Cyclophosphazene skeleton-based multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex catalyst as well as preparation method and application of cyclophosphazene skeleton-based multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex catalyst

Abstract

The invention relates to the technical field of catalysts, in particular to a polycentric metal multi-quaternary ammonium salt bifunctional porphyrin complex catalyst based on a cyclophosphazene framework and a preparation method and application thereof.The catalyst comprises the cyclophosphazene framework, the cyclophosphazene framework is connected with a metalloporphyrin complex LA and a quaternary ammonium salt group LB through phosphorus atoms, according to the catalyst, the distance between a reaction active center and a cocatalyst is shortened and fixed, the reaction activity is greatly improved, the catalyst is particularly suitable for the reaction of propylene oxide and carbon dioxide, and the catalyst has excellent catalytic activity (TOF / h <-1 >) which can reach 106 orders of magnitude when being used for telomerization synthesis of carbon dioxide-based polyol. The number of metal centers of the complex and the number of quaternary ammonium salts can be accurately adjusted, so that catalysts with different reaction activities are obtained. The complex can be used for catalytically preparing polyhydric alcohols with ultrahigh activity while maintaining high selectivity at a high temperature.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a catalyst based on a cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex, its preparation method and application. Background Technology

[0002] The copolymerization of carbon dioxide and epoxy compounds to prepare carbon dioxide-based polyols is an effective way to utilize abundant carbon dioxide resources. This not only reduces greenhouse gas emissions but also decreases dependence on non-renewable fossil fuels. In this field, the carbonate ether coexistence structure of the carbon dioxide-based polyols obtained through this copolymerization reaction gives the synthesized carbon dioxide-based polyurethanes superior properties such as high mechanical strength, hydrolysis resistance, and oxidation resistance, making them widely applicable in coatings, adhesives, elastomers, foams, and fibers.

[0003] Since Asano of Japan first reported the telomerization of carbon dioxide and propylene oxide to prepare polyols in 1985, various catalytic systems have been developed, such as zinc dicarboxylic acid complex catalysts, bimetallic cyanide catalysts, rare earth ternary catalysts, metalloporphyrin catalysts, metal Salen catalysts, polynuclear metal complex catalysts with macrocyclic ligands, and organoboron catalysts. These catalytic systems have greatly improved the activity and selectivity of polymerization reactions. However, current catalysts have relatively low activity and often use toxic co-catalysts such as PPNCl. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a catalyst based on a cyclophosphamide framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex, its preparation method and application. The catalyst based on the cyclophosphamide framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex provided by the present invention can prepare polyols with low molecular weight and narrow molecular weight distribution, and the activity is as high as 10. 5 Order of magnitude.

[0005] To achieve the above objectives, the present invention provides a catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex, comprising: a cyclophosphonitrile framework, wherein the cyclophosphonitrile framework is connected to a metal porphyrin complex LA and a quaternary ammonium salt group LB via phosphorus atoms;

[0006] The cyclophosphonitrile skeleton is selected from hexachlorocyclotriphosphonitrile, octachlorocyclotetraphosphonitrile or decachlorocyclopentaphosphonitrile;

[0007] The metalloporphyrin complex LA has the structure shown in Formula I:

[0008]

[0009] R1 is selected from O or NH;

[0010] R2~R 20 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups;

[0011] M is a metal atom;

[0012] X is selected from halogens, -NO3, ClO 4- -CN, N3, substituted or unsubstituted acetate, substituted or unsubstituted phenol oxo anion, substituted or unsubstituted benzoate, substituted or unsubstituted benzenesulfonate or substituted or unsubstituted borate;

[0013] The quaternary ammonium salt group LB has the structure shown in Formula II:

[0014]

[0015] Y is an anion;

[0016] p and q are independently selected from any integers between 1 and 7;

[0017] * indicates the connection point.

[0018] Optionally, the LA has the structure shown in Formula II-a:

[0019]

[0020] R1 is selected from O or NH;

[0021] R6, R 11 R 16 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups;

[0022] M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium;

[0023] X is selected from halogens, -NO3, ClO 4- -CN, N3, substituted or unsubstituted acetate, substituted or unsubstituted phenol oxo anion, substituted or unsubstituted benzoate, substituted or unsubstituted benzenesulfonate or substituted or unsubstituted borate;

[0024] * indicates the connection point.

[0025] Optionally, the LA has the structure shown in Formula II-b:

[0026]

[0027] * indicates the connection point.

[0028] Optionally, the Y is selected from halogens, NO. 3- CH3COO - CCl3COO - CF3COO - ,ClO 4- BF 4- BPh 4- CN - p-Toluenebenzoate, p-Toluenesulfonate, o-Nitrophenol oxygen anion, p-Nitrophenol oxygen anion, m-Nitrophenol oxygen anion, 2,4-Dinitrophenol oxygen anion, 3,5-Dinitrophenol oxygen anion, 2,4,6-Trinitrophenol oxygen anion, 3,5-Dichlorophenol oxygen anion, 3,5-Difluorophenol oxygen anion, 3,5-Di-trifluoromethylphenol oxygen anion, or pentafluorophenol oxygen anion.

[0029] Optionally, the LB has the structure shown in Formula II-a:

[0030]

[0031] * indicates the connection point.

[0032] Optionally, the catalyst based on the cyclophosphamide framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex has the following structure:

[0033]

[0034] This invention provides a method for preparing the above-mentioned catalyst based on a multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex with a cyclophosphamide framework, comprising:

[0035] S1) The compound shown in formula a, the compound shown in formula b, and the cyclophosphonitrile compound undergo a condensation reaction, so that the cyclophosphonitrile compound is connected to the R1' residue of the compound shown in formula a and the phenolic oxygen group of the compound shown in formula b through phosphorus atoms, respectively.

[0036] S2) Quaternize the product of step S1) using the compound shown in formula c;

[0037] S3) Metal coordination was performed using metal compounds to obtain a bifunctional porphyrin complex catalyst based on a multi-center metal multi-quaternary ammonium salt cyclophosphamide framework.

[0038]

[0039] Among them, R1 ’ Selected from hydroxyl or amino groups;

[0040] R2~R 20 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups;

[0041] X ’ It is a halogen;

[0042] p and q are independent integers selected from 1 to 7.

[0043] This invention provides the application of the above-mentioned catalyst based on the cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex as a catalyst for the reaction of carbon dioxide and epoxide to prepare poly(carbonate-ether) polyols.

[0044] Optionally, the reaction temperature is 25–150°C; the reaction time is 0.5–240 h; and the carbon dioxide pressure is 0.5–6 MPa.

[0045] Optionally, the reaction includes:

[0046] Under the catalytic action of the above catalyst, carbon dioxide, epoxide and initiator are used as raw materials to carry out non-dead polymerization reaction to obtain colorless poly(carbonate-ether) polyol with narrow distribution.

[0047] The initiator includes one or more of the following: water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers;

[0048] The molar ratio of the catalyst to the epoxide is 1:(2000~2000000).

[0049] Compared with existing technologies, the catalyst provided by this invention comprises a cyclophosphonitrile framework, wherein the cyclophosphonitrile framework is connected to a metalloporphyrin complex LA and a quaternary ammonium salt group LB via phosphorus atoms. This catalyst shortens and fixes the distance between the reactive center and the co-catalyst, greatly improving the reaction activity, and is particularly suitable for the reaction of propylene oxide with carbon dioxide. This catalyst exhibits excellent catalytic activity (TOF / h) in the telomerization reaction to synthesize carbon dioxide-based polyols. -1 ), up to 10 6The number of metal centers and quaternary ammonium salts in the complex can be precisely adjusted to obtain catalysts with different reactivity. The complex can maintain high selectivity at high temperatures while catalyzing the preparation of polyols with ultra-high activity. Attached Figure Description

[0050] Figure 1 The 1H NMR spectrum of product EL1;

[0051] Figure 2 The 1H NMR spectrum of product EL2;

[0052] Figure 3 Comparison of the 1H NMR spectra of products EL2 and EL3;

[0053] Figure 4 Comparison of the 1H NMR spectra of products EL3 and EL4. Detailed Implementation

[0054] This invention provides a catalyst based on a cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex, comprising: a cyclophosphonitrile framework, wherein the cyclophosphonitrile framework is connected to a metal porphyrin complex LA and a quaternary ammonium salt group LB via phosphorus atoms.

[0055] The catalyst based on the cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex can be represented by the following general formula A:

[0056]

[0057] The cyclophosphonitrile skeleton is selected from hexachlorocyclotriphosphonitrile, octachlorocyclotetraphosphonitrile or decachlorocyclopentaphosphonitrile;

[0058] When the cyclophosphonitrile skeleton is selected from hexachlorocyclotriphosphonitrile, the total number of m and n is 6.

[0059] In some embodiments, the cyclophosphamide framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex catalyst can be represented by any of the following general formulas:

[0060] When m=5 and n=1:

[0061]

[0062] When m=4 and n=2:

[0063]

[0064] When m=3 and n=3:

[0065]

[0066] When m=2 and n=4:

[0067]

[0068] When m=1 and n=5:

[0069]

[0070] When the cyclophosphonitrile skeleton is selected from octachlorocyclotetraphosphonitrile, the total number of m and n is 8. Its specific structure can be derived from the structural formulas 01-08 of hexachlorocyclotriphosphonitrile above, and will not be repeated here.

[0071] When the cyclophosphonitrile skeleton is selected from decachlorocyclopentaphosphazene, the total number of m and n is 10. Its specific structure can be derived from the structural formulas 01-08 of hexachlorocyclotriphosphazene above, and will not be repeated here.

[0072] In this invention, the asterisk (*) indicates a connection position, specifically a connection position with a phosphorus atom in the cyclophosphamide skeleton.

[0073] The metalloporphyrin complex LA has the structure shown in Formula I:

[0074]

[0075] R1 is preferably O or NH; more preferably O.

[0076] R2~R 20 The preferred independent groups are hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C. 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups; more preferably hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C6 aliphatic groups, substituted or unsubstituted C6-C6 groups. 10 Aromatic groups, substituted or unsubstituted C1-C 10 One or more of the heteroaryl groups; more preferably, hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C3 aliphatic groups, substituted or unsubstituted phenyl or naphthyl groups; most preferably, H or halogen. The above substitution is preferably by any one or more of halogens or C1-C3 alkyl groups, more preferably by one or more of F, Cl, Br, methyl, ethyl, n-propyl, and isopropyl. The heteroatoms of the above heteroaryl groups include one or more of N, O, S, P, and Si.

[0077] M is a metal atom; preferably magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; more preferably magnesium, aluminum, zinc or chromium; and even more preferably aluminum.

[0078] X is selected from halogens, -NO3, ClO 4- -CN, N3, substituted or unsubstituted acetate, substituted or unsubstituted phenol oxyanion, substituted or unsubstituted benzoate, substituted or unsubstituted benzenesulfonate, or substituted or unsubstituted borate; the above substitution is preferably by any one or more of halogens or C1 to C3 alkyl groups, and more preferably by one or more of F, Cl, Br, methyl, ethyl, n-propyl, and isopropyl; X is most preferably a halogen or p-methylbenzenesulfonate.

[0079] In some embodiments, the LA has the structure shown in Formula II-a:

[0080]

[0081] Among them, R1, R6, R 11 R 16 The ranges of M and X are the same as those mentioned above, and will not be repeated here.

[0082] In some embodiments, the LA has the structure shown in Formula II-b:

[0083]

[0084] The quaternary ammonium salt group LB preferably has the structure shown in Formula II:

[0085]

[0086] Y is an anion; preferably halogen or NO. 3- CH3COO - CCl3COO - CF3COO - ,ClO 4- BF 4- BPh 4- CN - p-Toluenebenzoate, p-Toluenesulfonate, o-nitrophenol oxy-anion, p-nitrophenol oxy-anion, m-nitrophenol oxy-anion, 2,4-dinitrophenol oxy-anion, 3,5-dinitrophenol oxy-anion, 2,4,6-trinitrophenol oxy-anion, 3,5-dichlorophenol oxy-anion, 3,5-difluorophenol oxy-anion, 3,5-di-trifluoromethylphenol oxy-anion, or pentafluorophenol oxy-anion; more preferably, halogens, such as F, Cl, Br, etc.

[0087] p and q are preferably independent integers between 1 and 7, such as 1, 2, 3, 4, 5, 6 or 7.

[0088] In some embodiments, the LB has the structure shown in Formula II-a:

[0089]

[0090] In some embodiments, the catalyst based on a cyclophosphamide framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex has the following structure:

[0091]

[0092] This invention provides a method for preparing the above-mentioned catalyst based on a multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex with a cyclophosphamide framework, comprising:

[0093] S1) The compound shown in formula a, the compound shown in formula b, and the cyclophosphonitrile compound undergo a condensation reaction, so that the cyclophosphonitrile compound is connected to the R1' residue of the compound shown in formula a and the phenolic oxygen group of the compound shown in formula b through phosphorus atoms, respectively.

[0094] S2) Quaternize the product of step S1) using the compound shown in formula c;

[0095] S3) Metal coordination was performed using metal compounds to obtain a bifunctional porphyrin complex catalyst based on a multi-center metal multi-quaternary ammonium salt cyclophosphamide framework.

[0096]

[0097] Among them, R1 ’ Selected from hydroxyl or amino; more preferably hydroxyl.

[0098] R2~R 20 The scope is the same as described above, and will not be repeated here.

[0099] X ’ It is a halogen, such as F, Cl or Br.

[0100] p and q are independently selected from any integer between 1 and 7, such as 1, 2, 3, 4, 5, 6 or 7, or range values ​​with any of the above values ​​as the upper or lower limit.

[0101] In this invention, the compound represented by formula a can be commercially available or prepared by methods known to those skilled in the art.

[0102] In some specific embodiments, the compound represented by formula a is prepared according to the following method:

[0103] Using substituted or unsubstituted benzaldehyde compounds and pyrrole as raw materials, a condensation reaction is carried out to obtain the compound shown in formula a.

[0104] In some specific embodiments, the substituted or unsubstituted benzaldehyde compounds include 4-hydroxybenzaldehyde and 4-bromobenzaldehyde.

[0105] The preferred reaction temperature for the condensation reaction is 100–150°C, for example, it can be 100, 110, 120, 130, 140 or 150°C, or any of the above values ​​can be used as the upper or lower limit.

[0106] The reaction time of the condensation reaction is preferably 1 to 3 hours, for example, it can be 1, 1.5, 2, 2.5 or 3 hours, or any of the above values ​​can be used as the upper or lower limit.

[0107] The solvent for the condensation reaction is preferably propionic acid.

[0108] The resulting compound of formula a is then subjected to a condensation reaction with the compound of formula b and the cyclophosphonitrile compound, so that the cyclophosphonitrile compound is linked to the R1' residue of the compound of formula a and the phenolic oxygen group of the compound of formula b through phosphorus atoms, respectively.

[0109] The R1' residue of the compound shown in Formula a refers to the group after R1' loses a hydrogen atom. This group can be connected to the phosphorus atom of the cyclophosphonitrile compound, for example, it can be an oxygen atom or an imino group.

[0110] The phenolic oxygen group of the compound shown in formula b refers to the group formed after the phenolic hydroxyl group of the compound shown in formula b loses a hydrogen atom, and this group can be attached to the phosphorus atom of the cyclophosphonitrile compound.

[0111] In some specific implementations, the compound represented by formula b is maltine.

[0112] Preferably, NaH is added as an acid-binding agent in the reaction.

[0113] The solvent for the reaction is preferably tetrahydrofuran.

[0114] The reaction temperature is preferably room temperature, for example, 15 to 25°C.

[0115] The reaction time is preferably 0.2 to 1 hour, for example, it can be 0.1, 0.5 or 1 hour, or any of the above values ​​can be the upper or lower limit of the range.

[0116] The reaction preferably uses cesium carbonate as a catalyst.

[0117] After the condensation reaction, the product of step S1) is quaternized using the compound shown in formula c. Specifically, the N atom of the structure of formula b after being linked with the cyclophosphonitrile compound is quaternized.

[0118] The present invention does not specify the specific method of the quaternization treatment, and can be any quaternization scheme known to those skilled in the art.

[0119] In some specific embodiments, the compound shown in formula c and the product of step S1) are contacted in a solvent and subjected to a quaternization reaction.

[0120] The solvent is preferably tetrahydrofuran.

[0121] The preferred reaction temperature for the quaternization reaction is 30–70°C, for example, it can be 30, 40, 50, 60 or 70°C, or any of the above values ​​can be the upper or lower limit.

[0122] The preferred reaction time for the quaternization reaction is 48 to 84 hours, for example, 48, 60, 72 or 84 hours, or any of the above values ​​as the upper or lower limit.

[0123] Finally, metal coordination can be performed.

[0124] The present invention does not impose any special limitation on the metal compound used for metal coordination selection, and can be a M-containing halide well known to those skilled in the art, such as chloride, bromide, etc.

[0125] In some specific embodiments, the metal compound is diethylaluminum chloride.

[0126] The preferred temperature for metal coordination is room temperature, for example, 15–25°C.

[0127] The metal coordination time is preferably 1 to 3 hours, for example, it can be 1, 2 or 3 hours, or any of the above values ​​can be the upper or lower limit of the range.

[0128] The preferred solvent for metal coordination is dichloromethane.

[0129] The reactions in steps S1), S2), and S3) above are preferably carried out in an inert gas atmosphere, which includes, but is not limited to, nitrogen, argon, etc.

[0130] The present invention also provides the application of the above-mentioned catalyst based on the cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex, or the catalyst based on the cyclophosphonitrile framework multicenter metal multiquaternary ammonium salt bifunctional porphyrin complex prepared by the above preparation method, as a catalyst for the reaction of carbon dioxide and epoxide to prepare poly(carbonate-ether) polyols.

[0131] The preferred temperature for the reaction is 25 to 150°C, for example, 25, 30, 50, 70, 90, 110, 130°C, or any of the above values ​​as the upper or lower limit.

[0132] The reaction time is 0.5 to 240 hours, more preferably 1 to 50 hours, for example, it can be 1 hour, 10 hours or 50 hours, or any of the above values ​​can be the upper or lower limit of the range.

[0133] The pressure of the carbon dioxide is 0.5 to 6 MPa, more preferably 3 to 5 MPa, for example, it can be 3, 4 or 5 MPa, or any of the above values ​​can be the upper or lower limit of the range.

[0134] Preferably, the reaction includes:

[0135] Under the catalytic action of the above catalyst, carbon dioxide, epoxide and initiator are used as raw materials to carry out non-dead polymerization reaction to obtain colorless poly(carbonate-ether) polyol with narrow distribution.

[0136] In some specific embodiments, under anhydrous and oxygen-free conditions, the epoxide, initiator, and the above-mentioned catalyst are mixed, and then carbon dioxide is added to carry out the reaction, yielding a narrowly distributed light-colored poly(carbonate-ether) polyol. The above reaction exhibits high reactivity.

[0137] The initiator preferably includes one or more of the following: water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers. The small molecule alcohol is preferably one or more of the following: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, octanediol, decanediol, dipropylene glycol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolpropane, glycerol, 1,2,4-butanetriol, polyester triol, pentaerythritol, xylitol, sorbitol, tripentapentolol, or polyglycidol oligomers. The phenol is preferably one or more of the following: catechol, resorcinol, hydroquinone, pyrogallol, 4,4'-ethylidene bisphenol, 4,4'-(2-methylpropylidene)bisphenol; 4,4-(2-ethylhexylidene)bisphenol, 2,2'-methylene bisphenol, or 2,2'-(1,2-cyclohexadiylbisnitrosylethylene)bisphenol. The thiol is preferably one or more of the following: n-dodecylthiol, n-octylthiol, tert-dodecylthiol, mercaptoethanol, thiophene, or p-toluenethiophenol. The carboxylic acid is preferably one or more of the following: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid, trimesic acid, trimesic acid, or oleic acid. The hydroxy acid is preferably one or more selected from lactic acid, hydroxybutyric acid, hydroxyvalerate, hydroxysuccinic acid, tartaric acid, citric acid, or salicylic acid. The hydroxyl-containing oligomer is preferably polyglycerol.

[0138] The molar ratio of the catalyst to the epoxide is preferably 1:(2000-2000000), more preferably 1:(10000-1000000), for example, it can be 1:20000, 1:30000, 1:100000 or 1:500000, or any of the above values ​​as the upper or lower limit.

[0139] Experimental results demonstrate that the catalyst provided by this invention, when used in the aforementioned polyol synthesis method, can achieve a TOF value of up to 50,000 h⁻¹. -1 .

[0140] In order to improve reaction activity and reduce the use of toxic co-catalysts, this invention links the catalyst and co-catalyst to a single molecule through a chemical chain, which can greatly improve the activity and selectivity of the catalyst.

[0141] To further illustrate the present invention, a detailed description is provided below with reference to embodiments. However, it should be understood that these descriptions are merely for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims.

[0142] There are no particular restrictions on the source of any raw materials used in this invention; they can be purchased from the market or prepared using conventional methods known to those skilled in the art.

[0143] Example 1

[0144]

[0145]

[0146] 15 g (120 mmol) of 4-hydroxybenzaldehyde, 68.1 g (370 mmol) of 4-bromobenzaldehyde and 33 g (490 mmol) of pyrrole were added to 500 mL of propionic acid. The mixture was refluxed at 130 °C for 1.5 h and then cooled to room temperature. 500 mL of methanol was added, and the product was filtered and purified by silica gel column chromatography to obtain the intermediate compound with a yield of approximately 20%.

[0147] Under nitrogen protection, 0.863 mol of maltol, 0.431 mmol of hexachlorotriphosphazene, and 1.73 mmol of sodium hydride were added to 60 mL of tetrahydrofuran solution. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 50 °C for 24 h. Then, 1.73 mmol of EL1 and 5.18 mmol of cesium carbonate were added, the reaction mixture was filtered, evaporated to dryness, and column chromatography was performed to give a purple solid EL2 in 40% yield.

[0148] Under nitrogen protection, 0.059 mol EL2 and 2.37 mmol bromopentane were added to 40 mL of tetrahydrofuran solution. The reaction mixture was stirred at room temperature for 0.5 h, followed by stirring at 50 °C for 72 h. After evaporating the solvent, the mixture was washed with n-hexane to give EL3 as a purple solid, with a yield of 98%.

[0149] Under nitrogen protection, the above ligand EL3 was dissolved in dichloromethane, and AlEt2Cl (diethylaluminum chloride) was added dropwise. The mixture was stirred at room temperature for 2 hours. The resulting product was purified by column chromatography and dried to obtain the desired complex EL4.

[0150] Example 2

[0151] In a glove box, 5.3 mg of the aluminum porphyrin complex EL4 prepared in Example 1, 1344.9 mg of sebacic acid, and 20 ml of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 70°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and samples were taken immediately after opening the reactor for analysis. 1 H NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate ether polyol;

[0152] pass 1 H NMR analysis of the polycarbonate ether polyol prepared in Example 2 showed that the polycarbonate contained 57% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 7000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 2300 and the molecular weight distribution was 1.03, as determined by GPC.

[0153] Example 3

[0154] In a glove box, 5.3 mg of the aluminum porphyrin complex EL4 prepared in Example 1, 1344.9 mg of sebacic acid, and 20 ml of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 90°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect samples for analysis. 1H NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate ether polyol;

[0155] pass 1 H NMR analysis of the polycarbonate ether polyol prepared in Example 3 showed that the polycarbonate contained 49% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 18000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 2100 and the molecular weight distribution was 1.03, as determined by GPC.

[0156] Example 4

[0157] In a glove box, 5.3 mg of the aluminum porphyrin complex EL4 prepared in Example 1, 1344.9 mg of sebacic acid, and 20 ml of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 110 °C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect samples for analysis. 1 H NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate ether polyol;

[0158] pass 1 H NMR analysis of the polycarbonate ether polyol prepared in Example 4 showed that the polycarbonate contained 47% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 27000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 2500 and the molecular weight distribution was 1.01, as determined by GPC.

[0159] Example 5

[0160] In a glove box, 5.3 mg of the aluminum porphyrin complex EL4 prepared in Example 1, 1344.9 mg of sebacic acid, and 20 ml of dry propylene oxide were added to a 50 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 130°C for polymerization for 1 hour. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect samples for analysis.1 H NMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate ether polyol;

[0161] pass 1 H NMR analysis of the polycarbonate ether polyol prepared in Example 5 showed that the polycarbonate contained 37% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 34000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 2300 and the molecular weight distribution was 1.02, as determined by GPC.

[0162] Example 6

[0163] In a glove box, 0.8 mg of the aluminum porphyrin complex EL4 prepared in Example 1, 13448.9 mg of sebacic acid, and 200 ml of dry propylene oxide were added to a 500 mL high-pressure reactor that had been dehydrated and deoxygenated. The high-pressure reactor was then removed from the glove box, and carbon dioxide was introduced into the reactor through a pressure-regulating carbon dioxide supply line to bring the pressure inside the reactor to 4 MPa. The temperature of the high-pressure reactor was controlled at 110 °C for polymerization reaction for 50 h. After the polymerization reaction was completed, the carbon dioxide in the high-pressure reactor was slowly released, and the reactor was opened immediately to collect samples for analysis. 1 HNMR analysis was performed. Unreacted propylene oxide was removed in a vacuum drying oven at 45°C to obtain polycarbonate ether polyol.

[0164] pass 1 H NMR analysis of the polycarbonate ether polyol prepared in Example 5 showed that the polycarbonate contained 40% carbonate units and less than 0.1% cyclic carbonate byproducts. The calculated TOF value of the catalytic system was 15000 h⁻¹. -1 The number-average molecular weight of the prepared polycarbonate was 2400 and the molecular weight distribution was 1.02, as determined by GPC.

[0165] As can be seen from the above embodiments, the catalyst prepared by the present invention based on the cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex has extremely high activity, good product selectivity, low concentration tolerance and high temperature stability when catalyzing the preparation of polycarbonate ether polyols.

[0166] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

[0167] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A catalyst based on a cyclophosphamide framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex, comprising: A cyclophosphonitrile skeleton, wherein the cyclophosphonitrile skeleton is connected to a metal porphyrin complex LA and a quaternary ammonium salt group LB via phosphorus atoms; The cyclophosphonitrile skeleton is selected from hexachlorocyclotriphosphonitrile, octachlorocyclotetraphosphonitrile, or decachlorocyclopentaphosphonitrile; The metalloporphyrin complex LA has the structure shown in Formula I: R1 is selected from O or NH; R2~R 20 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups; M is a metal atom; X is selected from halogens, -NO3, ClO 4- -CN, N3, substituted or unsubstituted acetate, substituted or unsubstituted phenol oxo anion, substituted or unsubstituted benzoate, substituted or unsubstituted benzenesulfonate or substituted or unsubstituted borate; The quaternary ammonium salt group LB has the structure shown in Formula II: Y is an anion; p and q are independently selected from any integers between 1 and 7; * indicates the connection point.

2. The catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to claim 1, characterized in that, The LA has the structure shown in formula II-a: R1 is selected from O or NH; R6, R 11 R 16 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups; M is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium; X is selected from halogens, -NO3, ClO 4- -CN, N3, substituted or unsubstituted acetate, substituted or unsubstituted phenol oxo anion, substituted or unsubstituted benzoate, substituted or unsubstituted benzenesulfonate or substituted or unsubstituted borate; * indicates the connection point.

3. The catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to claim 1, characterized in that, The LA has the structure shown in Formula II-b: * indicates the connection point.

4. The catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to claim 1, characterized in that, The Y is selected from halogens, NO. 3- CH3COO - CCl3COO - CF3COO - ,ClO 4- BF 4- BPh 4- CN - p-Toluenebenzoate, p-Toluenesulfonate, o-Nitrophenol oxygen anion, p-Nitrophenol oxygen anion, m-Nitrophenol oxygen anion, 2,4-Dinitrophenol oxygen anion, 3,5-Dinitrophenol oxygen anion, 2,4,6-Trinitrophenol oxygen anion, 3,5-Dichlorophenol oxygen anion, 3,5-Difluorophenol oxygen anion, 3,5-Di-trifluoromethylphenol oxygen anion, or pentafluorophenol oxygen anion.

5. The catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to claim 1, characterized in that, The LB has the structure shown in formula II-a: * indicates the connection point.

6. The catalyst based on a cyclophosphonitrile framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to claim 1, characterized in that, It has the following structure:

7. The preparation method of the catalyst based on the cyclophosphamide framework multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex according to any one of claims 1 to 6, comprising: S1) The compound shown in formula a, the compound shown in formula b, and the cyclophosphonitrile compound undergo a condensation reaction, so that the cyclophosphonitrile compound is connected to the R1' residue of the compound shown in formula a and the phenolic oxygen group of the compound shown in formula b through phosphorus atoms, respectively. S2) Quaternize the product of step S1) using the compound shown in formula c; S3) Metal coordination was performed using metal compounds to obtain a bifunctional porphyrin complex catalyst based on a multi-center metal multi-quaternary ammonium salt cyclophosphamide framework. Among them, R1 ’ Selected from hydroxyl or amino groups; R2~R 20 Independently selected from hydrogen, halogen, amino, nitro, cyano, substituted or unsubstituted C1-C 10 Aliphatic groups, substituted or unsubstituted C6-C 12 Aromatic groups, substituted or unsubstituted C1-C 12 One or more of the heteroaryl groups; X ’ It is a halogen; p and q are independent integers selected from 1 to 7.

8. The application of the cyclophosphonitrile-based multi-center metal multi-quaternary ammonium salt bifunctional porphyrin complex catalyst as described in any one of claims 1 to 6 as a catalyst for the reaction of carbon dioxide and epoxide to prepare poly(carbonate-ether) polyols.

9. The application according to claim 8, characterized in that, The reaction temperature is 25–150°C; the reaction time is 0.5–240 h; and the carbon dioxide pressure is 0.5–6 MPa.

10. The application according to claim 8, characterized in that, The reaction includes: Under the catalytic action of the above catalyst, carbon dioxide, epoxide and initiator are used as raw materials to carry out non-dead polymerization reaction to obtain colorless poly(carbonate-ether) polyol with narrow distribution. The initiator includes one or more of the following: water, small molecule alcohols, phenols, thiols, carboxylic acids, hydroxy acids, and hydroxyl-containing oligomers; The molar ratio of the catalyst to the epoxide is 1:(2000~2000000).

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