Easily modified chemically recyclable carbon dioxide-based polyesters, methods of synthesis and applications thereof

Abstract

The application belongs to the technical field of polymer synthesis, and relates to carbon dioxide-based polyester poly (deltaLH2) and a synthesis method and application thereof. The method is to carry out ring-opening polymerization reaction under the condition of an organic base and / or an initiator, using deltaLH2 as raw material, to obtain poly (deltaLH2). The poly (deltaLH2) has the characteristics of high transparency, high molecular weight, strong thermal stability and the like. The application also discloses a preparation method of deltaLH2. The preparation method of the poly (deltaLH2) is simple, high in yield and strong in controllability, the catalyst used is simple to prepare, low in cost, widely sourced and good in activity; the preparation method of the deltaLH2 is high in yield, simple in steps and low in cost. The method and the product obtained by the method have great application potential in the field of materials.

Description

[0001] This invention claims priority to patent application filed on November 25, 2021, with application number 2021114161422 and title "Polyester polymer compound and its preparation method and application".

[0002] Meanwhile, this invention claims priority to the patent application filed on March 17, 2022, with application number 2022102680288 and invention title "Easily Modifiable Chemically Recyclable Carbon Dioxide-Based Polyester and its Synthesis Method and Application". Technical Field

[0003] This invention belongs to the field of polymer synthesis technology, and relates to a CO2-based chemical recyclable polyester material, its synthesis method and application. In particular, it relates to the synthesis of an unsaturated six-membered ring lactone with a novel structure using inexpensive and readily available C1 source CO2 and bulk chemical raw material 1,3-butadiene, and the synthesis and chemical recycling degradation of the CO2-based polyester material are achieved through catalysis. Background Technology

[0004] Carbon dioxide, as a cheap and readily available C1 source, plays a crucial role in carbon neutrality and sustainable development through its efficient conversion and utilization. Introducing CO2 into polymer structures is a key pathway for utilizing CO2 to produce high-value-added chemicals. However, current CO2-based polymers are mainly limited to polycarbonates synthesized from CO2 and propylene oxide monomers, or polyolefins containing ester functional groups synthesized from CO2 and olefins. However, most polymers prepared from CO2 are difficult to degrade, require stringent degradation conditions, and have low monomer recovery rates, failing to achieve a green CO2 cycle. Therefore, incorporating biodegradability into CO2-based polymer systems is a strategy that can simultaneously meet the necessary conditions for both CO2 utilization and addressing white pollution.

[0005] The preparation of chemically recyclable polymers from CO2 and inexpensive bulk chemicals is a crucial strategy for achieving carbon neutrality and addressing today's white pollution problem. Therefore, synthesizing recyclable polyesters from CO2 and inexpensive chemicals—especially olefins—has been a major challenge for decades. However, despite significant progress in this field, the ability to prepare recyclable polyesters from CO2 and olefins remains an open challenge. Much scientific research has focused on synthesizing polyolefins containing ester functional groups via multi-step reactions, derived from the free radical polymerization of a six-membered ring unsaturated lactone derived from CO2 and 1,3-butadiene—δ-L (3-ethylidene-6-vinyl-tetrahydro-2H-pyran-2-one). However, all previous attempts to prepare polyester compounds from δ-L monomers via ring-opening polymerization have failed. The main reasons may be that the two substituents on the cyclic lactone skeleton have significant steric hindrance, which hinders the ring-opening process; and the conjugated olefin structure on the δ-L axis can undergo Michael addition with the nucleophilic active species in the ring-opening polymerization, thereby terminating the ring-opening chain growth process. Therefore, there is an urgent need to develop a method for synthesizing recyclable polymeric polyester compounds using CO2 and inexpensive chemicals as raw materials through simple operations and high efficiency, in order to achieve a green recycling of CO2. Summary of the Invention

[0006] In view of the above-mentioned shortcomings of the prior art, the purpose of this invention is to provide an easily modifiable chemically recyclable carbon dioxide-based polyester, its synthesis method and application, to solve the problems of complex preparation steps, low yield, high cost, low molecular weight of the prepared polyester, and low performance of related polyester products, such as low transparency and low stability in the prior art.

[0007] To achieve the above and other related objectives, the present invention provides a carbon dioxide-based polyester poly(δLH2), wherein the carbon dioxide-based polyester poly(δLH2) comprises repeating units as shown in Formula 4 below:

[0008]

[0009] Where n is a positive integer greater than or equal to 1.

[0010] The carbon dioxide-based polyester poly(δLH2) includes linear, cyclic, and star-shaped topologies.

[0011] Another object of the present invention is to provide the use of the polyester compounds described above in the preparation of polyurethanes or pressure-sensitive adhesives.

[0012] Another object of the present invention is to provide a method for synthesizing a carbon dioxide-based polyester poly(δLH2), the method comprising: δLH2 as shown in Formula 1, in an organic base as a catalyst, and a reagent R providing an active proton. 14 (OH)m and / or (MO) m R 14 Under the condition of using an initiator, the carbon dioxide-based polyester poly(δLH2) shown in Formula 2 was synthesized.

[0013] The reaction process is shown in reaction formula I:

[0014]

[0015] Reaction I

[0016] Among them, R 14 It 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.

[0017] M is K, Na, Li, Rb, or Cs;

[0018] n is a positive integer greater than or equal to 1;

[0019] m is a positive integer greater than or equal to 1;

[0020] The organic base is selected from one or more of phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups.

[0021] Another object of the present invention is to provide a carbon dioxide-based polyester poly(δLH2) synthesized by the method described above.

[0022] Another object of the present invention is to provide the use of an organic base in the synthesis of a carbon dioxide-based polyester poly(δLH2) of Formula 2 from δLH2 of Formula 1, wherein the organic base is selected from one or more of phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups.

[0023] Another object of the present invention is to provide a method for recovering δLH2 from carbon dioxide-based polyester poly(δLH2) of catalytic formula 2, the method comprising catalytic method and pyrolysis method;

[0024] The catalytic method includes: using at least one compound selected from inorganic salts, organometallic compounds, or organic compound catalysts to degrade the carbon dioxide-based polyester poly(δLH2) shown in Formula 2, and recovering δLH2 or its oligomer or derivative shown in Formula 1;

[0025] The pyrolysis method includes: heating and cracking the carbon dioxide-based polyester poly(δLH2) shown in Formula 2 to recover δLH2 or its oligomer or its derivative shown in Formula 1.

[0026] Another object of the present invention is to provide a method for preparing a disubstituted α,β-saturated six-membered ring lactone. The method uses a disubstituted α,β-unsaturated six-membered ring lactone as a raw material, a Stryker reagent or a mixture of reagents capable of generating a Stryker reagent in situ as a catalyst, and an organosilane as a hydrogen source, to prepare the lactone through a selective reduction reaction of a conjugated olefin. The selective reduction reaction process is shown in reaction formula A.

[0027]

[0028] Reaction A

[0029] Another object of the present invention is to provide a method for preparing δLH2 as described above for use in the preparation of carbon dioxide-based polyester poly(δLH2) or polyurethane or pressure-sensitive adhesives as shown in Formula 2.

[0030] As described above, the easily modifiable, chemically recyclable carbon dioxide-based polyester, its synthesis method, and its applications of the present invention have the following advantages:

[0031] Beneficial effects:

[0032] The method for preparing carbon dioxide-based polyester poly(δLH2) provided by this invention uses δLH2 as shown in Formula 1 as raw material, and employs an organic base as a catalyst and / or a reagent capable of providing active protons, such as R. 14 (OH)m and / or (MO) m R 14 Using a catalyst as an initiator, a ring-opening polymerization reaction is carried out to obtain a polyester polymer compound with controllable polymer molecules in one step. The preparation method of poly(δLH2) is simple, has high yield, and strong controllability; the catalyst used is simple to prepare, low in cost, and has good activity.

[0033] This invention allows for the control of the molecular weight and molecular weight distribution of the polyester compound poly(δLH2) by adjusting the types of raw materials, the amounts of each reagent, the reaction temperature, and the reaction time. The resulting poly(δLH2) is a flexible material that can be completely degraded into monomers. This polyester material also possesses excellent physicochemical properties, such as high transparency, high molecular weight, strong thermal stability, and good ductility.

[0034] The present invention provides a method for synthesizing CO2-based chemically recyclable polyester materials. This method utilizes readily available and inexpensive C1 source carbon dioxide and the bulk chemical product 1,3-butadiene as raw materials. First, a six-membered ring lactone δLH2 is synthesized, followed by ring-opening polymerization to synthesize the poly(δLH2). This method effectively mitigates the greenhouse effect. By chemically recovering the poly(δLH2), the monomer δLH2 is obtained, achieving a closed-loop green cycle.

[0035] The polyester material prepared by this invention has excellent ability to be modified and modified after polymerization. Poly(δLH2) can be modified after polymerization by post-modification methods, such as grafting olefin side chains of poly(δLH2) through photo-induced thiol-olefin click reaction, thereby regulating the properties of the polymer.

[0036] The present invention provides a method for preparing disubstituted α,β-saturated six-membered ring lactones such as δLH2, using disubstituted α,β-unsaturated six-membered ring lactones such as δ-L as raw materials, Stryker reagent or a mixture of reagents capable of generating Stryker reagent in situ as catalysts, and organosilane as a hydrogen source, through the selective reduction reaction of conjugated olefins. The method for preparing δLH2 has high yield, simple steps, and low cost.

[0037] The methods for preparing poly(δLH2) and δLH2 described in this invention have great application prospects in the field of materials, especially in the field of polymer materials. Attached Figure Description

[0038] Figure 1 This section describes the current state of poly(δLH2) synthesis and the technical approach outlined in this invention.

[0039] Figure 2 The image shows the 1H NMR spectrum of δLH2 prepared in Example 1.

[0040] Figure 3 The image shows the carbon NMR spectrum of δLH2 prepared in Example 1.

[0041] Figure 4 The hydrogen NMR spectrum of poly(δLH2) prepared in Example 8.

[0042] Figure 5 GPC curve of poly(δLH2) prepared in Example 9.

[0043] Figure 6 This is a superimposed GPC curve of poly(δLH2) prepared in Examples 13-16; where KOMe corresponds to Example 10, NaOMe corresponds to Example 13, and KO... t Bu corresponds to Example 14, NaO t Bu corresponds to Example 15, LiO t Bu corresponds to Example 16.

[0044] Figure 7 The hydrogen NMR spectrum of poly(δLH2) prepared in Example 10.

[0045] Figure 8 The carbon NMR spectrum of poly(δLH2) prepared in Example 10.

[0046] Figure 9 The NMR hydrocarbon HSQC plot of poly(δLH2) prepared in Example 10 is shown.

[0047] Figure 10 GPC diagrams of poly(δLH2) prepared in Examples 10-12.

[0048] Figure 11 The TGA curve of poly(δLH2) prepared in Example 6 is shown.

[0049] Figure 12 The TGA curve of poly(δLH2) prepared in Example 9 is shown.

[0050] Figure 13 The TGA curve of poly(δLH2) prepared in Example 10 is shown.

[0051] Figure 14 The TGA curve is for poly(δLH2) prepared in Example 11.

[0052] Figure 15 The DSC curve of poly(δLH2) prepared in Example 6 is shown.

[0053] Figure 16 The DSC curve of poly(δLH2) prepared in Example 11 is shown.

[0054] Figure 17 The image shows the appearance and light transmittance of poly(δLH2) prepared in Example 12, as used in Application Example 1.

[0055] Figure 18The degradation results of poly(δLH2) prepared in Example 8 are used in Example 18.

[0056] Figure 19 This is a graph showing the changes in GPC curves before and after modification of the poly(δLH2) sample prepared in Example 8, used in the post-polymerization modification experiment of Application Example 3 / Example 19.

[0057] Figure 20 The 1H NMR spectrum of purified poly(δLH2-SAr) is shown in the post-polymerization modification experiment of Application Example 3 / Example 19.

[0058] Figure 21 The fluorescence emission spectra of the poly(δLH2) samples prepared in Example 8 before and after modification are used in the post-polymerization modification experiment of Application Example 3 / Example 19.

[0059] Figure 22 The diagram shows the pattern imprinting experiment and the actual mask in the post-polymerization modification experiment of Example 3 / Example 19.

[0060] Figure 23 For the post-polymerization modification experiment in Application Example 3 / Example 19, the pattern imprinting experiment was conducted.

[0061] Figure 24 In the post-polymerization modification experiment of Application Example 3 / Example 19, the contact angle between water and the glass substrate was 55.7° (the scale bar in the upper left corner is 1 mm; the marked angle values ​​are 55.7° (left) and 55.5° (right)).

[0062] Figure 25 The hydrophilicity and hydrophobicity test diagram of one of the poly(δLH2) samples in the post-polymerization modification experiment of Application Example 3 / Example 19 (the contact angle between the three poly(δLH2) samples and water is 72.8±0.08°), the scale bar in the upper left corner is 0.5mm in size, and the marked angle values ​​are 72.8° (left) and 73.3° (right).

[0063] Figure 26 The hydrophilicity and hydrophobicity test diagram of one of the poly(δLH2-SAr) samples in the post-polymerization modification experiment of Application Example 3 / Example 19 (the contact angle between the three poly(δLH2-SAr) samples and water is 93.0±0.99°). The scale bar in the upper left corner is 1mm in size, and the marked angle values ​​are 94.4° (left) and 94.6° (right) respectively. Detailed Implementation

[0064] 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.

[0065] This invention aims to propose a highly efficient multi-step reaction strategy for the first time, thereby achieving the synthesis of a chemically recyclable carbon dioxide-based polyester poly(δLH2) from CO2 and butadiene. The invention uses CO2 and butadiene as raw materials to synthesize δ-L, and then selectively reduces δ-L with conjugated olefins to prepare a six-membered ring lactone with terminal olefin groups in its side chain—3-ethyl-6-vinyltetrahydro-2H-pyran-2-one (δLH2). Furthermore, through the ring-opening polymerization of this unusual six-membered ring lactone with dual-substituted groups, the synthesis of a carbon dioxide-based polyester poly(δLH2) is achieved for the first time. This polyester exhibits high CO2 content (preferably up to 29 wt%), good transparency, high molecular weight, and high thermal stability. This polyester can be completely degraded back to monomer with the participation of a catalyst. Furthermore, due to the presence of terminal olefin side chains in the repeating units of this polyester, the present invention allows for easy post-polymerization modification of the polymer poly(δLH2). For example, the present invention can graft olefin side chains onto poly(δLH2) via a photo-initiated thiol-olefin click reaction, thereby regulating the polymer properties. The synthetic route of the carbon dioxide-based polyester poly(δLH2) of the present invention is shown in reaction route 1; the current status of carbon dioxide-based polyester poly(δLH2) synthesis and the technical route of the present invention are discussed in [link to relevant documentation]. Figure 1 .

[0066]

[0067] Reaction route (1) Synthetic route of carbon dioxide-based polyester poly(δLH2)

[0068] This invention provides a disubstituted α,β-saturated six-membered ring lactone, the structure of which is shown in Formula 6 below:

[0069]

[0070] 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; R1 and R2 may be the same or different.

[0071] The halogen is selected from fluorine, chlorine, bromine, and iodine.

[0072] 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.

[0073] The substituted alkyl group is a substituted linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0074] The alkenyl group is a linear alkyl group, a branched alkyl group, or a cycloalkyl group; further, the alkenyl group can be a C2-C20 alkenyl group; or it can be a C2-C10 alkenyl group, including vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl; preferably, it is a vinyl group.

[0075] The substituted alkenyl group is a substituted linear alkenyl group, a branched alkenyl group, or a cycloalkenyl group.

[0076] The alkynyl group is a linear alkynyl group, a branched alkynyl group, or a cycloalkynyl group; further, the alkynyl group can be a C2-C20 alkynyl group; or it can be a C2-C10 alkynyl group, including ethynyl, propynyl, butynyl, pentynyl, hexynyl, hepynyl, octyynyl, nonynyl, and decynyl; preferably, it is an ethynyl group.

[0077] The substituted alkynyl group is a substituted linear alkynyl group, a branched alkynyl group, or a cyclic alkynyl group.

[0078] 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.

[0079] Preferably, R1 is a C1-C20 alkyl group, and R2 is selected from a C2-C20 alkenyl group; more preferably, R1 is a C1-C10 alkyl group (which can be C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 alkyl groups), and R2 is selected from a C1-C10 alkenyl group (which can be C2, C3, C4, C5, C6, C7, C8, C9, or C10 alkenyl groups). Even more preferably, R1 is methyl, and R2 is vinyl.

[0080] The present invention also provides a method for preparing a disubstituted α,β-saturated six-membered ring lactone as shown in Formula 6. The method uses a disubstituted α,β-unsaturated six-membered ring lactone as shown in Formula 5 as a raw material, Stryker reagent or a mixed reagent capable of generating Stryker reagent in situ as a catalyst, and organosilane as a hydrogen source, and prepares the lactone through a selective reduction reaction of conjugated olefins.

[0081]

[0082] Reaction A

[0083] R1 and R2 are defined as described in Equation 6 above.

[0084] The disubstituted α,β-saturated six-membered ring lactone is a six-membered ring lactone with bisubstituted groups.

[0085] In some embodiments, the disubstituted α,β-saturated six-membered ring lactone is a mixture of diastereomers.

[0086] The chemical formula of the Stryker reagent is [(Ph3P)CuH]6.

[0087] The mixed reagent capable of generating Stryker reagent in situ includes CuXp and phosphine ligands; wherein p = 0, 1, 2, and X represents any one of halogen atoms, anionic species, or ligand compounds; preferably, X represents halogen atoms such as F, Cl, Br, I, or anionic species such as sulfate, sulfite, bisulfite, nitrate, acetate, etc., or ligand compounds such as acetylacetone anion, bis(benzylacetone), triphenylphosphine, triethylphosphine, triethoxyphosphine, BINAP, etc.

[0088] The organosilane is a compound containing silicon-hydrogen bonds; preferably, the organosilane is SiH. q (R0) t Where q and t are integers within the range of 0 to 5, and q + t = 4, the R0 group can represent halogen atoms such as fluorine, chlorine, bromine, and iodine, or it can refer to one or more of different substituents such as 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 and polyheterocyclic aromatics refer to groups containing two or more monocyclic aromatics.

[0089] The halogen is selected from fluorine, chlorine, bromine, and iodine.

[0090] 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.

[0091] The substituted alkyl group is a substituted linear alkyl group, a branched alkyl group, or a cycloalkyl group.

[0092] 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.

[0093] More preferably, R0 is a C1-C20 alkyl group, and even more preferably, R0 is a C1-C10 alkyl group, which can be a C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10 alkyl group.

[0094] In the preparation method of the disubstituted α,β-saturated six-membered ring lactone of the present invention, the Stryker reagent can be generated in situ from CuXp and a phosphine ligand; wherein p = 0, 1, 2, X refers to halogen atoms such as F, Cl, Br, I, or anionic species such as sulfate, sulfite, bisulfite, nitrate, acetate, etc., or ligand compounds such as acetylacetone anion, bis(dibenzylacetone), triphenylphosphine, triethylphosphine, triethoxyphosphine, BINAP, etc. The preparation method of the disubstituted α,β-saturated six-membered ring lactone as shown in Formula 6 is shown in the following reaction formula A-1:

[0095]

[0096] Reaction formula A-1

[0097] The mass ratio of the disubstituted α,β-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), for example, it can be (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); More preferably, it is (3-10):(0.08-0.3):(8-15); Even more preferably, it is 5:0.11:11.9.

[0098] The temperature of the selective reduction reaction is not particularly limited, as long as it enables the preparation of the disubstituted α,β-saturated six-membered ring lactone. In some embodiments, the reaction temperature is 0–50°C, and can be 0–10, 10–20, 20–30, 30–40, or 40–50°C. Preferably, it is 10–40°C. More preferably, it is 15–35°C, for example, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, or 35°C. Even more preferably, it is room temperature (25 ± 5°C). Even more preferably, it is 25°C.

[0099] The time for the selective reduction reaction is not particularly limited, as long as it achieves the preparation of the disubstituted α,β-saturated six-membered ring lactone. In some embodiments, 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, or 120h-160h. Preferably, the reaction time is 1h-10h. More preferably, it is 2-8h. Even more preferably, it is 6h.

[0100] The solvent for the selective reduction reaction is selected from one or more of 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, and dimethyl sulfoxide. Preferably, it is toluene.

[0101] Preferably, the process for preparing disubstituted α,β-saturated six-membered ring lactones according to the present invention is carried out under stirring conditions.

[0102] Preferably, the process for preparing disubstituted α,β-saturated six-membered ring lactones according to the present invention specifically includes dissolving Stryker reagent and organosilane in a solvent, and then adding δ-L dropwise to the mixture to carry out the reaction.

[0103] In one specific embodiment, when R1 is methyl and R2 is vinyl in reaction formula A, such as the disubstituted α,β-saturated six-membered ring lactone of formula 6 being δLH2, its preparation method is shown in reaction formula A-2 below:

[0104]

[0105] Reaction A-2

[0106] In another specific embodiment, when R1 is methyl and R2 is vinyl in reaction formula A, such as the disubstituted α,β-saturated six-membered ring lactone of formula 6 being δLH2, its preparation method is shown in reaction formula A-3 below:

[0107]

[0108] Reaction formula A-3

[0109] The present invention also provides a carbon dioxide-based polyester poly(δLH2), wherein the carbon dioxide-based polyester poly(δLH2) comprises the following:

[0110] The repeating unit shown in Equation 4:

[0111]

[0112] Where 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.

[0113] The carbon dioxide-based polyester poly(δLH2) includes various topological structures such as linear, cyclic, and star-shaped.

[0114] Preferably, the structure of the carbon dioxide-based polyester poly(δLH2) is as shown in Formula 2:

[0115]

[0116] R 14 It 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 units with a molecular weight of 100,000 g / mol or less.

[0117] As a preferred option, R 14 It can represent aromatic groups, including phenyl, naphthyl, anthracene, phenanthrene, pyrene, benzo[a]pyrene and their derivatives, etc.; specifically, R 14 The following compounds can be selected from: phenyl, benzyl, mestribenzyl, 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, mestriethylphenyl, o-diethylphenyl, m-diethylphenyl, p-diethylphenyl, 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, mestri-n-propylphenyl, o-di-n-propylphenyl, m-di-n-propylphenyl, p-di-n-propylphenyl, 1,2,3-tri-n-propylphenyl, 1,2,4-tri-n-propylphenyl, 1,2,3... At least one of the following: 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, mesitylecithinylpropylphenyl, o-diisopropylphenyl, m-diisopropylphenyl, p-diisopropylphenyl, 1,2,3-triisopropylphenyl, 1,2,4-triisopropylphenyl, 1,2,3,4-tetraisopropylphenyl, 1,2,3,5-tetraisopropylphenyl, 1,2,4,5-tetraisopropylphenyl, penta-isopropylphenyl, hexa-diisopropylphenyl, 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, p-di-tert-butylphenyl.

[0118] As a preferred option, R 14It can also be a straight-chain or branched alkane; more preferably, R 14 It can be linear or branched alkanes with 10 or fewer carbon atoms, as well as alkyl substituents containing individual unsaturated bonds (unsaturated bonds refer to those that undergo SP). 2 Hybridized carbon-carbon double bonds and sp hybridized carbon-carbon triple bonds).

[0119] As a preferred option, R 14 It can also be a polymer group containing repeating units of polyvinyl alcohol or polyethylene glycol with a molecular weight of 100,000 g / mol or less.

[0120] More preferably, R 14 It is benzyl, p-dibenzyl, (CH2)3, (CH2)4.

[0121] The value of n represents the number of repeating units, where 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.

[0122] m represents the degree of branching, where 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 initiator R). 14 (OH)m and / or (MO) m R 14 (Functionality).

[0123] This invention also provides a method for synthesizing a carbon dioxide-based polyester poly(δLH2), the method comprising the steps of: δLH2 as shown in Formula 1, in an organic base as a catalyst, and a reagent R providing an active proton. 14 (OH)m and / or (MO) m R 14 Under the condition of using an initiator, carbon dioxide-based polyester poly(δLH2) as shown in Formula 2 was synthesized; the reaction process is shown in Formula I.

[0124]

[0125] Reaction I

[0126] Among them, R 14 The definition is the same as described above.

[0127] When an organic base acts as a catalyst and / or a reagent that provides active protons acts as an initiator, it means that the method described in this invention can be carried out in the presence of both a catalyst and an initiator, or it can be carried out only under the initiator condition. When only an initiator is used without a catalyst, preferably, the initiator is (MO). m R 14 、or R 14 (OH)m and (MO) m R 14 A mixture containing one or more R 14 (OH)m and one or more (MO) compounds m R 14 In some preferred embodiments, the mixture contains an R 14 (OH)m and a kind of (MO) m R 14 .

[0128] The carbon dioxide-based polyester poly(δLH2) of the present invention can also be synthesized under organic base catalyst conditions without the addition of an initiator.

[0129] In reaction formula I, the organic base can be a sterically hindered or non-nucleophilic base.

[0130] Preferably, the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:

[0131]

[0132] 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.

[0133] 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.

[0134] Preferably, the catalyst is one or more phosphazenes. 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:

[0135]

[0136] 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.

[0137] y is a positive integer greater than or equal to 1. Preferably, 1 ≤ y ≤ 3.

[0138] Preferably, the phosphazene is selected from... t Bu-P1、 t Bu-P2, t The structures of Bu-P4 are shown below:

[0139]

[0140] In reaction formula I, the initiator is a reagent R that can provide an active proton. 14 (OH)m and / or (MO) m R 14 , where R 14It 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 units with a molecular weight of 100,000 g / mol or less.

[0141] As a preferred option, R 14 This can represent linear or branched alkanes with 10 or fewer carbon atoms, as well as alkyl substituents containing individual unsaturated bonds (unsaturated bonds refer to those that undergo sp). 2 Hybridized carbon-carbon double bonds and sp-hybridized carbon-carbon triple bonds), aromatic groups.

[0142] As a further optimization, R 14 It can represent C1-C10 alkyl groups; aromatic groups, including phenyl, naphthyl, anthracene, phenanthrene, pyrene, benzo[a]pyrene and their derivatives, etc.; specifically, R can be selected from methyl, ethyl, propyl, isopropyl, phenyl, benzyl, mestribenzyl, 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, mesitylene, o-diethylphenyl, m-diethylphenyl, p-diethylphenyl, 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, o-di-n-propylphenyl, m-di-n-propylphenyl, p-di-n-propylphenyl, 1 2,3-Tri-n-propylphenyl, 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 At least one of 3,4-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.

[0143] More preferably, R 14 It is benzyl or methyl.

[0144] More preferably, M is K, Na, Li, Rb, or H.

[0145] More preferably, the initiator is selected from benzyl alcohol (BnOH), potassium methoxide (KOMe), sodium methoxide (NaOMe), and potassium tert-butoxide (KOMe). t Bu), sodium tert-butoxide (NaO) t Bu), lithium tert-butoxide (LiO) t Bu).

[0146] In reaction 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.

[0147] In reaction formula I, m represents 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 initiator R). 14 (OH)m and / or (MO) m R 14 (Functionality).

[0148] In the method of the present invention, the molar ratio of Formula 1, catalyst, and initiator is (5-200):(0-5):(0-1); the molar ratio of catalyst and initiator is not 0 at the same time. Preferably, it is (25-200):(0-1):(0-1); more 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):(0.5-0.6):(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); More preferably, it is 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.

[0149] The method described in this invention can be carried out under solvent-free conditions (i.e., bulk conditions) and solvent conditions.

[0150] 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).

[0151] When carried out under solvent conditions, the initial concentration of the solvent in the reaction of Formula 1, [δLH2]0, is 1-7 M; preferably, 3-7 M; more preferably, 5-6 M; even more preferably, 5.5-6 M; even more preferably, 5.62 or 5.82 M;

[0152] In the method described in this invention, the reaction temperature is not particularly limited, as long as the preparation of the carbon dioxide-based polyester poly(δLH2) 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.

[0153] In the method described in this invention, the reaction time is not particularly limited, as long as the preparation of the carbon dioxide-based polyester poly(δLH2) 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 12-48 h.

[0154] The carbon dioxide-based polyester poly(δLH2) includes various topological structures such as linear, cyclic, and star-shaped.

[0155] In the method described in this invention, when the initiator R 14 (OH)m and / or (MO) m R 14 When m is 1, a monohydroxy-terminated carbon dioxide-based polyester poly(δLH2) is generated; when the initiator is R 14 (OH)m and / or (MO) m R 14 When m is an integer greater than 1, a polyhydroxy-terminated carbon dioxide-based polyester poly(δLH2) is generated; the reaction formula is shown below:

[0156]

[0157] Reaction I

[0158] The present invention also provides a carbon dioxide-based polyester poly(δLH2) prepared by the above method.

[0159] The poly(δLH2) described in this invention is a flexible material with a variety of excellent physicochemical properties, including high transparency, high molecular weight, strong thermal stability, and good ductility. Based on this, this invention also provides the application of the carbon dioxide-based polyester poly(δLH2) or the carbon dioxide-based polyester poly(δLH2) prepared by the above method in the fields of polyurethane and pressure-sensitive adhesives.

[0160] 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.

[0161] 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.

[0162] 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 poly(δLH2) prepared in this invention, an inexpensive 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.

[0163] 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, which cannot be degraded after use. This invention, poly(δLH2), exhibits relatively good pressure-sensitive adhesive properties. Furthermore, because poly(δLH2) allows for the chemical recovery of its monomers, it has the potential to become the first pressure-sensitive adhesive on the market capable of monomer recovery, demonstrating a promising industrialization prospect.

[0164] This invention also provides the application of organic bases such as phosphazenes in the catalytic synthesis of the carbon dioxide-based polyester poly(δLH2) of Formula 2, as described above, from compounds of Formula 1. The organic base may be a sterically hindered or non-nucleophilic base.

[0165] Preferably, the organic base is an amine compound or a nitrogen-containing heterocyclic compound; the amine compound has the following formula:

[0166]

[0167] 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.

[0168] 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-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.

[0169] 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:

[0170]

[0171] 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.

[0172] y is a positive integer greater than or equal to 1. For example, 1≤y≤10, 10≤y≤20; preferably, 1≤y≤3.

[0173] More preferably, the phosphazene is selected from... t Bu-P1、 t Bu-P2, t The structures of Bu-P4 are shown below:

[0174]

[0175] The present invention also provides a method for recovering monomers from a catalytic polymer carbon dioxide-based polyester poly(δLH2), the method comprising catalysis and pyrolysis.

[0176] In the method described in this invention, when recovering δLH2 monomer from polymer Poly(δLH2), the reaction process is shown in reaction formula IV below:

[0177]

[0178] Reaction IV

[0179] In this invention, the catalytic method includes: in a solvent, using a catalyst such as a salt, organometallic compound, or organic compound to degrade the carbon dioxide-based polyester poly(δLH2) as shown in Formula 2, to obtain the heterocyclic compound, oligomer, or corresponding derivative of Formula 1 shown in Formula 1.

[0180] 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-dibromobenzene toluene, m-xylene, p-xylene, o-xylene, mesitylene, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; preferably, it is toluene or o-dichlorobenzene; more preferably, it is toluene.

[0181] 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, La[N(SiMe3)2]3, lanthanum trichloride, lanthanum alumina, lanthanum fluoride, lanthanum boride, lanthanum sulfate, lanthanum hydroxide, lanthanum carbonate, lanthanum oxalate, lanthanum acetate, lanthanum bromide, lanthanum nitrate, etc.; preferably, it is zinc chloride.

[0182] 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.

[0183] 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), and 1,3-di-methylene-imidazolium-2-ide (IMes). t Bu-P1、 t Bu-P2, t One or more of Bu-P4, etc.; preferably, DBU.

[0184] Preferably, the catalyst is an inorganic salt; more preferably, it is a lanthanum salt; even more preferably, it is La[N(SiMe3)2]3.

[0185] The degradation conditions are described as a hot bath method such as an oil bath or sand bath, with a temperature range of 100-300℃; preferably 120-180℃; more preferably 120℃.

[0186] The degradation time is 0.5-24h; preferably 0.5-8h; preferably 1-5h; preferably 2h.

[0187] In this invention, the pyrolysis method includes: heating and cracking the carbon dioxide-based polyester poly(δLH2) as described above to obtain the heterocyclic compound or its oligomer or the corresponding derivative of Formula 1.

[0188] Preferably, the thermal pyrolysis is carried out in a nitrogen atmosphere.

[0189] Preferably, the thermal pyrolysis is carried out under sealed conditions.

[0190] Preferably, the thermal pyrolysis is carried out under vacuum conditions.

[0191] 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 monomer of carbon dioxide-based polyester poly(δLH2). 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.

[0192] In this invention, the heating time is not limited, as long as the purpose of heating and pyrolysis can be achieved to recover the monomer of carbon dioxide-based polyester poly(δLH2). 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.

[0193] In a preferred embodiment, the step of using a catalytic method to catalyze the carbon dioxide-based polyester poly(δLH2) to recover the monomer δLH2 includes: catalytically cracking the carbon dioxide-based polyester poly(δLH2) of Formula 2 in toluene at 120°C for 2 hours using La[N(SiMe3)2]3 to obtain δLH2 of Formula 1 or its oligomer or a corresponding derivative of Formula 1.

[0194] In the method described in this invention, when the catalytic polymer poly(δLH2) recovers the δ-L monomer, the reaction process is shown in the following reaction formula IV:

[0195] 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.

[0196] 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.

[0197] The present invention does not limit the δ-L raw materials used in the following examples. They can be commercially available or prepared by the following methods: δ-L is synthesized from CO2 and 1,4-butadiene under Pd catalysis, and δ-L is synthesized under Stryker reagent catalysis and triethoxysilane (HSi(OEt)3) as hydrogen source. The reaction process is shown in the following reaction route (2).

[0198]

[0199] Reaction route (2)

[0200] To prepare the target monomer δLH2, this invention uses δ-L as raw material, Stryker reagent ([(Ph3P)CuH]6) as catalyst, triethoxysilane (His(OEt)3) as hydrogen source, and stirs in toluene solution for 6 h at room temperature, thus successfully preparing the δLH2 monomer for the first time.

[0201] Example 1 Preparation of δLH2 monomer

[0202] In a glove box under a nitrogen atmosphere, 109.7 mg (0.17 mol%) of Stryker's reagent and 11.9 g (2.2 equiv) of triethoxysilane were placed in a round-bottom flask, and 250 mL of toluene was added to dissolve them. The mixture was stirred at room temperature for 0.5 h. Next, approximately 5.0 g of δ-L was added dropwise to the flask, and the reaction was continued at room temperature for 6 h after the addition was complete. After the reaction was completed, the flask was removed from the glove box, and a large amount of saturated sodium bicarbonate solution was added to quench the reaction. The mixture was then extracted three times with chloroform and sodium bicarbonate solutions. The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was then separated by column chromatography (petroleum ether / ethyl acetate = 8 / 1). The obtained pure product was a colorless oily liquid. Its proton NMR spectrum and carbon NMR spectrum are shown below. Figures 2-3 As shown. The present invention achieves a yield of 83% for preparing δLH2 monomer, and the diastereomeric ratio of the obtained product is 55 / 45. The product is a colorless oily liquid.

[0203]

[0204] Reaction formula A-4

[0205] Examples 2-8 : t Bu-P4-catalyzed ring-opening polymerization of δLH2

[0206] This invention uses t Bu-P4 phosphazene catalyst was used as a catalyst for the anionic ring-opening polymerization of δLH2. t With a feed ratio of Bu-P4] = 500 / 1, the reaction was carried out in a THF solution at -25°C for 24 hours with stirring ([δLH2]0 = 5.82M). The conversion rate of δLH2 was 84%, and the resulting polymer poly(δLH2) had a high molecular weight M. n =246.0 kgmol -1 and a relatively wide molecular weight distribution ( Example 2If benzyl alcohol (BnOH) is used as the added alcohol initiator, and the polymerization reaction is carried out at a feed ratio of [δLH2] / [BnOH] molar ratio of 50 / 1, as the equivalent amount of phosphazene catalyst added decreases (from 2, 1, 0.4 to 0.2 mol%), the molecular weight and molecular weight distribution of the resulting polymer tend to decrease, that is, the molecular weight approaches the molecular weight calculated by the feed ratio. Examples 3-6 Similarly, if the benzyl alcohol initiator is replaced with dibenzyl alcohol, a similar trend in molecular weight and molecular weight distribution will be observed. Examples 7-8, The 1H NMR spectrum of poly(δLH2) prepared in Example 8 is shown below. Figure 4 (As shown).

[0207] Example 2

[0208] In a glove box under a nitrogen atmosphere, take 0.00134 mmol of... t The Bu-P4 catalyst was added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.016 mL of THF to dissolve the catalyst. 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 -25°C cryogenic bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.67 mmol of δLH2 was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 24 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 poly(δLH₂) 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 poly(δLH₂). 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 poly(δLH₂) 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.

[0209] Example 3

[0210] In a glove box under a nitrogen atmosphere, take 0.0134 mmol of... tBu-P4 catalyst and 0.0134 mmol of BnOH initiator were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.016 mL of THF 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 -25°C cryogenic bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.67 mmol of δLH2 was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 12 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 poly(δLH₂) 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 poly(δLH₂). 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 poly(δLH₂) 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.

[0211] Examples 4-6

[0212] The preparation steps are the same as in Example 3, except that... t The equivalent of the Bu-P4 catalyst was changed: Example 4 (0.0067 mmol), Example 5 (0.00268 mmol), and Example 6 (0.00134 mmol).

[0213] Example 7

[0214] The preparation steps are the same as in Example 3, except that the BnOH initiator in Example 3 is replaced with diphenylethanol (Ph2CHOH) initiator.

[0215] Example 8

[0216] The preparation steps are the same as in Example 6, except that the BnOH initiator in Example 6 is replaced with diphenylethanol (Ph2CHOH) initiator.

[0217] Encouraged by the initial ring-opening polymerization results, this invention further investigated the feasibility of using several alkali metal alkoxides as ROP initiators. Initially, in THF solution, this invention used KOMe (potassium methoxide) and BnOH as co-initiators, with a [δLH2] / [KOMe] / [BnOH] molar ratio of 50 / 0.5 / 1, achieving a δLH2 conversion rate of 86%. The resulting poly(δLH2) had a molecular weight of M. n =73.4 kg mol -1 The molecular weight distribution is as follows ( Example 9 This invention infers that this somewhat uncontrollable polymerization behavior may be caused by the competitive dual initiation of KOMe and BnOK after the addition of BnOH. Figure 5 Subsequently, using only KOMe as an initiator, the reaction was tested in THF at -25°C for 24 h at a feed ratio of [δLH2] / [KOMe] = 50 / 1. The conversion rate reached 94%, and the resulting poly(δLH2) had a very high molecular weight M. n = 442.8 kg mol -1 and a fairly narrow molecular weight distribution ( Example 10 ).

[0218] Examples 9-12: Ring-opening polymerization of δLH2 initiated by methanol as an initiator

[0219] Example 9

[0220] In a glove box under nitrogen atmosphere, 0.0067 mmol of KOMe initiator and 0.0134 mmol of BnOH initiator were added to a flame-dried 10 mL Schlenk tube, followed by the addition of 0.02 mL of THF for dissolution. 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 cryogenic bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.67 mmol of δLH2 was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 24 hours. 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 poly(δLH₂) 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 poly(δLH₂). 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 poly(δLH₂) 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.

[0221] Example 10

[0222] In a glove box under nitrogen atmosphere, 0.0134 mmol of KOMe initiator was added to a flame-dried 10 mL Schlenk tube, followed by 0.02 mL of THF for dissolution. 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 cryogenic bath until temperature equilibrium was reached. Once equilibrium was achieved, 0.67 mmol of δLH2 was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 24 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 poly(δLH₂) 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 poly(δLH₂). 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 poly(δLH₂) 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.

[0223] Example 11

[0224] The preparation steps were the same as in Example 10, except that the equivalent amount of KOMe initiator was reduced to 0.0067 mmol.

[0225] Example 12

[0226] The preparation steps were the same as in Example 10, except that the reaction time was extended to 48 h and the equivalent amount of KOMe initiator was reduced to 0.00335 mmol.

[0227] Table 1. Results of ring-opening polymerization of δLH2 catalyzed by different systems

[0228]

[0229] Next, under the same polymerization conditions, this invention screened several other common alkali metal alkoxides, including NaOMe and K2O. t Bu, NaO tBu and LiO t Bu( Figure 6 As shown in Tables 1 and 2, the poly(δLH2) prepared by KOMe and NaOMe initiation exhibits high molecular weight and ideal controllability. Example 10 and Figures 7-9 M n = 442.8 kg mol -1 , Example 13 M n = 534.6 kg mol -1 , As for KO t Bu and NaO t Bu, the bimodal distribution clearly detected in the GPC curve is likely due to the presence of a rapid and uncontrollable transesterification reaction in the system. Examples 14-15 ). By LiO t The poly(δLH2) prepared by Bu initiation exhibits a significantly reduced molecular weight and a narrow molecular weight distribution, but the monomer conversion rate also decreases accordingly, indicating that LiO t Bu is an initiator with low reactivity but good controllability. Example 16 Furthermore, in THF at -25°C, as the feed equivalent of KOMe decreased from 2 mol% to 1.0 mol% and 0.5 mol%, respectively, the M of the resulting polymers... n It increased slightly, but the molecular weight distribution remained very narrow. Figure 10 , Examples 10-12 Using 0.5 mol% KOMe ( Example 12 M n = 587.7 kg mol -1 , This generates poly(δLH2) with a very high molecular weight and a very low molecular weight distribution.

[0230] Examples 13-16 Ring-opening polymerization of δLH2 involving different alkali metal alkoxide initiators

[0231] The preparation steps are the same as in Example 10, except that KOMe is replaced: Example 13 (sodium methoxide, NaOMe), Example 14 (potassium tert-butoxide, KOMe). t Bu), Example 15 (Sodium tert-butoxide, NaO) t Bu), Example 16 (lithium tert-butoxide, LiO) t Bu).

[0232] Table 2 Results of ring-opening polymerization of δLH2 initiated by different initiator systems

[0233]

[0234] Example 17: Thermodynamic properties

[0235] The thermodynamic stability of poly(δLH2) prepared under different conditions can be analyzed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).

[0236] First, adopt t Bu-P4 was used as a catalyst and BnOH as an initiator (Example 6), and no catalyst was added, only the initiator KOMe was added (Example 7). 9～11 The poly(δLH2) prepared by this method all exhibited good thermal stability (5% thermogravimetric temperature was greater than 300℃). TGA curves revealed the T... d,5％ and T max It is related to the molecular weight of the sample. Its T max All are between 370 and 376℃. Figures 11-14 These correspond to Examples 6, 9, 10, and 11, respectively. However, Example 6 uses... t Bu-P4 t Sample T was prepared using Bu-P4 as a catalyst and BnOH as an initiator. d,5％ The temperature was 20-30°C lower than that of samples prepared using only the initiator KOMe (Examples 9-11). The main reason for this difference is likely due to the large molecular weight difference between the polymers prepared by the two systems.

[0237] The DSC curves show that the TLH2 of the poly(δLH2) prepared in Examples 6 and 11... g The temperatures are -30.5℃ and -27.0℃ respectively. picture 15-16 correspond to Examples 6 and 11, respectively. The second heating and first cooling curves of the sample at 10℃ / min only show the glass transition temperature (T). g The absence of crystallization and melting endothermic peaks indicates that this poly(δLH2) material is an amorphous polymer.

[0238] Application Example 1: Appearance and light transmittance of poly(δLH2) samples

[0239] To verify the appearance and light transmittance of the poly(δLH2) sample, the present invention prepared a strip-shaped material by hot pressing the sample obtained in Example 12. This material is a flexible, colorless, and transparent material with good ductility. picture 17 ).

[0240] Application Example 2 Chemical recycling

[0241] Next, the chemical recyclability of the poly(δLH2) sample was investigated (Example 18). The test sample selected was... Example 8 The poly(δLH2)(M) prepared in n =11.7kg mol -1 , In toluene, 5 mol% of the test sample La[N(SiMe3)2]3 was added as a catalyst, and the initial monomer concentration [δLH2]0 was controlled to be 0.18 M. After heating at 120 °C for 2 h, the polymer sample could be completely degraded into δLH2 monomer.

[0242] Example 18 Chemical recycling experiment

[0243] In a glove box under a nitrogen atmosphere, 200 mg of poly(δLH2) sample (prepared in Example 8) and 5 mol% La[N(SiMe3)2]3 were placed in a 50 mL Schlenk tube, and then 7.2 mL of toluene 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 120°C oil bath for heating and stirring for 2 hours. The solvent in the system was then removed, and 10 mg of the degradation product was taken out for further processing. 1 δLH2 yield was analyzed by H NMR, see Figure 18 .

[0244] Application Example 3 Post-aggregation modification

[0245] Because poly(δLH2) has a large number of olefin functional groups in its side chains, this invention allows for the regulation of polymer properties through post-polymerization modification. Photo-induced click chemistry between thiols and olefins is a good post-polymerization modification method. In this invention, a solution of poly(δLH2) sample, p-trifluoromethylthiophenol, and dimethyl benzoate was prepared, then coated onto a uniform thin film, and the film was irradiated with ultraviolet light at wavelengths of 254 nm and 365 nm for 12 hours. Example 19 NMR analysis revealed that approximately 87% of the olefin functional groups reacted, and GPC curves also showed a significant increase in the molecular weight of the polymer sample. Figure 19 In addition, the 1H NMR signal reveals a significant attenuation of the olefin signal in the poly(δLH2-SAr) sample, as well as the generation of characteristic signals for phenyl and thioether bonds. Figure 20 ).

[0246] Example 19 Photo-initiated click chemistry of thiols and alkenes

[0247] In air, 100 mg of poly(δLH2) sample (prepared according to Example 8), 5.0 equivalents of p-trifluoromethylthiophenol, and 10 mol% benzoin dimethyl ether were placed in a 10 mL sample vial, and then 0.5 mL of dichloromethane was added to dissolve them. After stirring for about 15 min, the solution was cast onto a circular PTFE mold. After the solvent evaporated, the formed film was placed under ultraviolet light at wavelengths of 254 and 365 nm and irradiated overnight. After sufficient irradiation time, the film was dissolved with a small amount of dichloromethane, reprecipitated multiple times with n-hexane, and dried. The resulting product was the polymerized and modified poly(δLH2-SAr).

[0248] Interestingly, during the photo-initiated thiol-olefin click chemistry reaction, this invention discovered that the film exhibited very pronounced blue fluorescence under 365 nm ultraviolet light irradiation. Therefore, this invention further characterized the optical properties of the synthesized poly(δLH2-SAr) using photoluminescence spectroscopy. Under 360 nm ultraviolet light excitation, a photoluminescence peak was detected at approximately 410 nm. Figure 21 In stark contrast, the poly(δLH2) sample did not exhibit this luminescence. Figure 22 The pattern imprinting experiment shown demonstrates the convenience of this optical modification. In this invention, a mask with a centrally cutout "CO2" pattern is placed over a photoresponsive thin film (containing poly(δLH2), p-trifluoromethylthiophenol, and dimethyl benzoate), and then exposed to ultraviolet light overnight. After illumination, a fluorescent "CO2" pattern appears on the photoresponsive thin film, while the area covered by the mask remains non-luminescent. Figure 23 This demonstrates that the generation of fluorescence is attributed to a successful thiol-olefin click chemistry reaction.

[0249] Similarly, this post-modification is also a means to easily alter the hydrophilic and hydrophobic properties of polymers. Testing showed that the contact angle between ultrapure water and the glass substrate was 55.7°. Figure 24 The contact angle between poly(δLH2) and ultrapure water is 72.8 ± 0.08°. Figure 25 However, the contact angle between poly(δLH2-SAr) containing fluorine atoms and ultrapure water reached 93.0 ± 0.99°. Figure 26 Perhaps it is because the trifluoromethyl group was grafted onto the polymer side chain that the post-modified poly(δLH2-SAr) exhibits significantly more hydrophobic material properties.

[0250] Example 20 Polyurethane was synthesized from δLH2 monomers via a one-pot, two-step process.

[0251] In a glove box under nitrogen atmosphere, 0.0063 mmol of tBu-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, placed in a pre-set -25°C ice bath until temperature equilibrium was reached. Once equilibrium was reached, 0.63 mmol of δLH2 was rapidly injected into the Schlenk tube using a syringe, and the mixture was stirred for 12 h. Then, 0.0063 mmol of diphenyl phosphate solution was added to quench the reaction, and the system was transferred to 50°C for equilibrium. After reaching equilibrium, the temperature was maintained for 5 min. Finally, 23.39 mg of 4,4'-methylenebis(phenyl isocyanate) was rapidly added to the system using a syringe, and the system was immediately returned to the -25°C ice bath to continue the reaction for 24 h. After the reaction was completed, the reaction system was diluted with 5 mL of tetrahydrofuran and added dropwise to a large amount of methanol that had been cooled to 0 °C beforehand. The mixture was centrifuged at 10,000 rpm for 5 min and the supernatant was discarded, keeping the solid. This process was repeated 3 times. Finally, the bottom solid was collected and dried under vacuum at 60 °C for 12 h to obtain a polyurethane sample with δLH2 as the monomer.

[0252] In summary, this invention has successfully developed a novel strategy that allows the ring-opening polymerization of a chemically recyclable polyester derived from CO2 and inexpensive, readily available olefins, consisting of a six-membered ring disubstituted lactone (δLH2). The tunable properties of this chemically recyclable polyester offer significant new opportunities for the future development of novel polymer materials, thereby meeting the urgent need for carbon-neutral production of new polymers and a circular economy for materials.

[0253] The above embodiments are for illustrating the implementation schemes disclosed in this invention and should not be construed as limiting the invention. Furthermore, various modifications listed herein, as well as variations in the methods and compositions of the invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. Although the invention has been specifically described in conjunction with various specific preferred embodiments, it should be understood that the invention should not be limited to these specific embodiments. In fact, various modifications as described above that are obvious to those skilled in the art to obtain the invention should be included within the scope of this invention.

Claims

1. A carbon dioxide-based polyester poly(δLH2), characterized in that, The carbon dioxide-based polyester poly(δLH2) comprises repeating units as shown in Formula 4 below: Where n is a positive integer greater than or equal to 1; The carbon dioxide-based polyester poly(δLH2) includes various topologies, including linear, cyclic, and star-shaped.

2. The carbon dioxide-based polyester poly(δLH2) as described in claim 1, characterized in that, The structure of the carbon dioxide-based polyester poly(δLH2) is shown in Formula 2: Among them, R 14 It is selected from any one of the following: C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 ynyl, substituted C2-C20 ynyl, 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; n is a positive integer greater than or equal to 1; m is a positive integer greater than or equal to 1.

3. The use of the carbon dioxide-based polyester poly(δLH2) as described in any one of claims 1 to 2 in the preparation of polyurethane or pressure-sensitive adhesives.

4. A method for synthesizing a carbon dioxide-based polyester poly(δLH2), characterized in that, The method includes: δLH2 as shown in Formula 1, with an organic base as a catalyst and a reagent R providing active protons. 14 (OH)m and / or (MO) m R 14 Under the condition of using an initiator, the carbon dioxide-based polyester poly(δLH2) shown in Formula 2 was synthesized. The reaction process is shown in reaction formula I: Among them, R 14 It is selected from any one of the following: C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 ynyl, substituted C2-C20 ynyl, 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; M is K, Na, Li, Rb, or Cs; 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 selected from one or more of phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups.

5. The synthesis method as described in claim 4, characterized in that, The phosphazene is a strong Lewis base containing a (R₂N)₂-P=N structure; the phosphazene structure is shown in Formula 3: In Equation 3, R3-R 10 Selected independently from C1-C 10 Alkyl group; y is a positive integer greater than or equal to 1.

6. The synthesis method according to claim 4, characterized in that, The phosphazene is selected from t Bu-P1、 t Bu-P2, t At least one of Bu-P4 has the following structure: 。 7. The synthesis method according to claim 4, characterized in that, The method includes any one or more of the following features 1) to 5): 1) The statement 1≤m≤10; 2) The molar ratio of Formula 1, organic base, and initiator is (5-200): (0-5): (0-1); and the amounts of organic base and initiator are not both 0. 3) 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, 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; 5) The reaction temperature is -100~200℃; 6) The reaction time is 10 s-360 h.

8. The synthesis method according to claim 4, characterized in that, The method includes any one or more of the following features 1) to 6): 1) The phosphazene is t Bu-P4; 2) The initiator is benzyl alcohol (BnOH), potassium methoxide (KOMe), sodium methoxide (NaOMe), or potassium tert-butoxide (KOMe). t Bu), sodium tert-butoxide (NaO) t Bu), lithium tert-butoxide (LiO) t One or more of the following: Bu; 3) The molar ratio of Formula 1, organic base, and initiator is (25-200): (0-1): (0-1); and the amounts of organic base and initiator are not both 0; 4) The solvent for the reaction is THF; 5) The reaction temperature is -80~200℃; 6) The reaction time is 1 min to 120 h.

9. A carbon dioxide-based polyester poly(δLH2), characterized in that, The carbon dioxide-based polyester poly(δLH2) is synthesized by the method described in any one of claims 4 to 8.

10. The use of an organic base in the catalytic synthesis of a carbon dioxide-based polyester poly(δLH2) of Formula 2 from δLH2 of Formula 1, characterized in that, The organic base is selected from one or more of phosphazenes, compounds containing guanidine groups, and compounds containing amidine groups; wherein, the structures of δLH2 shown in Formula 1 and the carbon dioxide-based polyester poly(δLH2) shown in Formula 2 are as follows: Among them, R 14 It is selected from any one of the following: C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 ynyl, substituted C2-C20 ynyl, 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; n is a positive integer greater than or equal to 1; m is a positive integer greater than or equal to 1.

11. A method for recovering δLH2 from carbon dioxide-based polyester poly(δLH2) of catalytic formula 2, characterized in that, The methods include catalysis and pyrolysis. Among them, R 14 It is selected from any one of the following: C1-C20 alkyl, substituted C1-C20 alkyl, C2-C20 alkenyl, substituted C2-C20 alkenyl, C2-C20 ynyl, substituted C2-C20 ynyl, 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; n is a positive integer greater than or equal to 1; m is a positive integer greater than or equal to 1; The catalytic method includes: using at least one compound selected from inorganic salts, organometallic compounds, or organic compound catalysts to degrade the carbon dioxide-based polyester poly(δLH2), and recovering the δLH2 or its oligomer or its derivative. The pyrolysis method includes: heating and cracking the carbon dioxide-based polyester poly(δLH2) to recover the δLH2 or its oligomer or its derivative.

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