A polymer catalyst containing a solvated monomer and a macrocyclic chelating ligand, its preparation method and use
By preparing polymer catalysts containing solvated monomers and macrocyclic chelate ligands, constructing a solvation microenvironment, and optimizing the catalyst structure, the problems of difficult catalyst separation and low activity in the carbonylation process of epoxides were solved, and efficient β-lactone preparation was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-04-30
- Publication Date
- 2026-07-28
AI Technical Summary
Existing catalysts for the carbonylation of epoxides to prepare β-lactones suffer from problems such as difficult catalyst separation, low activity, and poor selectivity. In particular, the solvent effect is not obvious in heterogeneous catalysts, resulting in low reaction efficiency.
Polymer catalysts containing solvated monomers and macrocyclic chelate ligands are used to prepare polymer supports via free radical or Heck coupling, and metal carbonyl species are loaded to construct a solvated microenvironment, thereby optimizing the catalyst structure to enhance the effect of the active center.
The solvation effect of homogeneous catalysts was simulated in heterogeneous catalytic systems, which improved the activity and selectivity of the catalysts, promoted the conversion of epoxides to β-lactones, and solved the problems of difficult catalyst separation and low activity.
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Figure CN118437403B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of epoxide carbonylation reaction technology, specifically relating to a polymer catalyst containing a solvated monomer and a macrocyclic chelating ligand, its preparation method, and its application in the ring-expansion carbonylation preparation of β-lactone. Background Technology
[0002] β-lactone compounds, as important intermediates, have wide applications in various fields. In particular, β-lactones can serve as key monomers for the preparation of biodegradable materials such as PHA (polyhydroxyalkanoates). Besides excellent physical properties, biocompatibility, and modifiability, PHA's most unique characteristic is its biodegradability in various environments, such as soil and water, where it can be degraded by microorganisms through PHA hydrolases, making it highly environmentally friendly. There is a huge demand for PHA in China, but its price is as high as 40,000 RMB / ton, far exceeding the 10,000 RMB / ton price of polypropylene. This high cost is a key issue limiting the widespread application of PHA. The 100% atom-economical carbonylation process for preparing β-lactones from epoxy compounds is an important strategy to address the problem of high PHA costs.
[0003] Most reported catalysts for the carbonylation of epoxides to β-lactones are homogeneous catalysts, with the most classic being the homogeneous bimetallic [Lewis acid] catalyst. + [Co(CO)4] - Lewis acids are catalysts that form mononuclear metal complexes with metals at the metal center, using porphyrin (TPP) derivatives, salen derivatives, and phthalocyanine derivatives as ligands. These complexes utilize N and O atoms to form the metal. This system exhibits outstanding advantages such as selectivity and high activity. + and [Co(CO)4] - The activation of epoxides and the nucleophilic attack-activated epoxides were respectively included, mainly involving the activation of epoxides and [Co(CO)4]. - The process involves four steps: nucleophilic attack on a carbon atom, CO insertion, and ring closure. However, homogeneous processes consistently face the challenge of catalyst separation, a problem that is expected to be solved by homogeneous heterogeneous processes. Currently, there are few reported heterogeneous carbonylation systems, and their activity is relatively low (generally only 10–20 h). -1The selectivity is also poor (Inorg. Chem. 2020, 59, 2881-2889). This is mainly due to several reasons: (1) Heterogeneous catalysts have limitations in diffusion and mass transfer, which greatly reduces the catalytic rate; (2) Heterogeneous catalysts have more complex structures, and the solvent in the reaction solution is difficult to contact the catalyst fully, so the solvent effect is often not obvious in heterogeneous catalysts and cannot achieve the selectivity and activity that should be in homogeneous systems; (3) At present, epoxy compound heterogeneous catalysts mainly include Lewis acid species and carbonyl metal species. There are few reports on the relevant research on modifying or altering the support in such heterogeneous catalysts to improve the performance of the catalyst. Summary of the Invention
[0004] To address the technical problems described in the background section, the present invention aims to provide a polymer catalyst containing a solvable monomer and a macrocyclic chelate ligand, its preparation method, and its applications. The catalyst of the present invention consists of two parts: a polymer support and a metal carbonyl species. The polymer support is prepared by polymerization of a solvent monomer and a macrocyclic chelate complex. The macrocyclic chelate complex consists of a macrocyclic chelate ligand and a coordinated metal species. The polymer support can be polymerized by free radical or Heck coupling of the solvent monomer and the macrocyclic chelate complex, or by polymerizing the solvent monomer and the macrocyclic chelate ligand by free radical or Heck coupling followed by loading the metal species coordinated to the macrocyclic chelate ligand. Functionally, the catalyst consists of three parts: a polymerizable solvent monomer providing a solvation environment, a macrocyclic chelate complex acting as Lewis acid, and a metal carbonyl species acting as a carbonylation active center. The solvated monomers in the catalyst help to construct a solvation microenvironment, providing a solvation effect while optimizing the species structure of the reactive center. This can effectively accelerate the carbonylation process of epoxides and improve carbonylation activity, exhibiting excellent performance in the catalytic conversion of epoxides to β-lactones.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] This invention provides a polymer catalyst containing a solvated monomer and a macrocyclic chelating ligand. The catalyst comprises a polymer support and a metal carbonyl species. The polymer support is obtained by polymerizing the solvated monomer and the macrocyclic chelating complex via free radical or Heck coupling, or by polymerizing the solvated monomer and the macrocyclic chelating ligand via free radical or Heck coupling and then loading a metal coordinated to the macrocyclic chelating ligand. The macrocyclic chelating complex consists of a macrocyclic chelating ligand and a coordinated metal. The metal coordinated to the macrocyclic chelating ligand is selected from Cr, Al, Ga, and Ti. The precursor of the metal carbonyl species is M. 1 x [M 2 (CO)w ], where M 1 M is an alkali metal. 2 The catalyst is composed of Co, x is 1, w is 4, and the metal coordinated with the macrocyclic chelate ligand accounts for 0.01 to 5.0 wt% of the total mass of the catalyst, preferably 0.2 to 3.0 wt% of the total mass of the catalyst; Co accounts for 0.01 to 5.0 wt% of the total mass of the catalyst, preferably 0.2 to 3.0 wt% of the total mass of the catalyst.
[0007] Based on the above technical solution, further, the solvent monomer is one of the following compounds AH; the macrocyclic chelating ligand is one of the following compounds IL; and the macrocyclic chelating complex is one of the following compounds MP:
[0008]
[0009] The present invention provides a method for preparing the above-mentioned polymer catalyst containing solvated monomers and macrocyclic chelate ligands, comprising the following steps: under an inert atmosphere, dispersing a polymer support (containing a coordination metal) and a precursor of a metal carbonyl species in a solvent, stirring at -80 to 100°C for 0.1-48 h, washing, filtering, and drying to obtain a polymer catalyst containing solvated monomers and macrocyclic chelate ligands.
[0010] Based on the above technical solution, the inert atmosphere further includes argon, helium, and neon.
[0011] Based on the above technical solution, the metal carbonyl compound precursor is further selected from Na[Co(CO)4] and K[Co(CO)4].
[0012] Based on the above technical solution, the solvent is further selected from tetrahydrofuran and ethylene glycol dimethyl ether.
[0013] Based on the above technical solution, the stirring reaction conditions are further specified as -40 to 20°C, and stirring is carried out for 5 to 48 hours.
[0014] Based on the above technical solution, the polymer support is further prepared by free radical polymerization, including the following steps:
[0015] Under an inert atmosphere, one of the vinyl solvent monomers A, C, E, F, G, and H, and one of the vinyl macrocyclic chelate ligands IK are added to an organic solvent, along with a free radical initiator. The mixture is then transferred to a hydrothermal reactor and allowed to stand for 1 to 100 hours under solvothermal polymerization conditions at 60–250°C. After washing, filtration, and drying, the resulting solid and the metal precursor coordinated with the vinyl macrocyclic chelate ligand are dispersed in an organic solvent under an inert atmosphere. The mixture is stirred at 20–100°C for 1–48 hours, washed, filtered, and dried to obtain a polymer carrier (containing the coordinated metal).
[0016] Alternatively, under an inert atmosphere, one of the vinyl macrocyclic chelating ligands IK and the coordinated metal precursor are added to an organic solvent, stirred at 20-100℃ for 1-48h, washed, filtered, and dried to obtain the vinyl macrocyclic chelate metal complex MO; one of the vinyl solvent monomers A, C, E, F, G, H and one of the vinyl macrocyclic chelate metal complex MO are added to an organic solvent, and a free radical initiator is added; the mixture is transferred to a hydrothermal reactor and allowed to stand for 1-100h under solvothermal polymerization conditions at 60-250℃ for polymerization reaction, washed, filtered, and dried to obtain the polymer carrier (containing the coordinated metal).
[0017] Based on the above technical solution, the free radical initiator further includes azobisisobutyronitrile, and the weight ratio of the vinyl solvent monomer to the free radical initiator is 0.5:1 to 100:1; the molar ratio of the vinyl solvent monomer to the vinyl macrocyclic chelating ligand or the vinyl macrocyclic chelating metal complex is 0.5:1 to 20:1.
[0018] Based on the above technical solution, the inert atmosphere further includes argon, helium, and neon.
[0019] Based on the above technical solution, the organic solvent is further described as N-methylpyrrolidone or N,N-dimethylformamide.
[0020] Based on the above technical solution, the coordinated metal precursor is further one of CrCl2, CrCl3·3THF, AlCl3, diethylaluminum chloride, and GaCl3.
[0021] Based on the above technical solution, the polymer support is further prepared by polymerization via Heck coupling, including the following steps:
[0022] Under an inert atmosphere, one of the vinyl solvent monomers A, C, E, F, G, and H, along with a halogen-containing macrocyclic chelating ligand L, is added to an organic solvent; or one of the halogenated solvent monomers B and D, along with a vinyl macrocyclic chelating ligand IK, is added to an organic solvent. Triethylamine and Pd(PPh3)2Cl2 are then added, and the mixture is stirred at 50–150 °C for 1–96 h. The mixture is then washed, filtered, and dried. Under an inert atmosphere, the obtained solid and the coordinated metal precursor are dispersed in an organic solvent, stirred at 20–200 °C for 1–48 h, washed, filtered, and dried to obtain a polymer carrier (containing the coordinated metal).
[0023] Alternatively, under an inert atmosphere, one of the macrocyclic chelating ligands IL and the coordinated metal precursor are added to an organic solvent, stirred at 20-200℃ for 1-48h, washed, filtered, and dried to obtain the macrocyclic chelate complex MP; one of the vinyl solvent monomers A, C, E, F, G, H and the halogen-containing macrocyclic chelate complex P are added to an organic solvent, or one of the halogenated solvent monomers B, D and the vinyl macrocyclic chelate complex MO are added to an organic solvent, along with triethylamine and Pd(PPh3)2Cl2, and stirred at 50-150℃ for 1-96h; washed, filtered, and dried to obtain the polymer carrier (containing the coordinating metal).
[0024] Based on the above technical solution, the weight ratio of Pd(PPh3)2Cl2 to solvent monomer is 0.01:1 to 0.5:1; the molar ratio of solvent monomer to macrocyclic chelating ligand or macrocyclic chelating complex is 0.5:1 to 20:1.
[0025] Based on the above technical solution, the inert atmosphere further includes argon, helium, and neon.
[0026] Based on the above technical solution, the organic solvent is further described as N-methylpyrrolidone or N,N-dimethylformamide.
[0027] Based on the above technical solution, the coordinated metal precursor is further one of CrCl2, CrCl3·3THF, AlCl3, diethylaluminum chloride, and GaCl3.
[0028] The present invention also provides the application of the above-mentioned polymer catalyst containing solvated monomers and macrocyclic chelating ligands in the preparation of β-lactone by epoxide ring expansion carbonylation.
[0029] Based on the above technical solution, the reactor used in the carbonylation reaction process is a batch reactor; the CO pressure is 1-7.0 MPa; and the reaction temperature is 40-70℃.
[0030] Based on the above technical solution, the epoxide is further defined as ethylene oxide (EO), propylene oxide (PO), or 1,2-epoxybutane (BO), with a molar ratio of 100 to 5000 for the epoxide and catalyst; the reaction time is 1 to 12 hours; and the reaction solvent is one of ethylene glycol dimethyl ether, tetrahydrofuran, toluene, or 1,4-dioxane.
[0031] Compared with the prior art, the present invention has the following beneficial effects:
[0032] (1) The present invention introduces solvated monomers into polymers to construct solvated microenvironments, simulates the solvation effect in homogeneous phases in multiphase systems, and improves catalyst activity and selectivity.
[0033] (2) The introduction of solvation monomers optimized the structure of the catalyst and strengthened the interrelationship and interaction between Lewis acid species and solvent species.
[0034] (3) By introducing solvated monomers, the carbonylation process was accelerated from the perspectives of solvation effect and catalyst structure optimization, thereby improving carbonylation activity.
[0035] (4) The present invention also provides a variety of functionalized oxygen-containing ether monomers and methods for constructing polymers thereof. Attached Figure Description
[0036] To more clearly illustrate the embodiments of the present invention, the accompanying drawings involved in the embodiments will be briefly described below.
[0037] Figure 1 The activity of the catalyst in Example 6 for catalyzing the carbonylation reaction of PO at different cycle numbers is shown.
[0038] Figure 2 This is a transmission electron microscope image of the polymer carrier-6 in Example 6. Detailed Implementation
[0039] The present invention will be described in detail below with reference to the embodiments. However, the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some embodiments of the present invention. For those skilled in the art, other similar embodiments can be obtained without creative effort and all fall within the protection scope of the present invention.
[0040] The solvent monomer structure in the examples is shown as AH; the macrocyclic chelate ligand structure is shown as IL; and the macrocyclic chelate complex structure is shown as MP.
[0041]
[0042]
[0043] The synthesis method of AH can be found in the references (J.Mol.Catal.A,2014,392,253-259; Nat.Commun.,2018,9,3236.); the synthesis method of IP can be found in the references (J.Catal.,2016,338,202-209; Sci.Rep.,2018,8,13243).
[0044] Example 1
[0045] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer H and 1 g of porphyrin complex monomer O (Cr content 4%) were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal polymerization method for 48 h. After the polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area and hierarchical porous structure, denoted as polymer-1, was obtained. Under an inert atmosphere, 0.11 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the polymer support-1 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-1 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1.1% by ICP-OES.
[0046] Example 2
[0047] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer C and 1 g of porphyrin monomer J were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.19 g of CrCl3·3THF was dissolved in 20 ml of N,N-dimethylformamide, and the 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure -2. The Cr content was determined to be 0.9% by ICP-OES. Under an inert atmosphere, 0.1 g Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-2 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-2 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1% by ICP-OES.
[0048] Example 3
[0049] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer E and 1 g of porphyrin monomer K were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.07 g of AlCl3 was dissolved in 20 ml of N,N-dimethylformamide, and the 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure -3. The Al content was determined to be 0.5% by ICP-OES. Under an inert atmosphere, 0.1 g Na[Co(CO)4] was dissolved in ethylene glycol dimethyl ether solvent, and then the above polymer material-3 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-3 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1% by ICP-OES.
[0050] Example 4
[0051] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer F and 1 g of porphyrin complex monomer M (Al content 2%) were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area and hierarchical porous structure, denoted as polymer-4, was obtained. Under an inert atmosphere, 0.1 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then polymer material-4 was added. The mixture was stirred at -20 °C for 24 hours. After washing, filtration, and vacuum drying, the final polymer catalyst-4 containing solvated monomers and macrocyclic chelate ligands was obtained. The Co content was determined to be 1% by ICP-OES.
[0052] Example 5
[0053] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer G and 1 g of porphyrin complex monomer N (Ga content 5%) were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area and hierarchical porous structure, denoted as polymer-5, was obtained. Under an inert atmosphere, 0.1 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then polymer material-5 was added. The mixture was stirred at -20 °C for 24 hours. After washing, filtration, and vacuum drying, the final polymer catalyst-5 containing solvated monomers and macrocyclic chelate ligands was obtained. The Co content was determined to be 1% by ICP-OES.
[0054] Example 6
[0055] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer A and 1 g of porphyrin monomer I were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal polymerization method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.065 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and the 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum, yielding a polymer material with a large surface area and hierarchical porous structure -6. TEM image shown. Figure 2 As shown. The Cr content was determined to be 0.9% by ICP-OES. Under an inert atmosphere, 0.1 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-6 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-6 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1% by ICP-OES.
[0056] Example 7
[0057] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer E and 1 g of porphyrin monomer I were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.065 g of CrCl2 was added to 20 ml of N,N-dimethylformamide, followed by the addition of the 1 g solid. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, material-7. The Cr content was determined to be 0.9% by ICP-OES. Under an inert atmosphere, 0.1 g Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-7 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-7 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1% by ICP-OES.
[0058] Example 8
[0059] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer G and 1 g of porphyrin monomer I were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.07 g of CrCl2 was added to 20 ml of N,N-dimethylformamide, followed by the addition of the 1 g solid. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum, yielding a polymer material with a large surface area and hierarchical porous structure, material-8. The Cr content was determined to be 1% by ICP-OES. Under an inert atmosphere, 0.11 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-8 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-8 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.1% by ICP-OES.
[0060] Example 9
[0061] Under a protective atmosphere of 298 K and Ar, 1 g of solvent monomer A and 1 g of porphyrin monomer I were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.05 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.05 g of CrCl2 was added to 20 ml of N,N-dimethylformamide, followed by the addition of the 1 g solid. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum, yielding a polymer material with a large surface area and hierarchical porous structure, material-9. ICP-OES analysis showed a Cr content of 0.9%. Under an inert atmosphere, 0.07 g Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-9 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-9 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1% by ICP-OES.
[0062] Example 10
[0063] Under a protective atmosphere of 298 K and Ar, 2 g of solvent monomer A and 1 g of porphyrin complex monomer M (Cr content 4%) were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area structure, denoted as Polymer Material-10, was obtained. Under an inert atmosphere, 0.11 g of Na[Co(CO)4] was dissolved in ethylene glycol dimethyl ether solvent, and then Polymer Material-10 was added. The mixture was stirred at -20 °C for 24 hours. After washing, filtration, and vacuum drying, the final polymer catalyst-10 containing solvated monomers and macrocyclic chelate ligands was obtained. The Co content was determined to be 1.1% by ICP-OES.
[0064] Example 11
[0065] Under a protective atmosphere of 298 K and Ar, 0.5 g of solvent monomer A and 1 g of porphyrin monomer I were dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.04 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.04 g of CrCl2 was added to 20 ml of N,N-dimethylformamide, followed by the addition of the 1 g solid. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, material-11. The Cr content was determined to be 1% by ICP-OES. Under an inert atmosphere, 0.06 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-11 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-11 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.1% by ICP-OES.
[0066] Example 12
[0067] Under a protective atmosphere of 298 K and Ar, 1 g of solvent monomer B, 1 g of porphyrin monomer I, 45 mg of PdCl2(PPh3)2, and 6 ml of Et3N were dissolved in 10.0 ml of N,N-dimethylformamide, and the mixture was stirred at 100 °C for 72 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.06 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and the 1 g solid was added. The mixture was stirred at room temperature for 24 hours. After washing with N,N-dimethylformamide and ethanol, the mixture was filtered, and the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, -12. ICP-OES analysis showed a Cr content of 1.1%. Under an inert atmosphere, 0.08 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-12 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-12 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.2% by ICP-OES.
[0068] Example 13
[0069] Under a protective atmosphere of 298 K and Ar, 1 g of solvent monomer D, 1 g of porphyrin monomer I, 45 mg of PdCl2(PPh3)2, and 6 ml of Et3N were dissolved in 10.0 ml of N,N-dimethylformamide, and the mixture was stirred at 100 °C for 72 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.06 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and the 1 g solid was added. The mixture was stirred at room temperature for 24 hours. After washing with N,N-dimethylformamide and ethanol, the mixture was filtered, and the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure -13. The Cr content was determined to be 1.1% by ICP-OES. Under an inert atmosphere, 0.08 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-13 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-13 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.2% by ICP-OES.
[0070] Example 14
[0071] Under a protective atmosphere of 298 K and Ar, 1 g of solvent monomer B, 1.1 g of porphyrin complex monomer M (Cr content 4%), 45 mg of PdCl2(PPh3)2, and 6 ml of Et3N were dissolved in 10.0 ml of N,N-dimethylformamide and reacted at 100 °C for 72 hours. After the above polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area structure -14 was obtained. Under an inert atmosphere, 0.085 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material -14 was added. The mixture was stirred at -20 °C for 24 hours, washed, filtered, and dried to obtain the final polymer catalyst -14 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1.2% by ICP-OES.
[0072] Example 15
[0073] Under a protective atmosphere of 298 K and Ar, 0.2 g of solvent monomer A, 2 g of porphyrin monomer L, 0.45 mg of PdCl2 (PPh3)2, and 6 ml of Et3N were dissolved in 10.0 ml of N,N-dimethylformamide, and the mixture was stirred at 100 °C for 72 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.06 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing with N,N-dimethylformamide and ethanol, the mixture was filtered, and the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure -15. The Cr content was determined to be 1.1% by ICP-OES. Under an inert atmosphere, 0.09 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-15 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-15 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.2% by ICP-OES.
[0074] Example 16
[0075] Under a protective atmosphere of 298 K and Ar, 0.2 g of solvent monomer E, 2 g of porphyrin monomer L, 0.45 mg of PdCl2(PPh3)2, and 6 ml of Et3N were dissolved in 10.0 ml of N,N-dimethylformamide, and the mixture was stirred at 100 °C for 72 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.07 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing with N,N-dimethylformamide and ethanol, the mixture was filtered, and the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, -16. The Cr content was determined to be 1.1% by ICP-OES. Under an inert atmosphere, 0.09 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-16 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-16 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.2% by ICP-OES.
[0076] Example 17
[0077] Under a protective atmosphere of 298 K and N2, 2 g of solvent monomer A and 1 g of porphyrin complex monomer P (Cr content 4%) were dissolved in 10 mL of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar atmosphere using a solvothermal polymerization method for 48 h. After the polymerized solution was cooled to room temperature, washed, and vacuum dried, a polymer material with a large surface area structure, -17, was obtained. Under an inert atmosphere, 0.12 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the polymer material -17 was added. The mixture was stirred at -20 °C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst -17 containing solvated monomers and macrocyclic chelate ligands. The Co content was determined to be 1.2% by ICP-OES.
[0078] Comparative Example 1
[0079] Under a protective atmosphere of 298 K and Ar, 3 g of porphyrin monomer I was dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.07 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing and filtering with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, -18. The Cr content was determined to be 1% by ICP-OES. Under an inert atmosphere, 0.11 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-18 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-18 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.1% by ICP-OES.
[0080] Comparative Example 2
[0081] Under a protective atmosphere of 298 K and Ar, 3 g of porphyrin monomer L was dissolved in 10.0 ml of N-methylpyrrolidone solvent. 0.075 g of azobisisobutyronitrile (AIBN) as a free radical initiator was added to the solution, and the mixture was stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 473 K and Ar under a protective atmosphere using a solvothermal method for 48 hours. After the polymerized solution was cooled to room temperature, it was washed and dried under vacuum. Then, under a protective atmosphere of 298 K and N2, 0.07 g of CrCl2 was dissolved in 20 ml of N,N-dimethylformamide, and 1 g of the solid was added. The mixture was stirred at room temperature for 24 hours. After washing and filtration with N,N-dimethylformamide and ethanol, the solvent was removed under vacuum to obtain a polymer material with a large surface area and hierarchical porous structure, material-19. The Cr content was determined to be 1% by ICP-OES. Under an inert atmosphere, 0.11 g of Na[Co(CO)4] was dissolved in tetrahydrofuran solvent, and then the above polymer material-19 was added. The mixture was stirred at -20°C for 24 h, washed, filtered, and dried to obtain the final polymer catalyst-19 containing solvated monomers and macrocyclic chelate ligands. The Co content was measured to be 1.1% by ICP-OES.
[0082] Application of the catalysts prepared in Examples 1-17 and Comparative Examples 1-2 in the preparation of β-lactones from ethylene oxide, propylene oxide and 1,2-epoxybutane.
[0083] Reactor conditions: The polymer catalyst with macrocyclic chelating ligands was added to a 50 mL reactor, along with 10 mL of ultra-dry THF, and 1.76 g of ethylene oxide, 1.63 g of propylene oxide, or 1.65 g of 1,2-epoxybutane, where n EO / n Co =300, n PO / n Co =300, n BO / n Co =300, the reactor is filled with 3.0 MPa of CO, and the reaction is carried out at 60°C for 3 hours.
[0084] Offline liquid chromatography was performed using a DB-1701 capillary column and an FID detector to analyze the content of epoxides and β-lactones.
[0085] The yield, selectivity, and TOF results of carbonylation of β-lactone prepared according to the above procedures are shown in Table 1.
[0086] Table 1. Results of epoxide carbonylation reactions catalyzed by catalysts in Examples 1-17 and Comparisons 1-2
[0087]
[0088]
[0089] Note: [a]n EO / n Co ;[b]n PO / n Co ;[c]n BO / n Co
[0090] In addition, the cyclic stability of the catalyst in Example 6 was investigated. The reaction conditions were as follows: In a glove box, the catalyst and product after the catalytic carbonylation reaction of propylene oxide were separated under vacuum at 40–60°C. The separated catalyst was added to the reactor, followed by a certain amount of propylene oxide. The reactor was then purged with 3.0 MPa of CO, and the reaction was carried out at 60°C for 3 hours. The cyclic conditions were the same for each reaction. The cyclic stability of the catalyst carbonylation was tested, and the test results are as follows: Figure 1 As shown.
[0091] Comparison of the results from the examples and comparative examples shows that the catalyst with the combination of compounds A+I exhibits the best catalytic performance. The solvent monomer in this catalyst can provide a solvation environment for the heterogeneous carbonylation process of epoxides, constructing dominant carbonylation species and improving carbonylation activity. Under certain temperature and pressure conditions, this type of catalyst demonstrates excellent performance in catalyzing the conversion of epoxides to β-lactones, laying the foundation for the industrial application of epoxide carbonylation reactions.
[0092] The present invention has been described in detail above, but it is not limited to the specific embodiments described herein. Other modifications and variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims
1. A polymer catalyst containing a solvated monomer and a macrocyclic chelate ligand, characterized in that, The catalyst consists of a polymer support and a metal carbonyl species. The polymer support is obtained by free radical polymerization or Heck coupling of a solvent monomer and a macrocyclic chelate complex, or by polymerizing a solvent monomer and a macrocyclic chelate ligand by free radical polymerization or Heck coupling, followed by loading a metal coordinated to the macrocyclic chelate ligand. The macrocyclic chelate complex consists of a macrocyclic chelate ligand and a coordinated metal, with the metal selected from Cr, Al, Ga, and Ti. The precursor of the metal carbonyl species is M. 1 x [M 2 (CO) w ], where M 1 M is an alkali metal. 2 The catalyst contains Co, with x = 1 and w = 4, and the metal coordinated with the macrocyclic chelate ligand accounts for 0.01–5.0 wt% of the total catalyst mass; Co accounts for 0.01–5.0 wt% of the total catalyst mass. The solvent monomer is one of the following compounds AH; the macrocyclic chelating ligand is one of the following compounds IL; and the macrocyclic chelating complex is one of the following compounds MP. 。 2. The polymer catalyst containing a solvated monomer and a macrocyclic chelate ligand according to claim 1, characterized in that, The metal coordinated with the macrocyclic chelate ligand accounts for 0.2–3.0 wt% of the total mass of the catalyst; Co accounts for 0.2–3.0 wt% of the total mass of the catalyst.
3. The method for preparing the polymer catalyst containing solvated monomers and macrocyclic chelate ligands as described in claim 1 or 2, characterized in that, The process includes the following steps: under an inert atmosphere, the polymer support and the precursor of the metal carbonyl species are dispersed in a solvent and stirred at -80~100℃ for 0.1-48 h to obtain a polymer catalyst containing a solvated monomer and a macrocyclic chelate ligand.
4. The preparation method according to claim 3, characterized in that, The inert atmosphere includes argon, helium, and neon; the metal carbonyl compound precursor is one of Na[Co(CO)4] and K[Co(CO)4]; the solvent is one of tetrahydrofuran and ethylene glycol dimethyl ether.
5. The preparation method according to claim 3, characterized in that, The polymer support is prepared by free radical polymerization, including the following steps: Under an inert atmosphere, one of the vinyl solvent monomers A, C, E, F, G, and H and one of the vinyl macrocyclic chelating ligands IK are added to an organic solvent, along with a free radical initiator. The polymerization reaction is carried out by standing at 60–250 °C for 1–100 hours. Under an inert atmosphere, the obtained solid and the metal precursor coordinated with the vinyl macrocyclic chelating ligand are dispersed in an organic solvent and stirred at 20–100 °C for 1–48 hours to obtain a polymer carrier. Alternatively, under an inert atmosphere, one of the vinyl macrocyclic chelating ligands IK and the coordinated metal precursor are added to an organic solvent and stirred at 20-100℃ for 1-48 h to obtain the vinyl macrocyclic chelate metal complex MO; one of the vinyl solvent monomers A, C, E, F, G, H and one of the vinyl macrocyclic chelate metal complex MO are added to an organic solvent, a free radical initiator is added, and polymerization is carried out at 60-250℃ for 1-100 hours to obtain a polymer carrier.
6. The preparation method according to claim 5, characterized in that, The free radical initiator includes azobisisobutyronitrile (AIBN), and the weight ratio of the vinyl solvent monomer to the free radical initiator is 0.5:1 to 100:1; the molar ratio of the vinyl solvent monomer to the vinyl macrocyclic chelating ligand or the vinyl macrocyclic chelating metal complex is 0.5:1 to 20:1; the inert atmosphere includes argon, helium, and neon; the organic solvent is N-methylpyrrolidone or N,N-dimethylformamide; and the coordinating metal precursor is one of CrCl2, CrCl3·3THF, AlCl3, diethylaluminum chloride, and GaCl3.
7. The preparation method according to claim 3, characterized in that, The polymer support is prepared by Heck coupling polymerization, comprising the following steps: Under an inert atmosphere, one of the vinyl solvent monomers A, C, E, F, G, and H, along with a halogenated macrocyclic chelating ligand L, is added to an organic solvent; or one of the halogenated solvent monomers B and D, along with a vinyl macrocyclic chelating ligand IK, is added to an organic solvent. Triethylamine and Pd(PPh3)2Cl2 are then added, and the mixture is stirred at 50–150 °C for 1–96 h. Under an inert atmosphere, the obtained solid and the coordinated metal precursor are dispersed in an organic solvent and stirred at 20–200 °C for 1–48 h to obtain a polymer carrier. Alternatively, under an inert atmosphere, one of the macrocyclic chelating ligands IL and the coordinated metal precursor are added to an organic solvent and stirred at 20-200℃ for 1-48 h to obtain the macrocyclic chelating complex MP; one of the vinyl solvent monomers A, C, E, F, G, H and the halogen-containing macrocyclic chelating complex P are added to an organic solvent, or one of the halogenated solvent monomers B, D and the vinyl macrocyclic chelating complex MO are added to an organic solvent, along with triethylamine and Pd(PPh3)2Cl2, and stirred at 50-150℃ for 1-96 h to obtain the polymer support.
8. The preparation method according to claim 7, characterized in that, The weight ratio of Pd(PPh3)2Cl2 to solvent monomer is 0.01:1 to 0.5:1; the molar ratio of solvent monomer to macrocyclic chelating ligand or macrocyclic chelating complex is 0.5:1 to 20:1; the inert atmosphere includes argon, helium, and neon; the organic solvent is N-methylpyrrolidone or N,N-dimethylformamide; and the coordinating metal precursor is one of CrCl2, CrCl3·3THF, AlCl3, diethylaluminum chloride, and GaCl3.
9. The polymer catalyst containing solvated monomers and macrocyclic chelating ligands as described in claim 1 or 2 for the preparation of epoxide ring-expansion carbonylation β - Applications in lactones.
10. The application according to claim 9, characterized in that, The carbonylation reaction process uses a batch reactor; the CO pressure is 1~7.0 MPa; the reaction temperature is 40~70 ℃; the epoxide is ethylene oxide, propylene oxide or 1,2-epoxybutane; the reaction time is 1~12 h; the reaction solvent is one of ethylene glycol dimethyl ether, tetrahydrofuran, toluene or 1,4-dioxane.