to 0.2 mol% makes the polymerization more controllable. In particular, when... t When the loading of Bu-P4 was reduced to 0.2 mol%, M was obtained. n = 9.2 kg mol -1 The polyHL, with a very low dispersion D = 1.09 (Table 2, run 7), indicates living ring-opening polymerization (ROP) of HL. However, as the initial monomer concentration of the system was gradually diluted in THF to 2.0, 1.6, and 1.3 M, the ROP of HL became less controlled: the conversion rate decreased significantly, and M... n With increased dispersibility (Table 2, runs 8-10), increasing the reaction temperature from -25°C to 41°C also leads to more uncontrollable polymerization. This invention also designed two sets of experiments with [HL] / [BnOH] ratios of 25 / 1 and 100 / 1. Both polymerization conditions achieved the highest monomer conversion of 88%, and the resulting polymers had a high M... n The [HL] / [BnOH] ratio increases linearly with increasing [HL] / [BnOH] ratio, while the dispersibility of the polymer remains low throughout.

[0180] Table 2. Results of ROP reaction of HL catalyzed by phosphazene / BnOH

[0181]

[0182] [M]0 refers to the initial concentration of HL monomer in the system, which is the concentration of the monomer in the entire system when the reaction feed is started.

[0183] Example 3

[0184] In a glove box under a nitrogen atmosphere, take 0.0063 mmol of... t Bu-P1 catalyst and 0.0126 mmol of BnOH were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of tetrahydrofuran to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was reached, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 72 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for further processing. 1 1H NMR analysis of monomer conversion rate.

[0185] Example 4

[0186] In a glove box under a nitrogen atmosphere, take 0.0063 mmol of... t Bu-P2 catalyst and 0.0126 mmol of BnOH were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of tetrahydrofuran to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was reached, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 120 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for further processing. 1 ¹H NMR was used to analyze the monomer conversion. To purify the polyHL product, the quenched reaction solution was added dropwise to 20 mL of ice-cold methanol. After centrifugation, the supernatant was discarded, and the precipitate was polyHL. The above purification steps were repeated 3-5 times. After obtaining the precipitate on the last attempt, it was dried in a vacuum drying oven to constant weight, and the resulting product was the final product. n (number average molecular weight) and (Molecular weight distribution) was determined by GPC method at 40°C in a tetrahydrofuran mobile phase after correction based on PMMA standard sample.

[0187] Examples 5-9

[0188] The preparation steps were the same as in Example 4, except that the molar concentration of the catalyst was adjusted in the range of 0.0126–0.126 mmol, and other conditions were as shown in Table 2. The characterization of the polymer sample obtained in Example 9 is described in Example 19.

[0189] Examples 10-12

[0190] The preparation steps are the same as in Example 9, except that the initial molar concentration of HL in the system is gradually reduced from 5.3M to 1.3M, and other conditions are as shown in Table 2.

[0191] Examples 13-15

[0192] The preparation steps are the same as in Example 9, except that the reaction temperature is increased from -25℃ to -9℃, 28℃ and 41℃ respectively, and other conditions are as shown in Table 2.

[0193] Examples 16-17

[0194] The preparation steps are the same as in Example 9, except that HL, t The feed ratios of Bu-P4 and BnOH were adjusted to 25 / 0.1 / 1 and 100 / 0.2 / 1, respectively, with other conditions as shown in Table 2. The characterization of the polymer sample obtained in Example 16 is described in Example 19.

[0195] Example 18: Synthesis of polyester diols using 1,3-propanediol as an initiator

[0196]

[0197] In the above formula, j and k are positive integers greater than 1, and j and k can be the same or different.

[0198] Specific implementation method: In a glove box under a nitrogen atmosphere, take 0.0063 mmol of... t Bu-P4 catalyst and 0.042 mmol of 1,3-propanediol were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of tetrahydrofuran to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 48 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for further processing. 1¹H NMR was used to analyze the monomer conversion rate. To purify the polyHL product, the quenched reaction solution was added dropwise to 20 mL of ice-cold methanol. After centrifugation, the supernatant was discarded, and the precipitate was polyHL. The above purification steps were repeated 3-5 times. After obtaining the precipitate on the last attempt, it was placed in a vacuum drying oven and dried to constant weight. The result was the final product. Figure 2 The image shows the MALDI-TOF characterization of the product.

[0199] Example 19: Synthesis of polyester diols using 1,4-butanediol as an initiator

[0200]

[0201] In the above formula, t and r are positive integers greater than 1, and t and r can be the same or different.

[0202] Specific implementation method: In a glove box under a nitrogen atmosphere, take 0.0063 mmol of... t Bu-P4 catalyst and 0.042 mmol of 1,4-butanediol were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of tetrahydrofuran to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 48 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for further processing. 1 ¹H NMR was used to analyze the monomer conversion rate. To purify the polyHL product, the quenched reaction solution was added dropwise to 20 mL of ice-cold methanol. After centrifugation, the supernatant was discarded, and the precipitate was polyHL. The above purification steps were repeated 3-5 times. After obtaining the precipitate on the last attempt, it was placed in a vacuum drying oven and dried to constant weight. The result was the final product. Figure 3 The image shows the MALDI-TOF characterization of the product.

[0203] Example 20: Study on the reaction characteristics of ring-opening polymerization (ROP) of Example 9

[0204] For the reaction system, reaction conditions, and reaction steps used to study the characteristics of ring-opening polymerization, please refer to Example 9. Multiple parallel polymerization reactions were carried out by changing only the reaction time to study the change in conversion rate over time. The reaction was quenched after a predetermined reaction time to avoid systematic errors in conversion rate caused by continuously sampling and testing from the same reaction system.

[0205] Figure 4 The data in a and 4b comes from 1Conversion rate data characterized by H NMR, Figure 4 The data in c and 4d are derived from GPC analysis. Polymerization kinetics data support that the polymerization under these conditions is a living polymerization: monomer conversion increases linearly with reaction time. Figure 4 a). The time-dependent curve of ln[M]0 / [M] exhibits very clear first-order dynamic characteristics. Figure 4 b). M of polyHL n The dispersion of the obtained polyHL is linearly correlated with the monomer conversion rate, and remains consistently low (D ~ 1.1) during the chain growth stage. Figure 4 c). Figure 4 The GPC curve with a unimodal distribution given by d also confirms this conclusion.

[0206] Example 21 characterizes the polymer molecules obtained in Examples 9 and 16.

[0207] The fidelity of the synthesized polyester (polyHL) chain end groups was investigated using matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS). The MS signal of polyHL showed only one set of molecular ion peaks, which is consistent with the desired structure of linear polyHL induced by BnOH in this invention. Figure 5 The structure of polyHL obtained by the tBu-P4 / BnOH system was further characterized by NMR spectroscopy, and it was observed that in the 1H NMR spectrum ( Figure 6 BnO - The proton signal on the methylene group (δ 5.12 ppm) and the proton signal on the methine group connected to the hydroxyl terminal group (δ 3.49 ppm) were observed, and in... 13 The corresponding signal can also be observed in the CNMR spectrum. Figure 7 ).

[0208] MALDI-TOF Experimental Procedure: The selected sample was the purified polymer sample from Example 9. The experiment was conducted using a Bruker Autoflex Speed ​​MALDI-TOF mass spectrometer in positive ion, reflectance mode. First, a drop of 1% NaI solution was added to the stainless steel target plate. Then, 1 μL of a mixture of matrix and polymer sample was added (DHB is the matrix concentration, an abbreviation for 2,5-dihydroxybenzoic acid, with a matrix concentration of 20 mg / mL). -1 (The solvent was THF). MALDI-TOF performs external molecular weight calibration by adding a peptide calibration standard sample next to the sample well on the target plate. Raw data processing was performed in FlexAnalysis software, and the acquired raw data was used for the aforementioned spectra. Figure 5The rendering was performed using Origin Pro 2019b.

[0209] Figure 6 and Figure 7 The sample used for NMR testing was obtained in Example 16. Since the polymers initiated by BnOH belong to the same substance (with completely identical chemical structures), the difference in molecular weight has no effect on the chemical shift and characteristic peaks in the NMR spectrum. Only the integral area of ​​the polymer end groups differs. Therefore, the characteristic spectrum of the polymer obtained under the preferred conditions in the example is used as a representative for illustration.

[0210] by t Bu-P4 and 1,4-benzenedimethanol (1,4-BDM) are catalysts in [HL] / [ t Under the conditions of Bu-P4] / [1,4-BDM]=15 / 0.15 / 1, a telechelic polymer polyHL (dihydroxy-terminated polyHL) with good chain-end fidelity was synthesized. MALDI-TOF MS signal showed M n A set of signal peaks, =n×156.1+161.1, matches the expected end-group structure of the diol-terminated structure. Figure 8 ).

[0211] Example 22: Preparation method of 1,4-benzenedimethanol as a linear polyHL diol sample

[0212]

[0213] In the above formula, p and q are positive integers greater than 1, and p and q can be the same or different.

[0214] In a glove box under a nitrogen atmosphere, take 0.0063 mmol of... t Bu-P4 catalyst and 0.042 mmol of 1,4-BDM were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of tetrahydrofuran to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, and removed from the glove box. It was placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was reached, 0.63 mmol of HL was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 48 h. Then, 1 mL of 5% HCl-methanol solution was added to quench the reaction, and 50 μL of the reaction solution was used for further processing. 1¹H NMR was used to analyze the monomer conversion rate. To purify the polyHL product, the quenched reaction solution was added dropwise to 20 mL of ice-cold methanol. After centrifugation, the supernatant was discarded, and the precipitate was polyHL. The above purification steps were repeated 3-5 times. After obtaining the precipitate on the last attempt, it was placed in a vacuum drying oven and dried to constant weight. The result was the final product.

[0215] Example 23: Determination of physical properties of polyHL

[0216] This invention analyzed Example 17 using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). t Thermal stability of polyHL prepared by the Bu-P4 / BnOH system.

[0217] Linear polyHL exhibits excellent thermal stability: its TGA and DTG curves show that its T d,5％ =326.0℃,T max =335.3℃ Figure 9 ); Second heating scan curve of linear polyHL sample (5℃ min) -1 The DSC curve of the sample showed a glass transition temperature (Tg) of -30.6℃, and no crystallization peak was observed. Figure 10 The results show that polyHL is an amorphous polymer material with good thermal stability.

[0218] Example 24 Determination of the chemical recyclability of PolyHL in solvents

[0219] Thermodynamic experimental sample preparation: The experimental conditions for the PolyHL samples used were all the same as in Example 9, except that the reaction temperature was changed to -26℃, -16℃, -9℃, 28℃ and 41℃, and the reaction time was changed accordingly to obtain the conversion rate information at different times. Figure 11 This shows the curves showing the change in HL monomer concentration over time under different temperature conditions. Figure 12 Display the Van't Hoff analysis curve for HL.

[0220] This invention further investigates the effects at different temperatures (-25, -16, -9, 28, 41°C). t Bu-P4 / BnOH catalyzes the ROP reaction of HL, thereby calculating its polymerization thermodynamic parameters. Figure 11 and 12 According to the Dainton equation, the THF concentration at [HL]0 = 1.0 mol / L was calculated. -1 enthalpy change over time (ΔH) o p ) and entropy change (ΔS) op The values ​​are -13.12 kJ / mol. -1 and -49.09 J mol -1 K -1 To further obtain T c The temperature is -6℃. Compared with other monosubstituted and unsubstituted six-membered ring lactones, this T... c The values ​​are significantly lower. Therefore, introducing substituents at the α- and δ- positions of δ-VL is an effective strategy to improve the chemical recyclability of the monomer.

[0221] Example 25 Determination of the chemical recyclability of PolyHL in solvents

[0222] Chemical recovery experimental procedure: In a glove box under a nitrogen atmosphere, 200 mg of polyHL sample (Example 9) and 5 mol% zinc chloride were placed in a 10 mL Schlenk tube, and then 2.6 mL of o-dichlorobenzene (o-DCB) was added to dissolve them. The Schlenk tube was then sealed with a rubber stopper, wrapped with sealing film, removed from the glove box, and placed in a pre-set 160°C oil bath for heating and stirring for 12 hours. The solvent in the system was then removed, and 10 mg of the degraded liquid product was taken out for further processing. 1 HL yield was analyzed by 1H NMR.

[0223] The recycling results are as follows Figure 13 As shown in the figure, the recovery rate of HL can reach 100%, indicating that using ZnCl2 as a catalyst for the catalytic reaction is effective for the chemical recovery of linear polyHL.

[0224] Example 26: Determination of the chemical recyclability of PolyHL under solvent-free conditions by thermal decomposition.

[0225] In a glove box under a nitrogen atmosphere, 200 mg of polyHL sample (Example 9) was placed into a 10 mL Schlenk tube, sealed with a rubber stopper, wrapped with sealing film, and then removed from the glove box. The tube was then placed in a pre-set 220°C sand bath and heated with stirring for 3 hours, while a rotary vane vacuum pump was used to continuously evacuate the system. After 3 hours, a colorless oily liquid was formed in the system. 10 mg of this liquid was taken out for use in… 1 HL yield was analyzed by 1H NMR.

[0226] The recycling results are as follows Figure 14 As shown, the recovery rate of HL can reach 100%, indicating that PolyHL can be effectively recovered by pyrolysis under solvent-free conditions.

[0227] In summary, the method for preparing carbon dioxide-based polyester polymer of the present invention can effectively utilize carbon dioxide and mitigate the greenhouse effect by using inexpensive and readily available materials as raw materials. The polyester polymer is a chemically recyclable polymer with excellent physicochemical properties. Therefore, the present invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0228] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A method for synthesizing a polyester polymer compound, the method comprising: The heterocyclic lactone shown in Formula 1 was used as a catalyst, and the reagent R(OH)m, which can donate active protons, was used as an initiator to synthesize the polyester polymer shown in Formula 2; the reaction process is shown in Reaction Formula I: 1 2 Reaction formula (I) R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, substituted polyheterocyclic aromatic, or a polymeric group containing a repeating unit structure of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less. R1 and R2 are each independently selected from any one of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, and substituted polyheterocyclic aromatic; the monocyclic aromatic includes phenyl, azirroaromatic, and oxaaromatic; the polycyclic aromatic and polyheterocyclic aromatic refer to groups containing two or more monocyclic aromatic groups; R1 and R2 may be the same or different; X is selected from O; n is a positive integer greater than or equal to 1; m is a positive integer greater than or equal to 1; The organic base is t Bu-P4, the structure is as follows: 。 2. The synthesis method according to claim 1, characterized in that, The polyester polymer compounds include linear, cyclic, and star-shaped topologies.

3. The synthesis method as described in claim 1, characterized in that, The method includes any one or more of the following features 1) to 7): 1) R1 is a C1-C10 alkyl group; 2) R2 is selected from C1-C10 alkyl groups; 3) The condition 1≤m≤10; 4) The molar ratio of Formula 1, organic base, and initiator is (5-200): (0.01-5): 1; 5) The reaction is carried out under solvent-free conditions or under solvent conditions; When the method is carried out under solvent conditions, the solvent for the reaction is selected from one or more of tetrahydrofuran (THF), benzene, toluene, xylene, dichlorobenzene, mesitylene, dichloromethane, chloroform, 1,2-dichloroethane, tetrahydropyrrole, tetrahydropyran, hexahydropyridine, ethyl acetate, diethyl ether, dimethyl ether, methyl ethyl ether, n-hexane, cyclohexane, cyclopentane, acetonitrile, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide; 6) The reaction temperature is -100~200℃; 7) The reaction time is 10 s-360 h.

4. The synthesis method according to claim 1, characterized in that, The method includes one or more of the following features i) to vi): i) R1 is ethyl and R2 is ethyl, that is, Formula 1 is 3,6-diethyltetrahydro-2h-pyran-2-one; ii) The initiator is one or more of benzyl alcohol, 1,4-benzyl alcohol, 1,3-propanediol, and 1,4-butanediol; iii) The molar ratio of Formula 1, organic base, and initiator is (25-100): (0.1-1): 1; iv) The reaction solvent is THF; v) The reaction temperature is -80~200℃; vi) The reaction time is 1 min-120 h.

5. The use of an organic base in the catalytic synthesis of a heterocyclic lactone of formula 1 into a polyester polymer of formula 2, characterized in that, The organic base is t Bu-P4, the structure is as follows: ； The structures of the heterocyclic lactone shown in Formula 1 and the polyester polymer compound shown in Formula 2 are as follows: Formula 1 Formula 2; R is selected from any one of the following: alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, substituted polyheterocyclic aromatic, or a polymeric group containing a repeating unit structure of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less. R1 and R2 are each independently selected from any one of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, monocyclic aromatic, substituted monocyclic aromatic, polycyclic aromatic, substituted polycyclic aromatic, polyheterocyclic aromatic, and substituted polyheterocyclic aromatic; the monocyclic aromatic includes phenyl, azirroaromatic, and oxaaromatic; the polycyclic aromatic and polyheterocyclic aromatic refer to groups containing two or more monocyclic aromatic groups; R1 and R2 may be the same or different; X is selected from O; n is a positive integer greater than or equal to 1; m is a positive integer greater than or equal to 1.

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