CN105753894A - Preparation method of porphyrin aluminum complex and preparation method of polycarbonate - Google Patents

Abstract

The invention provides an aluminum-based porphyrin complex having a structure represented by formula (I) or formula (II), its preparation method and a preparation method of polycarbonate. Under the catalysis of the aluminum-based porphyrin complex main catalyst and co-catalyst provided by the present invention, carbon dioxide and epoxides carry out a copolymerization reaction to obtain polycarbonate; during this copolymerization reaction, the aluminum-based porphyrin complex acts as The main catalyst participates in the reaction process, has high catalytic activity, especially has excellent chemoselectivity (>99%), and prepares polycarbonate with low ether segment and high alternation.

Description

Preparation method of aluminum-based porphyrin complex and polycarbonate

technical field

The invention relates to the technical field of polymers, in particular to a preparation method of an aluminum-based porphyrin complex and polycarbonate.

Background technique

Since Professor Inoue of Japan first used ZnEt ₂ /H ₂ O to catalyze the reaction of CO ₂ and propylene oxide (PO) to prepare polycarbonate (PPC) in 1969, the preparation of polycarbonate has gradually attracted the attention of scientific researchers. Many efficient catalytic systems have been developed for the reaction of carbon dioxide and epoxides. Polycarbonate is a polymer containing carbonate groups in its molecular chain. It is a fully degradable polymer material with good air permeability, oxygen and water barrier properties, and has been used in biodegradable pollution-free materials, new liquid crystal materials, gas barrier materials, reinforcing agents for rubber materials, composite materials and many other fields.

Carbon dioxide and epoxide can undergo copolymerization reaction to synthesize polycarbonate under the action of a catalyst. Currently, the common catalytic systems for this copolymerization reaction include alkyl zinc-active hydrogen catalytic system, zinc carboxylate catalytic system, zinc phenate catalytic system, di A series of catalysts such as imine zinc catalyst system, double metal cyanide catalyst system, rare earth three-way catalyst system and metal porphyrin catalyst system. Among the existing catalysts, SalenCo is a catalytic system with good comprehensive catalytic performance, but metal cobalt is highly toxic, especially when it is used as a biodegradable plastic, the composting process strictly limits the cobalt residue, thus greatly limiting its application. The active center of aluminum-based porphyrin catalysts is environmentally friendly metal aluminum, which meets the needs of biodegradable plastics, and can effectively catalyze the copolymerization of carbon dioxide and epoxides. Therefore, aluminum-based porphyrin complexes have been widely used in the field of carbon dioxide and epoxide catalysts. Pay attention to.

In the copolymerization reaction of carbon dioxide and epoxide to polycarbonate catalyzed by aluminum-based porphyrin complexes, the chemical structure selectivity of polycarbonate is involved. The selectivity of the polymer chemical structure means that because the alkoxy group (-OR) also has nucleophilicity, it can attack the carbon adjacent to the oxygen atom of the peroxide. This situation is called the continuous insertion of the epoxide. When ether segments appear in the polymer chain structure, it is no longer a completely alternating structure. It is worth mentioning that the increase of polyether segment content will greatly reduce the degradation performance of the polymer. However, the two-component aluminum-based porphyrin complexes disclosed in the prior art cannot achieve high chemical structure selectivity (>99%) when catalyzing the copolymerization of carbon dioxide and epoxides, and generate highly alternating polycarbonates.

Contents of the invention

The technical problem solved by the present invention is to provide a method for preparing polycarbonate, and the polycarbonate prepared by the present application has high alternation.

In view of this, the application provides an aluminum-based porphyrin complex with a structure of formula (I) or formula (II),

Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic Group, aryl or substituted aryl;

X is selected from halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate Acid radical, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6 -one of trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion kind.

Preferably, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, chlorine, and C1-C15 fatty acids One of aromatic groups, substituted C1-C5 aliphatic groups, aryl groups with 1-3 benzene rings and halogen-substituted aryl groups with 1-3 benzene rings.

Preferably, when the aluminum-based porphyrin complex has a structure of formula (2), the preparation method of the aluminum-based porphyrin complex comprises:

The ligand compound shown in formula (1) is reacted with an organic or inorganic salt of aluminum in a solvent to obtain an aluminum-based porphyrin complex with a structure of formula (2),

Wherein, R is selected from one of hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl and substituted aryl;

The organic or inorganic salt of aluminum is selected from diethyl aluminum chloride, dimethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum dichloride and aluminum chloride kind of.

Preferably, when the aluminum-based porphyrin complex has a structure of formula (3), the preparation method of the aluminum-based porphyrin complex comprises:

Reacting a ligand compound represented by formula (1) with a solution containing an organic or inorganic salt of aluminum to obtain an aluminum-based porphyrin complex with a structure of formula (2);

Substituting the aluminum-based porphyrin complex with the structure of formula (2) obtained above with the corresponding negative ions of other substituents except chlorine to obtain the aluminum-based porphyrin complex with the structure of formula (3);

Wherein, R is selected from one of hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl and substituted aryl;

X ₁ is selected from halogens other than chlorine, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6-Trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-di-trifluoromethylphenol oxyanion, and pentafluorophenol One of the oxygen negative ions;

The organic or inorganic salt of aluminum is selected from diethyl aluminum chloride, dimethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum dichloride and aluminum chloride kind of.

Preferably, when the aluminum-based porphyrin complex has a structure of formula (5), the preparation method of the aluminum-based porphyrin complex comprises:

The ligand compound shown in formula (4) is reacted with an organic or inorganic salt of aluminum in a solvent to obtain an aluminum-based porphyrin complex with a structure of formula (5),

Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic One of family group, aryl group and substituted aryl group;

The organic or inorganic salt of aluminum is selected from diethyl aluminum chloride, dimethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum dichloride and aluminum chloride kind of.

Preferably, when the aluminum-based porphyrin complex has a structure of formula (6), the preparation method of the aluminum-based porphyrin complex comprises:

Reacting the ligand compound shown in formula (4) with an organic or inorganic salt of aluminum in a solvent to obtain an aluminum-based porphyrin complex with a structure of formula (5);

Substituting the aluminum-based porphyrin complex with the structure of formula (5) obtained above with the corresponding negative ions of other substituents except chlorine to obtain the aluminum-based porphyrin complex with the structure of formula (6);

Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic One of family group, aryl group and substituted aryl group;

X ₁ is selected from halogens other than chlorine, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6-Trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-di-trifluoromethylphenol oxyanion, and pentafluorophenol One of the oxygen negative ions;

The organic or inorganic salt of aluminum is selected from diethyl aluminum chloride, dimethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum dichloride and aluminum chloride kind of.

The application also provides a preparation method of polycarbonate, comprising:

Under the action of the main catalyst and the co-catalyst, carbon dioxide and epoxide are copolymerized to obtain polycarbonate;

The main catalyst is an aluminum-based porphyrin complex having a structure of formula (I) and/or a structure of formula (II);

The cocatalyst is selected from one or more of quaternary ammonium salts, quaternary phosphorus salts and organic bases;

Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic One of family group, aryl group and substituted aryl group;

X is selected from halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate Acid radical, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6 -one of trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion kind.

Preferably, the molar ratio of the main catalyst, co-catalyst and epoxide is 1:(0.5-1.5):(1000-10000).

Preferably, the pressure of the carbon dioxide is 0.1MPa-8MPa; the temperature of the copolymerization reaction is 20-120°C, and the time of the copolymerization reaction is 1h-12h.

Preferably, the epoxide is selected from ethylene oxide, propylene oxide, 1,2-butylene oxide, cyclohexane, cyclopentane, epichlorohydrin, glycidyl methacrylate One or more in ether, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide; The cocatalyst includes tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutyl chloride Ammonium chloride, tetrabutylammonium bisulfate, bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphine nitroamine, 4-dimethylaminopyridine and γ-chloropropylmethyl One or more of dimethoxysilanes.

The application provides a kind of preparation method of polycarbonate, and it is under the effect of procatalyst and cocatalyst, carbon dioxide and epoxide are carried out copolymerization reaction to obtain; The procatalyst that the application prepares polycarbonate has formula ( I) and or the aluminum-based porphyrin complex of the structure shown in formula (II), which has 1,2,3,4,5,6,7,8-hydrogen-1:4,5:8-dimethyl bridge The large steric hindrance of anthracene substituents; the cocatalyst includes one or more of quaternary ammonium salts, quaternary phosphonium salts and organic bases; the method for preparing polycarbonate provided by the invention is due to the use of 1,2,3,4, 5,6,7,8-Hydrogen-1:4,5:8-Dimethylpyronthracene substituted aluminum porphyrin complex is used as the main catalyst, and the introduction of the large steric hindrance substituent makes the copolymerization product of carbon dioxide and epoxide The content of polycarbonate units is significantly improved, and the experimental results show that: the aluminum porphyrin complex provided by the invention is used to catalyze carbon dioxide and epoxy compounds to carry out polymerization reaction, and the content of carbonate units of the obtained polymerization products is all higher than 99%, which shows that , Carbon dioxide and alkylene oxide are completely alternately copolymerized.

detailed description

In order to further understand the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than limiting the claims of the present invention.

The embodiment of the present invention discloses an aluminum-based porphyrin complex having a structure of formula (I) or formula (II),

Wherein, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic Group, aryl or substituted aryl;

X is selected from halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate Acid radical, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6 -one of trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion kind.

In the aluminum porphyrin complex shown in formula (I), the R is selected from one of hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl group and substituted aryl group; As a preferred version, R is selected from hydrogen, chlorine, C1-C15 aliphatic groups, substituted C1-C5 aliphatic groups, aryl groups with 1-3 benzene rings and 1 halogen-substituted benzene rings One of ~3 aryl groups; more preferably, the R is selected from hydrogen, fluorine, chlorine, iodine, methyl, ethyl, propyl, methoxy, ethoxy, propoxy, phenyl , one of biphenyl and 3-chlorophenyl. The present application has no special limitation on the groups used for R, which may be the same or different, and the present application has no special limitation on this.

X is selected from halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate Acid radical, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6 -one of trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion species; as a preferred solution, the X is preferably halogen, -NO ₃ , CH ₃ COO-, BF ₄ -, p-methylbenzoate, o-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion , 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions, 3,5-dichlorophenol oxyanions and pentafluorophenol oxyanions, more preferably halogen, One of -NO ₃ , CH ₃ COO- and BF ₄ -, most preferably -Cl.

Specifically, when R is hydrogen in formula (I), and X is -Cl, the aluminum-based porphyrin complex has the structure shown in formula (7):

When R in formula (I) is -OCH ₃ and X is -Cl, the aluminum-based porphyrin complex has the structure shown in formula (8):

In the aluminum porphyrin complex shown in formula (II), R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently One selected from hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl group and substituted aryl group; as a preferred embodiment, the R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from the group consisting of hydrogen, chlorine, aliphatic groups with 1 to 5 carbon atoms, and substituted aliphatic groups with 1 to 5 carbon atoms One of group, aryl group with 1 to 3 benzene rings, and aryl group with 1 to 3 benzene rings substituted by halogen, more preferably, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, fluorine, chlorine, iodine, methyl, ethyl, propyl, methoxy, ethoxy, propoxy One of base, phenyl, biphenyl and 3-chlorophenyl. In the present application, there is no special limitation on R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ , which may be the same or different.

X is selected from halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ -, -BF ₄ , -BPh ₄ , -CN, -N ₃ , p-toluate, p-toluenesulfonate Acid radical, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanion, 2,4,6 -one of trinitrophenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion species; as a preferred solution, the X is preferably halogen, -NO ₃ , CH ₃ COO-, BF ₄ -, p-methylbenzoate, o-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion , 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions, 3,5-dichlorophenol oxyanions and pentafluorophenol oxyanions, more preferably halogen, One of -NO ₃ , CH ₃ COO- and BF ₄ -, most preferably -Cl.

Specifically, when R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ in formula (II) are all hydrogen, and X is -Cl, then Described aluminum series porphyrin complex has structure shown in formula (9):

In the present invention, when R, R ₂ , R ₄ , R ₇ and R ₉ are hydrogen in formula (II), R ₁ , R ₃ , R ₅ , R ₆ , R ₈ and R ₁₀ are -Cl, and X is -Cl, the aluminum-based porphyrin complex has a structure shown in formula (10):

When R in formula (II) is -OCH ₃ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are all hydrogen, and X is Cl-, The aluminum-based porphyrin complex has a structure shown in formula (11):

When R in formula (II) is -OCH ₃ , R ₂ , R ₄ , R ₇ , R ₉ are hydrogen, R ₁ , R ₃ , R ₅ , R ₆ , R ₈ and R ₁₀ are -Cl, and X is - Cl, the aluminum-based porphyrin complex has a structure shown in formula (12):

The preparation method of the aluminum-based porphyrin complex with the structure of formula (I) described in the application comprises the following steps:

A), under anhydrous and oxygen-free reaction conditions, compound A and pyrrole are dissolved in a solvent, and the first reaction is carried out under the action of a catalyst to obtain the first compound; the first compound is mixed with 2,3-dichloro- 5,6-dicyano-1,4-p-benzoquinone is subjected to a second reaction to obtain a second compound having a structure shown in formula (1);

The structural formula of the compound A is

Wherein, R is selected from one of hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl group or substituted aryl group.

B), the second compound obtained in A) and the metal salt compound are subjected to a third reaction in a solvent to obtain an aluminum-based porphyrin complex having a structure shown in formula (I); X in the formula (I) is Halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ , BF ₄ -, BPh ₄ -, -CN, -N ₃ , p-toluate, p-toluenesulfonate, o-nitrate phenylphenol oxyanions, p-nitrophenol oxyanions, m-nitrophenol oxyanions, 2,4-dinitrophenol oxyanions, 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions One of phenol oxyanion, 3,5-dichlorophenol oxyanion, 3,5-difluorophenol oxyanion, 3,5-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion;

In step A), under the action of a catalyst, compound A is reacted with pyrrole for the first time, and the obtained first product is reacted with 2,3-dichloro-5,6-dicyano-1,4-p-benzoquinone (DDQ) is subjected to a second reaction to obtain a second compound having the structure of formula (1). In step A) among the present invention, the catalyst is preferably trifluoroacetic acid and or boron trifluoride ether, most preferably trifluoroacetic acid; the solvent is preferably dichloromethane, more preferably dry dichloromethane; the The molar ratio of compound A, pyrrole, catalyst, solvent and 2,3-dichloro-5,6-dicyano-1,4-p-benzoquinone is preferably (0.5～1.5):1:(2～4) : (1200～1800): (1～3); more preferably (0.8～1.2): 1: (2.5～3.5): (1200～1800): (1～3); most preferably 0.9:1:2.8: 1500:2;

In step A), in order to make the reaction more complete, the process for preparing the second compound is specifically:

Add compound A and pyrrole to the solvent to obtain a mixed solution, then add the catalyst to the mixed solution to perform the first reaction, after the first reaction is completed, add DDQ to the first reaction product to perform the second reaction , to obtain a second compound of formula (1).

In the above process, the temperature of the first reaction is preferably 20°C to 40°C, more preferably 25°C to 35°C; the time of the first reaction is preferably 0.5h to 1.5h, more preferably 1h; The temperature of the second reaction is preferably 20°C-40°C, more preferably 25°C-35°C; the time of the second reaction is preferably 0.5h-1.5h, more preferably 1h;

After the second reaction is completed, the present invention preferably removes the solvent from the obtained second reaction product in vacuo to obtain a crude product of the second compound, and further purifies the obtained crude product to obtain a pure product of the second compound. The present invention has no special limitation on the above-mentioned vacuum solvent removal method, and the vacuum solvent removal technology method well known to those skilled in the art can be used. The present invention preferably adopts the silica gel column chromatography method to carry out the crude product purification of the second compound; the eluent used in the silica gel column chromatography purification process is preferably n-hexane and dichloromethane, and more preferably the mass ratio is (5～15 ): 1 n-hexane and dichloromethane, most preferably n-hexane and dichloromethane with a mass ratio of 9:1.

In the present invention, the second compound is preferably added to the solvent, and then the obtained second compound solution is subjected to a third reaction with a metal salt compound to obtain an aluminum-based porphyrin complex with the structure of formula (I), more preferably the metal salt The compound is added to the above solution of the second compound to carry out the third reaction to obtain the aluminum-based porphyrin complex with the structure of formula (I).

In the present invention, the active center of the aluminum-based porphyrin complex is aluminum, and when X is -Cl, the metal salt compound is preferably diethylaluminum chloride (AlEt ₂ Cl); the solvent is preferably diethylaluminum chloride (AlEt 2 Cl); Methylene chloride, more preferably dry dichloromethane; the mass ratio of the second compound, the metal salt compound and the solvent is 1:(0.1～0.2):(24～30), more preferably 1:(0.13～ 0.18): (26-29), most preferably 1:0.16:28.

The present invention preferably dissolves the second compound obtained by the above technical scheme to obtain a solution of the second compound, and then adds a metal salt compound into the solution of the second compound to perform a third reaction to obtain an active center of aluminum, and X is The third compound of -Cl. In the present invention, the temperature of the third reaction for preparing the third compound whose active center is aluminum and X is -Cl is preferably 20°C to 40°C, more preferably 25°C to 35°C; the time for the third reaction is preferably 0.5h～1.5h, more preferably 1h.

In the present invention, when X is a halogen other than chlorine, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ , BF ₄ -, BPh ₄ -, -CN, -N ₃ , p-methylbenzene Formate, p-toluenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions, 3,5-dichlorophenol oxyanions, 3,5-difluorophenol oxyanions, 3,5-bis-trifluoromethylphenol oxyanions and One of the pentafluorophenol oxyanions, when the metal center is an aluminum element, the present invention carries out a substitution reaction with the third compound whose metal center is an aluminum element and X is -Cl and corresponding anions of other substituents to obtain An aluminum-based porphyrin complex with a structure of formula (I). The present invention has no special limitation on the substitution method, which can be carried out after the step A) in the above technical scheme by using the substitution method known to those skilled in the art.

After the third reaction is completed, the present invention preferably removes the solvent from the obtained reaction solution to obtain a crude product of the third compound, and then purifies the crude product to obtain a pure product of the third compound. In the present invention, X is different, and the process of removing the solvent miscibility in the third reaction solution to purify the crude product of the third compound is also different, specifically:

When X is -Cl, the present invention preferably adopts the spin-drying solvent method or the solvent-drying method metal salt compound solvent to obtain the crude product of the third compound where X is-Cl. The method of the solvent is not particularly limited, and the technical solution of spin-drying the solvent or draining the solvent well known to those skilled in the art can be used; the present invention preferably uses silica gel column chromatography to purify the crude product of the third compound; the silica gel column The eluent used in the chromatographic purification process is preferably dichloromethane and methanol, more preferably dichloromethane and methanol with a mass ratio of (8-15): 1, and most preferably dichloromethane with a mass ratio of 10:1 and methanol.

When X is a substituent other than -Cl, after the substitution reaction is completed, the present invention preferably dissolves and filters the obtained reaction solution after removing the solvent in a vacuum, and finally drains the filtered product from the solvent to obtain X as the above-mentioned technology Scheme The pure product of the third compound with substituents other than -Cl. In the present invention, the solvent is preferably dichloromethane; the present invention has no special restrictions on the methods of vacuum solvent removal, dissolving, filtering and draining the solvent, and adopts vacuum solvent removal, dissolution, The technical scheme of filtering and draining the solvent is enough.

After the third reaction is completed, the present invention removes the solvent from the preferred third reactant in vacuum to obtain an aluminum-based porphyrin complex having a structure represented by formula (I). In the present invention, there is no special limitation on the method for removing the solvent in vacuum, and a technical solution for removing the solvent in vacuum well known to those skilled in the art can be used.

The present invention adopts the methods of hydrogen spectrum and mass spectrometry to characterize the obtained aluminum-based porphyrin complex, and the experimental results show that the aluminum-based porphyrin complex provided by the present invention has the structure shown in formula (I).

The preparation method of the aluminum series porphyrin complex shown in formula (II) in the present invention, comprises the following steps:

A), the fourth compound having the structure shown in formula (13) is reacted with pyrrole under the action of indium trichloride for the fourth reaction, and the fifth compound obtained is reacted with sodium hydroxide for the fifth to obtain the compound having the formula ( 14) the sixth compound of the shown structure;

Wherein, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl group or substituted aryl group;

B), carry out the sixth reaction with the seventh compound having the structure shown in formula (15) and pyrrole under the effect of indium trichloride, and carry out the seventh reaction with the eighth compound obtained with sodium hydroxide to obtain the compound having the formula ( 16) the ninth compound of the shown structure;

Wherein, R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic group, substituted aliphatic group, aryl group or substituted aryl group;

C), under anhydrous and oxygen-free reaction conditions, the sixth compound obtained in A), the ninth compound obtained in B) and compound A are dissolved in a solvent, and then the eighth reaction is carried out under the action of a catalyst to obtain the sixth compound Tenth compound; the tenth compound obtained and 2,3-dichloro-5,6-dicyano-1,4-p-benzoquinone are subjected to the ninth reaction to obtain the eleventh compound having the structure shown in formula (4) compound;

The structural formula of the compound A is

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , and R ₁₀ are each independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, Aryl or substituted aryl.

D), performing the tenth reaction on the eleventh compound obtained in C) and the metal salt compound in a solvent to obtain an aluminum-based porphyrin complex having a structure shown in formula (II);

In the formula (II), X is halogen, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ , BF ₄ -, BPh ₄ -, -CN, -N ₃ , p-toluate , p-toluenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions, 3,5-dichlorophenol oxyanions, 3,5-difluorophenol oxyanions, 3,5-bis-trifluoromethylphenol oxyanions and One of the pentafluorophenol oxygen anions;

The steps A) and B) are not limited in order.

In step A), the formula (13) is consistent with R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the above technical solution, and will not be described again. Preferred R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen at the same time, the fourth compound is benzaldehyde; when R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are fluorine at the same time, the fourth compound is pentafluorobenzaldehyde; when R ₁ , When R ₃ and R ₅ are chlorine at the same time, and R ₂ and R ₄ are hydrogen at the same time, the fourth compound is 2,4,6-trichlorobenzaldehyde; when R ₁ , R ₂ , R ₄ and R ₅ are at the same time hydrogen, R ₃ is methoxy, the fourth compound is 4-methoxybenzaldehyde; when R ₁ , R ₂ , R ₄ and R ₅ are hydrogen at the same time, R ₃ is methyl, the fourth compound is p-tolualdehyde; when R ₁ , R ₂ , R ₄ and R ₅ are hydrogen at the same time, and R ₃ is ethyl, the fourth compound is p-ethylbenzaldehyde. The pyrrole is preferably dry pyrrole; the sodium hydroxide is preferably 200-300 mesh powdered sodium hydroxide. The mass ratio of the fourth compound, pyrrole, indium trichloride and sodium hydroxide is preferably (4-7): (240-260): 1: (15-25); more preferably (5-6): (245-255):1:(18-22), most preferably 5.5:250:1:20. The source of the fourth compound in the present invention is not limited.

The present invention preferably carries out the fourth reaction with the fourth compound having the structure shown in formula (13) and pyrrole under the effect of indium trichloride, and carries out the fifth reaction with the fifth compound obtained with sodium hydroxide to obtain the compound having the formula ( 14) The sixth compound of the shown structure; more preferably indium trichloride is added to the mixed system of the fourth compound and pyrrole to carry out the fourth reaction, after the fourth reaction is completed, sodium hydroxide is added to obtain The fifth reaction is carried out in the fifth reaction product to obtain the sixth compound having the structure shown in formula (14). In the present invention, the temperature of the fourth reaction is preferably 20°C-40°C, more preferably 25°C-35°C; the time of the fourth reaction is preferably 1h-2h, more preferably 1h. The temperature of the fifth reaction is preferably 20°C-40°C, more preferably 25°C-35°C; the time of the fourth reaction is preferably 30min-60min, more preferably 40min-50min, most preferably 45min;

After the fifth reaction is completed, in the present invention, the obtained fifth reaction product is preferably filtered, and then the filtrate is dried to obtain a crude product of the fifth compound, and the crude product is purified to obtain a pure product of the fifth compound. The present invention has no special limitation on the method of filtering and drying in the step A), and the technical solution of filtering and drying familiar to those skilled in the art can be adopted. The present invention preferably adopts silica gel column chromatography to purify the crude product of the fifth compound; the eluent used in the silica gel column purification process is preferably petroleum ether and dichloromethane, more preferably a mass ratio of 1:(1 ~3) petroleum ether and dichloromethane, most preferably petroleum ether and dichloromethane with a mass ratio of 1:2.

The present invention carries out the sixth reaction with the seventh compound having the structure shown in formula (15) and pyrrole under the effect of indium trichloride, and carries out the seventh reaction with the eighth compound obtained with sodium hydroxide to obtain the compound having the formula (16) ) the ninth compound of the structure shown. In the present invention, R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ in the formula (5) are consistent with R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ in the above technical scheme, No more details; the type and source of the seventh compound are consistent with the fourth compound type and source described in the above technical solution, so no more details; the present invention preferably adopts the preparation method for preparing the sixth compound described in the above technical solution to prepare Obtain the ninth compound, no longer repeat.

In step C), R is independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, aryl or substituted aryl, preferably hydrogen, halogen, aliphatic and substituted aliphatic One of the groups, most preferably one of -H and -OCH ₃ .

In the present invention, under the action of a catalyst, compound A, the sixth compound and the ninth compound are subjected to the eighth reaction, and the obtained tenth product is subjected to the ninth reaction with DDQ to obtain the eleventh compound having the formula (4). In step C) of the present invention, the catalyst is preferably trifluoroacetic acid or boron trifluoride ether, most preferably trifluoroacetic acid. The solvent is preferably dichloromethane, more preferably dry dichloromethane; the compound A, the sixth compound, the ninth compound, catalyst, solvent and 2,3-dichloro-5,6-dicyano- The molar ratio of 1,4-p-benzoquinone is (0.5～1.5): 1: (0.5～2): (2～4): (1200～1800): (1～3); more preferably (0.8～1.2 ): 1: (0.8～1.2): (2.5～3.5): (1400～1600): (1.5～2.5,), most preferably 0.9:1:1:2.8:1500:2;

In the present invention, preferably under the action of a catalyst, compound A, the sixth compound, and the ninth compound are added to the solvent to perform the eighth reaction, and the obtained tenth reaction product is reacted with DDQ for the ninth to obtain a formula (4) the eleventh compound; more preferably, compound A, the sixth compound, and the ninth compound are added to the solvent to obtain a mixed solution, and then the catalyst is added to the mixed solution to perform the eighth reaction, and the eighth reaction After completion, DDQ is added to the obtained tenth reaction product to carry out the ninth reaction to obtain the eleventh compound having the formula (4). In the present invention, the temperature of the eighth reaction is preferably 20°C-40°C, more preferably 25°C-35°C; the eighth reaction time is preferably 0.5h-1.5h, more preferably 1h; The temperature of the ninth reaction is preferably 20°C-40°C, more preferably 25°C-35°C; the time of the ninth reaction is preferably 0.5h-1.5h, more preferably 1h.

After the ninth reaction is completed, the present invention preferably removes the solvent from the obtained eleventh reactant in vacuum to obtain a crude product of the eleventh compound, and further purifies the obtained crude product to obtain a pure product of the eleventh compound. In the present invention, there is no special limitation on the method of spin-drying the solvent in the step C), and the method of vacuum solvent removal well known to those skilled in the art can be used. The present invention preferably adopts the silica gel column chromatography method to carry out crude product purification to the eleventh compound; the eluent used in the silica gel column chromatography purification process is preferably petroleum ether and dichloromethane, more preferably a mass ratio of (0.5 ~1.5):1 petroleum ether and dichloromethane, most preferably petroleum ether and dichloromethane with a mass ratio of 1:1.

In the present invention, the eleventh compound is preferably added to the solvent, and then the obtained eleventh compound solution is subjected to the tenth reaction with a metal salt compound to obtain an aluminum-based porphyrin complex having a structure shown in formula (II); moreover Preferably, the metal salt compound is added to the above solution of the eleventh compound to carry out the tenth reaction to obtain an aluminum-based porphyrin complex having a structure represented by formula (II).

In the present invention, the metal active center is aluminum, and when X is -Cl, the metal salt compound is preferably an organic or inorganic salt of aluminum, more preferably selected from diethyl aluminum chloride, dimethyl aluminum chloride , one of diisobutyl aluminum chloride, ethyl aluminum dichloride, methyl aluminum dichloride and aluminum chloride, more preferably diethyl aluminum chloride (AlEt ₂ Cl); the solvent is preferably It is dichloromethane, more preferably dry dichloromethane; the mass ratio of the eleventh compound, the metal salt compound and the solvent is 1:(0.1～0.2):(24～30), more preferably 1: (0.13-0.18): (26-29), most preferably 1:0.16:28. In the present invention, the eleventh compound obtained by the above technical scheme is preferably dissolved to obtain a solution of the eleventh compound, and then the metal salt compound is added to the solution of the eleventh compound to perform the tenth reaction to obtain a compound whose active center is aluminum , X is an aluminum-based porphyrin complex of -Cl. In the present invention, the temperature of the tenth reaction for preparing a metal porphyrin complex whose active center is aluminum and X is -Cl is preferably 20°C to 40°C, more preferably 25°C to 35°C; the time for the tenth reaction is preferably 0.5h to 1.5h, more preferably 1h.

In the present invention, when X is a halogen other than chlorine, -NO ₃ , CH ₃ COO-, CCl ₃ COO-, ClO ₄ , BF ₄ -, BPh ₄ -, -CN, -N ₃ , p-methylbenzene Formate, p-toluenesulfonate, o-nitrophenol oxyanion, p-nitrophenol oxyanion, m-nitrophenol oxyanion, 2,4-dinitrophenol oxyanion, 3,5-dinitrophenol oxyanions, 2,4,6-trinitrophenol oxyanions, 3,5-dichlorophenol oxyanions, 3,5-difluorophenol oxyanions, 3,5-bis-trifluoromethylphenol oxyanions and One of the pentafluorophenol oxyanions, when the metal center is aluminum element, the present invention performs substitution reaction with the obtained aluminum-based porphyrin complex whose metal center is aluminum element and X is -Cl and corresponding anions of other substituents , to obtain an aluminum-based porphyrin complex having a structure shown in formula (II). In the present invention, there is no special limitation on the substitution method, which can be carried out after step D) in the above-mentioned technical solution by using the substitution-Cl method well known to those skilled in the art.

After the tenth reaction is completed, the present invention preferably removes the solvent from the obtained reaction solution to obtain a crude product of the aluminum-based porphyrin complex, and then purifies the crude product to obtain a pure product of the aluminum-based porphyrin complex. In the present invention, X is different, and the process of purifying the crude product of the aluminum-based porphyrin complex is also different except that the solvent in the tenth reaction solution is miscible, preferably specifically:

When X is -Cl, the present invention preferably uses vacuum to remove the solvent to obtain the crude product of the aluminum-based porphyrin complex in which X is -Cl. The present invention has no special restrictions on the method for vacuum removal of the solvent. The technical scheme of removing the solvent in a vacuum well known to personnel can be used; the present invention preferably adopts the silica gel column chromatography method to carry out the crude product purification of the aluminum-based porphyrin complex; the eluent used in the silica gel column chromatography purification process is preferably two Chloromethane and methanol are more preferably dichloromethane and methanol with a mass ratio of (8-15):1, most preferably dichloromethane and methanol with a mass ratio of 10:1.

When X is a substituent other than -Cl described in the above technical scheme, after the substitution reaction is completed, the present invention preferably removes the solvent from the obtained reaction solution in a vacuum, dissolves and filters it, and finally drains the filtered product out of the solvent, Obtain the pure product of the aluminum-based porphyrin complex whose X is other substituents than -Cl described in the above technical scheme. In the present invention, the solvent is preferably dichloromethane; the present invention has no special restrictions on the methods of vacuum solvent removal, dissolving, filtering and draining the solvent, and adopts vacuum solvent removal, dissolution, The technical scheme of filtering and draining the solvent is enough.

After the tenth reaction is completed, the present invention removes the solvent from the preferred tenth reaction solution in vacuum to obtain an aluminum-based porphyrin complex having a structure represented by formula (II). In the present invention, there is no special limitation on the method for removing the solvent in vacuum, and a technical solution for removing the solvent in vacuum well known to those skilled in the art can be used.

The present invention adopts the methods of hydrogen spectrum and mass spectrometry to characterize the obtained aluminum-based porphyrin complex, and the experimental results show that the aluminum-based porphyrin complex provided by the present invention has the structure shown in formula (II).

The present invention also provides a kind of preparation method of polycarbonate, comprising:

Under the action of the main catalyst and the co-catalyst, carbon dioxide and epoxide are copolymerized to obtain polycarbonate;

The main catalyst is an aluminum-based porphyrin complex having a structure of formula (I) and/or a structure of formula (II);

The cocatalyst is selected from one or more of quaternary ammonium salts, quaternary phosphorus salts and organic bases.

In the process of preparing polycarbonate, in order to fully react, the present application preferably adds carbon dioxide, epoxide, main catalyst, and cocatalyst into the high-pressure reactor to carry out copolymerization reaction to obtain low-ether segment and high-alternating polycarbonate; More preferably in the glove box, the epoxide, the main catalyst, the co-catalyst are added to the high-pressure reactor through the process of dewatering and oxygen removal in advance, then the reactor is moved out of the glove box, and then to the reaction Fill the kettle with carbon dioxide to carry out the copolymerization reaction.

In the present invention, the main catalyst is the aluminum-based porphyrin complex described in the above technical solution or the aluminum-based porphyrin complex prepared by the method described in the above technical solution.

In the present invention, the cocatalyst is preferably selected from tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, bistriphenylphosphine ammonium chloride, bis One or more of triphenylphosphine ammonium bromide, bistriphenylphosphine nitroamine, 4-dimethylaminopyridine and γ-chloropropylmethyldimethoxysilane.

The present invention is not limited to the source and type of the epoxide, and the epoxide well known to those skilled in the art can be used, such as being available from the market. In the present invention, the epoxide is preferably ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, styrene oxide , epichlorohydrin, methacrylate glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and glycosyl glycidyl ether, more preferably ethylene oxide, propylene oxide or cyclohexane oxide.

In the present invention, the molar ratio of the main catalyst, co-catalyst and epoxide is preferably 1: (0.5-1.5): (1000-10000); more preferably 1: (0.8-1.2): (1500-6000 ); most preferably 1:1: (2000-5000). The carbon dioxide is preferably gaseous carbon dioxide with a purity of 99.99%; the pressure of the carbon dioxide is preferably 0.1MPa-8MPa, more preferably 1.5MPa-5MPa, most preferably 3MPa. The reaction temperature of the copolymerization reaction is preferably 20°C-120°C, more preferably 20°C-90°C, most preferably 25°C-60°C; the copolymerization reaction time is preferably 1h-12h, more preferably 2h-8h , most preferably 3h to 5h.

After the end of the copolymerization reaction, the present invention preferably cools the reactor to room temperature, releases the carbon dioxide in the reactor, and prepares low-ether segment, high-alternating polycarbonate.

The aluminum-based porphyrin complex provided by the invention has a structure represented by formula (I) or formula (II). In the presence of the aluminum-based porphyrin complex and cocatalyst provided by the invention, carbon dioxide and epoxide undergo copolymerization reaction to prepare low ether segment and high alternating polycarbonate. In the process of copolymerization, the aluminum-based porphyrin complex has high catalytic activity as the main catalyst, and has good chemical structure selectivity (>99%), and can prepare low ether segment and high alternating polycarbonate. At the same time, the invention uses non-toxic aluminum metal as the active center, which can effectively prevent the content of toxic metals in the polycarbonate produced by catalysis from exceeding the standard, so it is beneficial to the popularization and application of polycarbonate in degradable materials and the like.

In order to further understand the present invention, the aluminum-based porphyrin complex provided by the present invention, its preparation method and the preparation method of polycarbonate are described in detail below in conjunction with the examples, and the protection scope of the present invention is not limited by the following examples.

Example 1

Compound A (1,2,3,4,5,6,7,8-hydrogen-1:4,5:8-dimethylponthracene-9-carbaldehyde) used in this embodiment has a structure such as formula (17 ), R is hydrogen.

(Step 1-1) Under anhydrous and anaerobic reaction conditions, 1.43g of compound A shown in formula (17) and 0.40g of pyrrole were dissolved in 600ml of dry dichloromethane solvent, followed by compound A and Add 1.2ml trifluoroacetic acid to the reaction solution of pyrrole, and carry out the first reaction at 25°C. After the first reaction time is 1h, add 3.5gDDQ to the obtained first reaction solution, and carry out the second reaction at 25°C , after the second reaction was carried out for 1 h, the obtained second reaction solution was spin-dried to obtain the crude product of the second compound, and then the crude product was purified by silica gel column chromatography to obtain a pure product, and the silica gel column The eluent used in the purification process was n-hexane and dichloromethane at a mass ratio of 9:1.

Structural identification of the pure product is carried out, and the pure product is a second compound having a structure shown in formula (18); the yield of the second compound is 15%;

(Step 1-2) Add 1.14 g of the second compound obtained in (Step 1-1) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the resulting mixed solution was subjected to a third reaction at 25° C., and after the third reaction was carried out for 3 hours, the solvent was removed from the obtained third reaction in vacuo to obtain a crude product of the third compound , the crude product is purified with a silica gel column to obtain a pure product, the eluent used in the silica gel column purification process is dichloromethane and methanol with a mass ratio of 10:1; the structure of the pure product is identified, the obtained The pure product is an aluminum-based porphyrin complex having a structure shown in formula (7); the yield of the aluminum-based porphyrin complex is 95%;

After the metalloporphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for dehydration treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses a high-pressure pump every 30 minutes during the dehydration process. Pure argon was ventilated once, and the drained metalloporphyrin complex was stored in a glove box.

The present invention carries out mass spectrometry analysis to the prepared aluminum-based porphyrin complex, and mass spectrometry results show that the molecular weight of the complex prepared in this embodiment is 1203, and according to the theoretical calculation of the structure shown in formula (7), its molecular weight is 1203.9, so the present invention The aluminum-based porphyrin complexes prepared in the examples have the structure shown in formula (7).

Example 2

Compound A (1,2,3,4,5,6,7,8-Hydro-1:4,5:8-Dimethylpyronthracene-10-methoxy-9-carbaldehyde) used in this example , the structure is shown in formula (19), R is a methoxyl group.

(Step 1-1) Under anhydrous and oxygen-free reaction conditions, 1.61 g of compound A shown in formula (19) and 0.40 g of pyrrole were dissolved in 600 ml of dry dichloromethane solvent, and then compound A and Add 1.2ml trifluoroacetic acid to the reaction solution of pyrrole, and carry out the first reaction at 25°C. After the first reaction time is 1h, add 3.5gDDQ to the obtained first reaction solution, and carry out the second reaction at 25°C , after the second reaction was carried out for 1 h, the obtained second reaction was vacuum removed to remove the solvent to obtain the crude product of the second compound, and then the crude product was purified by silica gel column chromatography to obtain a pure product, and the silica gel column The eluent used in the purification process was n-hexane and dichloromethane with a mass ratio of 9:1. Structural identification of the pure product, the pure product is a second compound having a structure shown in formula (20); the yield of the second compound is 12%;

(Step 1-2) Add 1.26 g of the second compound obtained in (Step 1-1) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the resulting mixed solution was subjected to a third reaction at 25°C, and after the third reaction was carried out for 3 hours, the solvent was removed from the third reaction in vacuo to obtain an aluminum-based porphyrin complex The crude product, the crude product is purified with a silica gel column to obtain a pure product, and the eluent used in the silica gel column purification process is dichloromethane and methanol with a mass ratio of 10:1; the structure of the pure product is carried out Identification, the pure product is an aluminum-based porphyrin complex having a structure shown in formula (8); the yield of the aluminum-based porphyrin complex is 95%;

After the aluminum-based porphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for drying treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses it every 30 minutes during the drying process. The high-purity argon gas was ventilated once, and the metalloporphyrin complex was stored in a glove box after being drained.

The present invention carries out mass spectrometry analysis to the prepared aluminum-based porphyrin complex, and the mass spectrometry results show that the molecular weight of the complex prepared in this embodiment is 1322, and according to the theoretical calculation of the structure shown in formula (8), its molecular weight is 1324.1, so the present invention The aluminum-based porphyrin complexes prepared in the examples have the structure shown in formula (8).

Example 3

(Step 1-1) 2.12g of benzaldehyde is added to 104ml of dry pyrrole, and then 0.4g of indium trichloride is added to the mixed system of benzaldehyde and pyrrole to carry out the fourth reaction at 25°C. After the fourth reaction was carried out for 2 hours, 8 g of 200-300 mesh powdered sodium hydroxide was added to the obtained fourth reaction solution, and the fifth reaction was carried out at 25° C. After the fifth reaction was carried out for 45 minutes, the obtained fifth The reaction solution was filtered. Then the filtered solution was spin-dried to obtain the crude product of the fifth compound. Then the crude product was purified with a silica gel column to obtain a pure product, the mass ratio of the eluent used in the silica gel column purification process was 1:2 petroleum ether and dichloromethane; the structure identification of the pure product was carried out. The pure product is the fifth compound having a structure shown in structural formula (21); the yield of the fifth compound is 75%;

(Step 2-2) Compound A (1, 2, 3, 4, 5, 6, 7, 8-hydrogen-1:4, 5:8-dimethanthracene-9-carbaldehyde) used in this example , the structure is shown in formula (17), R is hydrogen.

Under anhydrous and oxygen-free reaction conditions, 1.43g of compound A shown in formula (17) and the fifth compound shown in 1.33g of formula (21) are jointly dissolved in 600ml of dry dichloromethane solvent, and then Add 1.2ml trifluoroacetic acid to the reaction solution of compound A and pyrrole, and carry out the eighth reaction at 25°C. After the eighth reaction time is 1h, add 3.5gDDQ to the obtained eighth reaction solution, Carry out the ninth reaction, after the ninth reaction is carried out for 1 h, the obtained ninth reaction solution is vacuum-removed to obtain the crude product of the ninth compound, and then the crude product is purified by silica gel column chromatography to obtain a pure product, The eluent used in the silica gel column purification process is petroleum ether and dichloromethane with a mass ratio of 1:1.

Structural identification of the pure product, the pure product is the ninth compound having the structure shown in formula (22); the yield of the ninth compound is 18%;

(Step 2-3) Add 0.88 g of the ninth compound obtained in (Step 2-2) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the obtained mixed solution was subjected to the tenth reaction at 25°C, and after the tenth reaction was carried out for 3 hours, the solvent was removed from the obtained tenth reaction solution in vacuum to obtain the aluminum-based porphyrin complex crude product of

The crude product is purified with a silica gel column to obtain a pure product, and the eluent used in the silica gel column purification process is dichloromethane and methanol with a mass ratio of 10:1; the structure of the pure product is identified, and the The pure product is an aluminum-based porphyrin complex having a structure shown in formula (9); the yield of the aluminum-based porphyrin complex is 95%;

After the aluminum-based porphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for drying treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses it every 30 minutes during the drying process. The high-purity argon gas was ventilated once, and the metalloporphyrin complex was stored in a glove box after being drained.

The present invention performs mass spectrometry analysis on the prepared aluminum-based porphyrin complex, and the mass spectrometry results show that the molecular weight of the complex prepared in this example is 902. According to the theoretical calculation of the structure shown in formula (9), the molecular weight of (9-Cl) is 903.37, and (9-Cl) represents the ionic group obtained after the aluminum-based porphyrin complex with the structure shown in formula (9) loses one Cl. Therefore, the aluminum-based porphyrin complex prepared in this example has the structure shown in formula (9).

Example 4

(Step 2-1) 4.19g of 2,4,6-trichlorobenzaldehyde was added to 104ml of dry pyrrole, then 0.4g of indium trichloride was added to the mixed system of benzaldehyde and pyrrole at 25°C Carry out the fourth reaction, after the fourth reaction is carried out for 2h, add 8g of 200-300 mesh powdered sodium hydroxide to the obtained fourth reaction solution, and carry out the fifth reaction at 25°C, the fifth reaction is carried out After 45 minutes, the obtained fifth reaction solution was filtered. Then the filtered solution was spin-dried to obtain the crude product of the fifth compound. Then the crude product was purified with a silica gel column to obtain a pure product, the mass ratio of the eluent used in the silica gel column purification process was 1:2 petroleum ether and dichloromethane; the structure identification of the pure product was carried out. The pure product is the fifth compound having a structure shown in structural formula (23); the yield of the fifth compound is 75%;

(Step 2-2) Compound A (1, 2, 3, 4, 5, 6, 7, 8-hydrogen-1:4, 5:8-dimethanthracene-9-carbaldehyde) used in this example , the structure is shown in formula (17), R is hydrogen.

Under anhydrous and oxygen-free reaction conditions, 1.43g of compound A shown in formula (17) and the fifth compound shown in 1.95g of formula (23) were dissolved in 600ml of dry dichloromethane solvent, and then Add 1.2ml trifluoroacetic acid to the reaction solution of compound A and pyrrole, and carry out the eighth reaction at 25°C. After the eighth reaction time is 1h, add 3.5gDDQ to the obtained eighth reaction solution, Carry out the ninth reaction, after the ninth reaction is carried out for 1 h, the obtained ninth reaction solution is vacuum-removed to obtain the crude product of the ninth compound, and then the crude product is purified by silica gel column chromatography to obtain a pure product, The eluent used in the silica gel column purification process is petroleum ether and dichloromethane with a mass ratio of 1:1. Structural identification of the pure product, the pure product is the ninth compound having the structure shown in formula (24); the yield of the ninth compound is 18%;

(Step 2-3) Add 1.08 g of the ninth compound obtained in (Step 2-2) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the obtained mixed solution was subjected to the tenth reaction at 25°C, and after the tenth reaction was carried out for 3 hours, the solvent was removed from the obtained tenth reaction solution in vacuum to obtain the aluminum-based porphyrin complex The crude product of product, described crude product is purified with silica gel column, obtains pure product, and the eluent that described silica gel column purification process adopts is the dichloromethane and methanol that mass ratio is 10:1; Described pure product is carried out According to structural identification, the pure product is an aluminum-based porphyrin complex having a structure shown in formula (10); the yield of the aluminum-based porphyrin complex is 95%;

After the metalloporphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for dehydration treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses a high-pressure pump every 30 minutes during the dehydration process. Pure argon was ventilated once, and the drained metalloporphyrin complex was stored in a glove box.

The present invention performs mass spectrometry analysis on the prepared aluminum-based porphyrin complex, and the mass spectrometry results show that the molecular weight of the complex prepared in this example is 1109. According to the theoretical calculation of the structure shown in formula (10), the molecular weight of (10-Cl) is 1110.5, and (10-Cl) represents the ionic group obtained after the aluminum-based porphyrin complex with the structure shown in formula (10) loses one Cl. Therefore, the aluminum-based porphyrin complex prepared in this example has the structure shown in formula (10).

Example 5

(Step 1-1) 2.12g of benzaldehyde is added to 104ml of dry pyrrole, and then 0.4g of indium trichloride is added to the mixed system of benzaldehyde and pyrrole to carry out the fourth reaction at 25°C. After the fourth reaction was carried out for 2 hours, 8 g of 200-300 mesh powdered sodium hydroxide was added to the obtained fourth reaction solution, and the fifth reaction was carried out at 25° C. After the fifth reaction was carried out for 45 minutes, the obtained fifth The reaction solution was filtered. Then the filtered solution was spin-dried to obtain the crude product of the fifth compound. Then the crude product was purified with a silica gel column to obtain a pure product, the mass ratio of the eluent used in the silica gel column purification process was 1:2 petroleum ether and dichloromethane; the structure identification of the pure product was carried out. The pure product is the fifth compound having a structure shown in structural formula (21); the yield of the fifth compound is 75%;

(Step 2-2) Compound A used in this example has the structure shown in formula (19), and R is methoxy.

Under anhydrous and oxygen-free reaction conditions, 1.62g of compound A shown in formula (19) and the fifth compound shown in 1.33g of formula (21) were dissolved in 600ml of dry dichloromethane solvent, and then Add 1.2ml trifluoroacetic acid to the reaction solution of compound A and pyrrole, and carry out the eighth reaction at 25°C. After the eighth reaction time is 1h, add 3.5gDDQ to the obtained eighth reaction solution, Carry out the ninth reaction, after the ninth reaction is carried out for 1 h, the obtained ninth reaction solution is vacuum-removed to obtain the crude product of the ninth compound, and then the crude product is purified by silica gel column chromatography to obtain a pure product, The eluent used in the silica gel column purification process is petroleum ether and dichloromethane with a mass ratio of 1:1. Structural identification of the pure product, the pure product is the ninth compound having the structure shown in formula (25); the yield of the ninth compound is 15%;

(Step 2-3) Add 0.94 g of the ninth compound obtained in (Step 2-2) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the mixed solution obtained was subjected to the tenth reaction at 25°C, and after the tenth reaction was carried out for 3 hours, the solvent was removed from the tenth reaction solution obtained in vacuum to obtain the aluminum complex Crude product, the crude product is purified with a silica gel column to obtain a pure product, the eluent used in the silica gel column purification process is dichloromethane and methanol with a mass ratio of 10:1; the structure of the pure product is identified , the pure product is an aluminum-based porphyrin complex having a structure shown in formula (11); the yield of the aluminum-based porphyrin complex is 95%;

After the metalloporphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for dehydration treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses a high-pressure pump every 30 minutes during the dehydration process. Pure argon was ventilated once, and the drained metalloporphyrin complex was stored in a glove box.

The present invention performs mass spectrometry analysis on the prepared aluminum-based porphyrin complex, and the mass spectrometry results show that the molecular weight of the complex prepared in this example is 963. According to the theoretical calculation of the structure shown in formula (11), the molecular weight of (11-Cl) is 964.13, and (11-Cl) represents the ionic group obtained after the aluminum-based porphyrin complex with the structure shown in formula (11) loses one Cl. Therefore, the aluminum-based porphyrin complex prepared in this example has the structure shown in formula (11).

Example 6

(Step 2-1) 4.19g of 2,4,6-trichlorobenzaldehyde was added to 104ml of dry pyrrole, then 0.4g of indium trichloride was added to the mixed system of benzaldehyde and pyrrole at 25°C Carry out the fourth reaction, after the fourth reaction is carried out for 2h, add 8g of 200-300 mesh powdered sodium hydroxide to the obtained fourth reaction solution, and carry out the fifth reaction at 25°C, the fifth reaction is carried out After 45 minutes, the obtained fifth reaction solution was filtered. Then the filtered solution was spin-dried to obtain the crude product of the fifth compound. Then the crude product was purified with a silica gel column to obtain a pure product, the mass ratio of the eluent used in the silica gel column purification process was 1:2 petroleum ether and dichloromethane; the structure identification of the pure product was carried out. The pure product is the fifth compound having a structure shown in structural formula (23); the yield of the fifth compound is 75%;

(Step 2-2) Compound A used in this example has the structure shown in formula (19), and R is methoxy.

Under anhydrous and oxygen-free reaction conditions, 1.62g of compound A shown in formula (19) and the fifth compound shown in 1.95g of formula (23) are jointly dissolved in 600ml of dry dichloromethane solvent, and then Add 1.2ml trifluoroacetic acid to the reaction solution of compound A and pyrrole, and carry out the eighth reaction at 25°C. After the eighth reaction time is 1h, add 3.5gDDQ to the obtained eighth reaction solution, Carry out the ninth reaction, after the ninth reaction is carried out for 1 h, the obtained ninth reaction solution is vacuum-removed to obtain the crude product of the ninth compound, and then the crude product is purified by silica gel column chromatography to obtain a pure product, The eluent used in the silica gel column purification process is petroleum ether and dichloromethane with a mass ratio of 1:1. Structural identification of the pure product, the pure product is the ninth compound having the structure shown in formula (26); the yield of the ninth compound is 15%;

(Step 2-3) Add 1.08 g of the ninth compound obtained in (Step 2-2) to 20 ml of dry dichloromethane, and add 1.2 ml of diethyl chloride to the solution at room temperature in the glove box. Aluminum (1M/L n-hexane solution), the obtained mixed solution was subjected to the tenth reaction at 25°C, and after the tenth reaction was carried out for 3 hours, the solvent was removed from the obtained tenth reaction solution in vacuum to obtain the aluminum-based porphyrin complex The crude product of product, described crude product is purified with silica gel column, obtains pure product, and the eluent that described silica gel column purification process adopts is the dichloromethane and methanol that mass ratio is 10:1; Described pure product is carried out According to structural identification, the pure product is an aluminum-based porphyrin complex having a structure shown in formula (12); the yield of the aluminum-based porphyrin complex is 95%;

After the metalloporphyrin complex is prepared, the present invention puts the obtained aluminum-based porphyrin complex into an ampoule for dehydration treatment, uses a vacuum pump to continuously pump for 12 hours at 50°C, and uses a high-pressure pump every 30 minutes during the dehydration process. Pure argon was ventilated once, and the drained metalloporphyrin complex was stored in a glove box.

The present invention carries out spectral analysis to the prepared aluminum-based porphyrin complex, and the mass spectrometry result shows that the molecular weight of the complex prepared in this embodiment is 1169, and theoretical calculation is carried out according to the structure shown in formula (12), (12-Cl) The molecular weight is 1170.78, and (12-Cl) represents the ionic group obtained after the aluminum-based porphyrin complex with the structure shown in formula (12) loses one Cl. Therefore, the aluminum-based porphyrin complex prepared in this example has the structure shown in formula (12).

Example 7

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 1 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 25°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared by the embodiment is detected by ¹ H-NMR nuclear magnetic resonance, and the result shows that the carbonate unit content in the polycarbonate is higher than 99%, and the cyclic carbonate by-product content is less than 4%; The TOF value of the system is 24h ^-1 ; the number average molecular weight of the prepared polycarbonate measured by GPC is 46000, and the molecular weight distribution is 1.20.

Example 8

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 1 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 40°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared by the embodiment is detected by ¹ H-NMR, and the result shows that the carbonate unit content in the polycarbonate is higher than 99%, and the cyclic carbonate by-product content is less than 7%; The TOF value of the system is 149h ^-1 ; the number average molecular weight of the prepared polycarbonate measured by GPC is 25000, and the molecular weight distribution is 1.15.

Example 9

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 1 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 40°C to carry out the polymerization reaction for 10h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

Detect the polycarbonate obtained by ¹ H-NMR, the result shows that the carbonate unit content in polycarbonate is higher than 99%, and the content of cyclic carbonate by-product is less than 7%; The TOF value of the system is 113h ^-1 ; the number average molecular weight of the prepared polycarbonate measured by GPC is 56000, and the molecular weight distribution is 1.15.

Example 10

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 1 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 50°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off the unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-grade, high-alternation polycarbonate.

The polycarbonate prepared by the embodiment is detected by ¹ H-NMR nuclear magnetic resonance, and the result shows that the carbonate unit content in the polycarbonate is higher than 99%, and the cyclic carbonate by-product content is less than 15%; The TOF value of the system is 192h- ¹ ; the number average molecular weight of the prepared polycarbonate measured by GPC is 15000, and the molecular weight distribution is 1.19.

Example 11

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 1 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off the unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-grade, high-alternation polycarbonate.

The polycarbonate prepared in the embodiment is detected by ¹ H-NMR nuclear magnetic resonance, and the result shows that the content of carbonate units in the polycarbonate is higher than 99%, and the content of cyclic carbonate by-products is less than 40%; The TOF value of the system is 231h ^-1 ; the number average molecular weight of the prepared polycarbonate measured by GPC is 16000, and the molecular weight distribution is 1.16.

Example 12

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 2 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared by the embodiment is detected by ¹ H-NMR nuclear magnetic resonance, and the result shows that the carbonate unit content in the polycarbonate is higher than 99%, and the cyclic carbonate by-product content is less than 30%; The TOF value of the system is 251h- ¹ ; the number average molecular weight of the prepared polycarbonate measured by GPC is 18000, and the molecular weight distribution is 1.12.

Example 13

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 2 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 24°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off the unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-grade, high-alternation polycarbonate.

The polycarbonate prepared in the embodiment is detected by ¹ H-NMR nuclear magnetic resonance, and the result shows that the carbonate unit content in the polycarbonate is higher than 99%, and the cyclic carbonate by-product content is less than 3%; The TOF value of the system is 28h ^-1 ; the number average molecular weight of the prepared polycarbonate measured by GPC is 48000, and the molecular weight distribution is 1.10.

Example 14

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 3 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 24°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off the unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-grade, high-alternation polycarbonate.

The polycarbonate prepared in the example was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 11h- ¹ .

Example 15

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 3 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared in the embodiment was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 217h- ¹ .

Example 16

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 4 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 25°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared in the embodiment was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 14h- ¹ .

Example 17

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 4 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-segment, high-alternation polycarbonate.

The polycarbonate prepared in the embodiment was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 238h- ¹ .

Example 18

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 5 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 24°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum drying oven at 25°C to obtain low-segment, high-alternation polycarbonate.

The polycarbonate prepared in the embodiment was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 17h- ¹ .

Example 19

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 5 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared in the example was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 244h- ¹ .

Example 20

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.03mmol of the aluminum-based porphyrin complex prepared in Example 6 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 25°C to carry out the polymerization reaction for 48h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared in the embodiment was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 23h- ¹ .

Example 21

In the present invention, carbon dioxide and epoxides are polymerized in the autoclave. Before the polymerization, the autoclave must be dehydrated and oxygen-removed. The specific method is as follows:

The high-pressure reactor was decompressed and replaced with argon in a vacuum oven at 80°C, and the decompression and argon replacement operation was repeated every hour for a total of three times to achieve the purpose of removing water and oxygen from the high-pressure reactor. The autoclave was placed in the glove box.

In the glove box, 0.015mmol of the aluminum-based porphyrin complex prepared in Example 6 and 75mmol of dry propylene oxide were added to the 15ml autoclave after the dehydration and oxygen removal process, and then the autoclave was removed from the glove box Take it out, and then fill the autoclave with carbon dioxide through the carbon dioxide supply line with pressure adjustment function, so that the pressure in the autoclave reaches 3MPa, and control the temperature of the autoclave at 60°C to carry out the polymerization reaction for 5h. After the polymerization reaction is finished, the autoclave is cooled to 25° C., the carbon dioxide in the autoclave is slowly released, and the autoclave is opened to collect ¹ H-NMR NMR samples for NMR determination. Suck off unreacted propylene oxide in a vacuum oven at 25°C to obtain polycarbonate with low ether segment and high alternation.

The polycarbonate prepared in the example was detected by ¹ H-NMR nuclear magnetic resonance, and the result showed that the carbonate unit content in the polycarbonate was higher than 99%; the TOF value of the catalytic system was calculated to be 256h- ¹ .

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

The above description of the disclosed embodiments is provided to enable any person 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 present invention will not 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 (10)

1. there is an aluminum system metalloporphyrin complex for formula I or formula (II) structure,

Wherein, R, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀It is independently selected from the aryl of hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl or replacement；

X is selected from halogen ,-NO₃、CH₃COO-、CCl₃COO-、ClO₄-、-BF₄、-BPh₄、-CN、-N₃, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, onitrophenol negative oxygen ion, paranitrophenol negative oxygen ion, metanitrophenol negative oxygen ion, 2,2, 4-dinitrophenol negative oxygen ion, 3,5-dinitrophenol,DNP negative oxygen ion, 2,4,6-trinitrophenol negative oxygen ion, 3, one in 5-chlorophenesic acid negative oxygen ion, 3,5-difluorophenol negative oxygen ions, 3,5-di-trifluoromethyl phenol negative oxygen ions and pentafluranol negative oxygen ion.

2. aluminum system according to claim 1 metalloporphyrin complex, it is characterised in that described R, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀Be independently selected from hydrogen, chlorine, the aliphatic group of C1～C15, the aliphatic group of C1～C5 of replacement, phenyl ring number are the one in the aryl of 1～3 and the aryl that phenyl ring quantity is 1～3 of halogen substiuted.

3. aluminum system according to claim 1 metalloporphyrin complex, it is characterised in that when described aluminum system metalloporphyrin complex has formula (2) structure, the preparation method of described aluminum system metalloporphyrin complex includes:

React having the organic or inorganic salt with aluminum of the ligand compound shown in formula (1) in a solvent, obtain the aluminum system metalloporphyrin complex with formula (2) structure,

Wherein, R one in the aryl of hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl and replacement；

The organic or inorganic salt of described aluminum one in diethyl aluminum chloride, dimethylaluminum chloride, diisobutyl aluminum chloride, ethylaluminum dichloride, methylaluminum dichloride and aluminum chloride.

4. aluminum system according to claim 1 metalloporphyrin complex, it is characterised in that when described aluminum system metalloporphyrin complex has formula (3) structure, the preparation method of described aluminum system metalloporphyrin complex includes:

To have the ligand compound shown in formula (1) and reaction in the solution of the organic or inorganic salt containing aluminum, obtain the aluminum system metalloporphyrin complex with formula (2) structure；

By the aluminum system metalloporphyrin complex with formula (2) structure obtained above with dechlorination outside the corresponding anion of other substituent group carry out substitution reaction, obtain the aluminum system metalloporphyrin complex with formula (3) structure；

Wherein, R one in the aryl of hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl and replacement；

X₁Halogen outside dechlorination ,-NO₃、CH₃COO-、CCl₃COO-、ClO₄-、-BF₄、-BPh₄、-CN、-N₃, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, onitrophenol negative oxygen ion, paranitrophenol negative oxygen ion, metanitrophenol negative oxygen ion, 2,2, 4-dinitrophenol negative oxygen ion, 3,5-dinitrophenol,DNP negative oxygen ion, 2,4,6-trinitrophenol negative oxygen ion, 3, one in 5-chlorophenesic acid negative oxygen ion, 3,5-difluorophenol negative oxygen ions, 3,5-di-trifluoromethyl phenol negative oxygen ions and pentafluranol negative oxygen ion；

The organic or inorganic salt of described aluminum one in diethyl aluminum chloride, dimethylaluminum chloride, diisobutyl aluminum chloride, ethylaluminum dichloride, methylaluminum dichloride and aluminum chloride.

5. aluminum system according to claim 1 metalloporphyrin complex, it is characterised in that when described aluminum system metalloporphyrin complex has formula (5) structure, the preparation method of described aluminum system metalloporphyrin complex includes:

React having the organic or inorganic salt with aluminum of the ligand compound shown in formula (4) in a solvent, obtain the aluminum system metalloporphyrin complex with formula (5) structure,

Wherein, R, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀It is independently selected from the one in the aryl of hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl and replacement；

The organic or inorganic salt of described aluminum one in diethyl aluminum chloride, dimethylaluminum chloride, diisobutyl aluminum chloride, ethylaluminum dichloride, methylaluminum dichloride and aluminum chloride.

6. aluminum system according to claim 1 metalloporphyrin complex, it is characterised in that when described aluminum system metalloporphyrin complex has formula (6) structure, the preparation method of described aluminum system metalloporphyrin complex includes:

React having the organic or inorganic salt with aluminum of the ligand compound shown in formula (4) in a solvent, obtain the aluminum system metalloporphyrin complex with formula (5) structure；

By the aluminum system metalloporphyrin complex with formula (5) structure obtained above with dechlorination outside the corresponding anion of other substituent group carry out substitution reaction, obtain the aluminum system metalloporphyrin complex with formula (6) structure；

Wherein, R, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀It is independently selected from the one in hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl and substituted aryl；

X₁Halogen outside dechlorination ,-NO₃、CH₃COO-、CCl₃COO-、ClO₄-、-BF₄、-BPh₄、-CN、-N₃, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, onitrophenol negative oxygen ion, paranitrophenol negative oxygen ion, metanitrophenol negative oxygen ion, 2,2, 4-dinitrophenol negative oxygen ion, 3,5-dinitrophenol,DNP negative oxygen ion, 2,4,6-trinitrophenol negative oxygen ion, 3, one in 5-chlorophenesic acid negative oxygen ion, 3,5-difluorophenol negative oxygen ions, 3,5-di-trifluoromethyl phenol negative oxygen ions and pentafluranol negative oxygen ion；

The organic or inorganic salt of described aluminum one in diethyl aluminum chloride, dimethylaluminum chloride, diisobutyl aluminum chloride, ethylaluminum dichloride, methylaluminum dichloride and aluminum chloride.

7. a preparation method for Merlon, including:

Under the major catalyst effect with promoter, carbon dioxide and epoxide are carried out copolyreaction, obtains Merlon；

Described major catalyst is have formula I structure and or have the aluminum system metalloporphyrin complex of formula (II) structure；

Described promoter is selected from one or more in quaternary ammonium salt, quaternary alkylphosphonium salt and organic base；

Wherein, R, R₁、R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉And R₁₀It is independently selected from the one in the aryl of hydrogen, halogen, aliphatic group, the aliphatic group of replacement, aryl and replacement；

X is selected from halogen ,-NO₃、CH₃COO-、CCl₃COO-、ClO₄-、-BF₄、-BPh₄、-CN、-N₃, p-methylbenzoic acid root, p-methyl benzenesulfonic acid root, onitrophenol negative oxygen ion, paranitrophenol negative oxygen ion, metanitrophenol negative oxygen ion, 2,2, 4-dinitrophenol negative oxygen ion, 3,5-dinitrophenol,DNP negative oxygen ion, 2,4,6-trinitrophenol negative oxygen ion, 3, one in 5-chlorophenesic acid negative oxygen ion, 3,5-difluorophenol negative oxygen ions, 3,5-di-trifluoromethyl phenol negative oxygen ions and pentafluranol negative oxygen ion.

8. preparation method according to claim 7, it is characterised in that the mol ratio of described major catalyst, promoter and epoxide is 1:(0.5～1.5): (1000～10000).

9. preparation method according to claim 7, it is characterised in that the pressure of described carbon dioxide is 0.1MPa～8MPa；The temperature of described copolyreaction is 20～120 DEG C, and the time of described copolyreaction is 1h～12h.

10. preparation method according to claim 7, it is characterized in that, described epoxide is selected from one or more in oxirane, expoxy propane, 1,2-epoxy butane, 7-oxa-bicyclo[4.1.0, cyclopentane epoxide, epoxychloropropane, methyl propenoic acid glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether and styrene epoxyalkane；Described promoter includes one or more in tetraethylammonium bromide, tetrabutyl ammonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, bi triphenyl phosphine ammonium chloride, bi triphenyl phosphine ammonium bromide, bi triphenyl phosphorus nitra-amine, DMAP and gamma-chloropropylmethyldimethoxysilane.