CN111454433A - Bifunctional oligomeric metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate - Google Patents

Bifunctional oligomeric metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate Download PDF

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CN111454433A
CN111454433A CN202010411237.4A CN202010411237A CN111454433A CN 111454433 A CN111454433 A CN 111454433A CN 202010411237 A CN202010411237 A CN 202010411237A CN 111454433 A CN111454433 A CN 111454433A
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卓春伟
王献红
王佛松
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention provides a bifunctional oligomeric metalloporphyrin complex with a structure shown as a formula (I). The invention is based on ring-opening metathesis polymerization, creatively prepares the random oligomeric metalloporphyrin catalyst with the main chain having quaternary ammonium salt or quaternary phosphonium salt functional group functional modification, and the provided bifunctional complex has excellent catalytic performance in the copolymerization reaction of carbon dioxide and epoxide. The bifunctional metalloporphyrin complex has high catalytic activity and high selectivity, and the conversion number (TOF) of a catalytic system can reach up to 15000h‑1(ii) a The cyclic carbonate by-product in the product is less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 20 to 90 percent; the number average molecular weight of the copolymerization product is 6,000-200,000 g/mol, and the molecular weight distribution is 1.20-1.35. Realizes the new breakthrough of the catalytic performance of the metalloporphyrin complex and provides a new design strategy for the functional design of the catalyst.

Description

Bifunctional oligomeric metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate
Technical Field
The invention relates to the technical field of catalysts, in particular to a bifunctional oligomeric metalloporphyrin complex, a preparation method thereof and a preparation method of polycarbonate.
Background
Carbon dioxide (CO)2) Is a main greenhouse gas and is a cheap carbon-oxygen resource with rich sources. CO 22The method is concerned by people as a basic research and an industrial application research of chemical and energy chemical raw materials. Up to now, CO2Has been used to synthesize urineVarious small molecular compounds and high molecular materials such as sodium carbonate, salicylic acid, methanol, formic acid and the like. In which cheap CO is used2The CO can be realized for the route of monomer synthesis of high molecular materials2The method has high added value utilization, and has very high economic value and application potential. ZnEt was used by Inoue, Japan scientist, 19692/H2O system successfully catalyzes CO for the first time2CO preparation by epoxide copolymerization2Based on a polycarbonate. The polycarbonate material not only can greatly utilize CO2(CO in Polymer)2In excess of 40%) and has good biodegradability, thus receiving high attention from both academia and industry. The basic synthesis reaction is as follows: under the action of catalyst, CO2Copolymerization with alkylene oxide to form polycarbonate (usually containing a small amount of polyether segments) and cyclic carbonate.
The design and synthesis of the high-efficiency catalyst are to realize CO2The key problem of high activity and high selectivity copolymerization reaction with epoxide. After decades of accumulation and development, CO2The heterogeneous catalyst mainly comprises a plurality of systems such as a zinc carboxylate catalyst, a double metal cyanide catalyst, a rare earth ternary catalyst and the like, the catalytic performance of the heterogeneous catalyst is stable, although the heterogeneous catalyst has the defects of low catalytic efficiency, poor selectivity, undefined structure and the like, the industrial application is realized firstly[14]In particular, the presence of bifunctional Salenco catalysts significantly increased CO2Activity of copolymerization, product selectivity, regioselectivity, and polymer molecular weight. But CO2The base polycarbonate must meet the environmental requirements of being "compostableThe practical application of cobalt-centered catalytic systems is severely limited. Therefore, the field presents the development trend of high-activity, high-selectivity, low-toxicity and environment-friendly catalysts.
Metalloporphyrin complexes are catalytic systems earlier applied to the field, wherein few aluminum porphyrin complexes can effectively catalyze CO2An environment-friendly catalytic system for copolymerization with PO. In 1978 aluminum porphyrin complexes were first used to catalyze CO2The catalyst has low activity and poor selectivity when being copolymerized with PO, and a subsequently developed two-component system improves the catalytic performance of the aluminum porphyrin but is still unsatisfactory. In 2014, Wang and the like successfully develop a bifunctional mononuclear aluminum porphyrin catalyst, the complex has higher catalytic activity and selectivity, and the TOF value can reach 3407h-1[CN201310400892.X；Polym.Sci,Part A:Polym.Chem.2014,52(16),2346-2355.；RSCAdv.2014,4,54043-54050.；]In addition, the influence relationship among steric effect, electronic effect and catalytic performance of porphyrin ligand substituent is deeply researched [ Chin.J.Polym.Sci.2018,36, 252-260-; Chen.J.chem.2018, 36,299-305.]. Although the aluminum porphyrin complex is used for catalyzing CO2The reactivity of the copolymerization is markedly improved, but satisfactory results are still not achieved. Based on the CO2With the understanding of PO copolymerization reaction mechanism, the number of active centers in a single catalyst molecule has a significant influence relationship with catalytic performance, and the double-center or multi-center synergistic catalytic action becomes one of the key factors for improving the catalytic performance. Based on the above, Wang and other innovations in 2019 developed an aluminum porphyrin catalyst with a low polymerization degree structure, so that a multi-metal center synergistic reaction under a homogeneous catalysis condition is realized, the catalytic activity of the catalyst is increased by 3-5 times, and the catalyst concentration (PO/[ Al ] is extremely low]100,000) retained good activity (TOF 870 h)-1) In research, multi-metal catalysts composed of active center molecules can increase the local concentration of the catalyst and enhance the metal-metal synergy to a greater extent [ CN 201810550759.5; ACS Catal.2019,9,8669 and 8676; CN201910324732.9]. The structural design of the oligomeric metalloporphyrin provides a new design strategy for increasing the catalytic performance, but is still a two-component catalytic system,a certain amount of cocatalyst needs to be added, so the economic cost and the catalytic performance of the catalytic system need to be further optimized.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a bifunctional oligomeric metalloporphyrin complex, which does not require a catalytic assistant in the copolymerization reaction of carbon dioxide and epoxide, and has high catalytic activity and high selectivity.
Compared with the prior art, the invention provides a bifunctional oligomeric metalloporphyrin complex with a structure shown as a formula (I). The invention is based on ring-opening metathesis polymerization, creatively prepares the random oligomeric metalloporphyrin catalyst with the main chain having quaternary ammonium salt or quaternary phosphonium salt functional group functional modification, and the provided bifunctional complex has excellent catalytic performance in the copolymerization reaction of carbon dioxide and epoxide. In the copolymerization reaction, the bifunctional metalloporphyrin complex is used for preparing polycarbonate with high catalytic activity and high selectivity, and the conversion number (TOF) of a catalytic system can reach 15000h < -1 > at most; the cyclic carbonate by-product in the product is less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 20 to 90 percent; the number average molecular weight of the copolymerization product is 6,000-200,000 g/mol, and the molecular weight distribution is 1.20-1.35. Realizes the new breakthrough of the catalytic performance of the metalloporphyrin complex and provides a new design strategy for the functional design of the catalyst.
Detailed Description
The invention provides a bifunctional oligomeric metalloporphyrin complex, a preparation method thereof and a preparation method of polycarbonate, and a person skilled in the art can use the contents to appropriately improve process parameters for realization. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention provides a bifunctional oligomeric metalloporphyrin complex with a structure shown as a formula (I):
Figure BDA0002493333740000031
wherein x is an integer of 1-25; preferably an integer of 2 to 23, more preferably an integer of 3 to 20; y is an integer of 1-25, preferably an integer of 2-23, more preferably an integer of 3-20, and the value of x: y is 1 (1-10); more preferably 1 (1-8); specifically, the ratio may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1: 8.
The above-mentioned
Figure BDA0002493333740000032
Is a linking group; the linking group has a structure of formula (VII) or formula (VIII):
Figure BDA0002493333740000033
wherein: p is an integer of 1 to 10. Preferably an integer of 1 to 8; and may be 1,2, 3, 4, 5, 6, 7 or 8.
Ra is
Figure BDA0002493333740000034
The above-mentioned
Figure BDA0002493333740000035
Is one of quaternary ammonium salt functional group and quaternary phosphonium salt functional group;
the above-mentioned
Figure BDA0002493333740000036
Is one of quaternary ammonium salt functional group with a structure of formula (III) and quaternary phosphonium salt functional group with a structure of formula (IV):
Figure BDA0002493333740000037
wherein n, m and k are independently selected from integers of 1-6; specifically, it may be 1,2, 3, 4, 5 or 6.
Y1 -And Y2 -Independently selected from halogen anion, NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -One or more of p-methyl benzenesulfonic acid group, p-methyl benzoate group, 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-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion.
Said Rb is
Figure BDA0002493333740000038
The above-mentioned
Figure BDA0002493333740000039
Is a metalloporphyrin complex having the structure of formula (II):
Figure BDA0002493333740000041
wherein M is a metal element; preferably one selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; more preferably iron, cobalt or aluminium.
X is independently selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3One or more of p-methylbenzoyl, p-methylbenzenesulfonic, o-nitrophenol oxy, p-nitrophenol oxy, m-nitrophenol oxy, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-bis-trifluoromethylphenol oxy or pentafluorophenol oxy anions;
the R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Independently selected from one of hydrogen, halogen, aliphatic groups of C1-C5, substituted aliphatic groups of C1-C5, aryl groups with 1-3 benzene rings or substituted aryl groups with 1-3 benzene rings. Wherein the aryl of C6-C30 is preferably the aryl with 1-3 benzene rings; the substituted aryl of C6-C30 is preferably substituted aryl with 1-3 benzene rings.
According to the invention, the metalloporphyrin complex is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106;
Figure BDA0002493333740000042
Figure BDA0002493333740000051
the invention provides a bifunctional metalloporphyrin complex which has a structure shown in a formula (I), is an oligomer structure formed by a ring-opening metathesis polymerization method, has a multi-active center aggregation state, and contains a quaternary ammonium salt functional group or a quaternary phosphonium salt functional group component.
The invention provides a preparation method of a bifunctional oligomeric metalloporphyrin complex, which comprises the following steps:
polymerizing the compound shown as the formula (i-2) and the compound shown as the formula (i-4) by using a Grubbs III catalyst to obtain a compound shown as the formula (i-5);
reacting the compound shown in the formula (i-5) with a metal salt compound to obtain a compound shown in a formula (i-6);
reacting a tertiary amine compound shown as a formula (I-6) to obtain a compound shown as a formula (I);
Figure BDA0002493333740000061
wherein p is an integer of 1-10; and may be 1,2, 3, 4, 5, 6, 7, 8, 9 or 10.
x is an integer of 1-25; y is an integer of 1-25, and the value of x: y is 1 (1-10);
the above-mentioned
Figure BDA0002493333740000062
Is a linking group; ra is
Figure BDA0002493333740000063
The above-mentioned
Figure BDA0002493333740000064
Is one of quaternary ammonium salt functional group and quaternary phosphonium salt functional group; said Rb is
Figure BDA0002493333740000065
The above-mentioned
Figure BDA0002493333740000066
Is a metalloporphyrin complex having the structure of formula (II): x is independently selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3One or more of p-methylbenzoyl, p-methylbenzenesulfonic, o-nitrophenol oxy, p-nitrophenol oxy, m-nitrophenol oxy, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-bis-trifluoromethylphenol oxy or pentafluorophenol oxy anions.
The R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Independently selected from hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, 1-3 benzene ring number aryl or 1-3 substituted benzene ring number aryl.
Preferably, the tertiary amine compound is one of trimethylamine, tributylamine and trihexylamine; the metal in the metal salt compound is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
According to the preparation method of the bifunctional oligomeric metalloporphyrin complex, firstly, a compound shown as a formula (i-2) and a compound shown as a formula (i-4) are polymerized under a Grubbs III catalyst to obtain a compound shown as a formula (i-5). The polymerization is a ring opening metathesis polymerization.
The feeding molar ratio of the compound shown in the formula (i-2) to the compound shown in the formula (i-4) is preferably 1 (0.1-10); the reaction temperature is 40-50 ℃; the reaction time is 3-4 h.
Reacting the compound shown in the formula (i-5) with a metal salt compound to obtain a compound shown in a formula (i-6); the metal in the metal salt compound is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
Calculating the mole number of the porphyrin complex component in the compound shown in the formula (i-5) according to the feeding mole ratio of the compound shown in the formula (i-4), wherein the feeding ratio of the mole number to the mole number of the metal salt compound is 1 (1.0-1.2); the reaction temperature is 25-30 ℃; the reaction time is 4-6 h.
Reacting a tertiary amine compound shown as a formula (I-6) to obtain a compound shown as a formula (I);
the tertiary amine compound is one of trimethylamine, tributylamine and trihexylamine. The reaction temperature is 25-40 ℃; the reaction time is 0.5-1.5 h.
Calculating the mole number of the porphyrin complex component in the compound shown in the formula (i-6) according to the feeding mole ratio of the compound shown in the formula (i-4), wherein the feeding ratio of the mole number to the mole number of the tertiary amine or tertiary phosphine compound is 1 (30-45).
In the present invention, the compound represented by the formula (i-2) is preferably prepared by the following method:
under the action of a catalyst, reacting a compound with a structure shown in a formula (i-1) with 5-norbornene-2-carboxylic acid to obtain a compound shown in a formula (i-2); the reaction temperature is preferably 50-60 ℃; the reaction time is preferably 16-20 h.
Figure BDA0002493333740000071
p is an integer of 1-10; and may be 1,2, 3, 4, 5, 6, 7, 8, 9 or 10.
Y is a negative ion in the quaternary ammonium salt functional group or a negative ion in the quaternary phosphonium salt functional group.
The catalyst of the present invention is preferably 4-dimethylaminopyridine; the feeding molar ratio of the compound with the structure shown in the formula (i-1) to 5-norbornene-2-acyl chloride is 1 (5-20).
The compound represented by the formula (i-4) is preferably produced by the following method:
under the action of a catalyst, reacting a compound shown as a formula (i-3) with 5-norbornene-2-acyl chloride, wherein the feeding molar ratio of the compound shown as the formula (i-3) to the 5-norbornene-2-acyl chloride is 1 (5-20), and the reaction temperature is 25-30 ℃; the reaction time is 20-24 h;
or reacting with the compound shown in the formula (i-2) obtained in the step a) to obtain the compound shown in the formula (i-4). The feeding molar ratio of the compound shown in the formula (i-3) to the compound shown in the formula (i-2) is (5-20): 1; the reaction temperature is 50-60 ℃; the reaction time is 40-48 h.
Figure BDA0002493333740000081
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Independently selected from one of hydrogen, halogen, aliphatic groups of C1-C5, substituted aliphatic groups of C1-C5, aryl groups with 1-3 benzene rings or substituted aryl groups with 1-3 benzene rings; in the formula (4)
Figure BDA0002493333740000082
Is the linking group.
The present invention does not limit the preparation method of the formula (i-3), and those skilled in the art are familiar with the method.
The invention provides a bifunctional metalloporphyrin complex which has a structure shown in a formula (I), is an oligomer structure formed by a ring-opening metathesis polymerization method, has a multi-active center aggregation state, and contains a quaternary ammonium salt functional group or a quaternary phosphonium salt functional group component.
The invention provides a preparation method of polycarbonate, which comprises the following steps:
taking the metalloporphyrin complex as defined in any one of claims 1 to 5 or the metalloporphyrin complex prepared by the method as defined in any one of claims 6 to 7 as a catalyst, and carrying out copolymerization reaction on carbon dioxide and epoxide to obtain the polycarbonate.
The bifunctional metalloporphyrin complex is used as a catalyst, and carbon dioxide and epoxide are subjected to copolymerization reaction without adding a cocatalyst to obtain the polycarbonate.
According to the invention, the molar ratio of the metalloporphyrin complex to the epoxide is preferably 1 (2000-500000); more preferably 1 (3000-400000);
the pressure of the carbon dioxide is preferably 0.1-8.0 MPa; more preferably 0.5 to 7.0 MPa; most preferably 1 to 6.0 MPa.
The temperature of the copolymerization reaction is preferably 0-150 ℃; more preferably 10 ℃ to 130 ℃; most preferably 30 ℃ to 120 ℃; the time of the copolymerization reaction is preferably 0.5 h-48 h; more preferably 0.5h to 40 h; most preferably 0.5h to 20 h.
The epoxide of the invention comprises one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
The invention provides a bifunctional oligomeric metalloporphyrin complex with a structure shown as a formula (I). The invention is based on ring-opening metathesis polymerization, creatively prepares the random oligomeric metalloporphyrin catalyst with the main chain having quaternary ammonium salt or quaternary phosphonium salt functional group functional modification, and the provided bifunctional complex has excellent catalytic performance in the copolymerization reaction of carbon dioxide and epoxide. In the copolymerization reaction, the bifunctional metalloporphyrin complex has high catalytic activity and high selectivity for preparing polycarbonate, and the conversion number (TOF) of a catalytic system can reach 15000h at most-1(ii) a The cyclic carbonate by-product in the product is less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 20 to 90 percent; the number average molecular weight of the copolymerization product is 6,000-200,000 g/mol, and the molecular weight distribution is 1.20-1.35. Realizes the new breakthrough of the catalytic performance of the metalloporphyrin complex and provides a new design strategy for the functional design of the catalyst.
In order to further illustrate the present invention, the following examples are given to describe in detail a bifunctional oligomeric metalloporphyrin complex, a preparation method thereof and a preparation method of polycarbonate according to the present invention.
Preparation example 1
Step a1), adding 5-norbornene-2-carboxylic acid (3.62mmol, 1equiv) and dichloromethane (30m L) into a dry single-neck flask (100m L), stirring and dissolving, adding dicyclohexylcarbodiimide (DCC, 3.62mmol, 1equiv), a first compound (3.62mmol, 1equiv) having a structure shown in formula (8), 4-dimethylaminopyridine (catalyst equivalent) into the reaction solution, stirring and dissolving under the protection of argon, heating and refluxing for 16H, diluting the reaction solution with dichloromethane after the reaction is finished, filtering, drying the filtrate with anhydrous magnesium sulfate, and removing the solvent in vacuum, and collecting an oily product.
Figure BDA0002493333740000091
Step b1), adding 5-norbornene-2-carboxylic acid (12mmol) into a 250m L three-neck flask filled with dry tetrahydrofuran (150m L) under the protection of argon, placing the system in an ice-water bath at 0 ℃, dropwise adding oxalyl chloride (60mmol), adding N, N-dimethylformamide (DMF, 0.2m L) after the completion of the reaction, stirring for 30min, recovering to room temperature, and stirring for reaction for 6 h.
Under the protection of argon, a third compound (6mmol) with a structure shown in a formula (10) is added into a 250m L three-neck flask, dried dichloromethane (100m L) is stirred and dissolved by magnetic force, a purple reaction liquid is cooled to 0 ℃, synthesized 5-norbornene-2-acyl chloride (12mmol) is dissolved by dried dichloromethane (10m L), then the obtained solution is dropwise added into a reaction system, pyridine (2m L) is added by a syringe, the reaction system is stirred for 30min and then is stirred for 24H at room temperature, after the reaction is finished, the reaction system is washed by a dilute hydrochloric acid solution, after removing a pyridine component, saturated sodium bicarbonate, saturated sodium chloride and water are respectively used for three times, an organic layer is collected, the obtained organic layer is dried by anhydrous sodium sulfate, a purple filtrate is collected by filtration, a crude product is obtained by concentration, and a first component is collected by silica gel column chromatography for purification (dichloromethane/petroleum ether is 1/1, V/V), a fourth compound with a structure shown in a formula (11) is obtained, a purple solid target product is analyzed by high-resolution electrospray analysis, and analysis result [ C52H38N 2: 389 64: 387: 64.
Figure BDA0002493333740000101
Step c1), drying the polymerization tube (15m L) in a glove box under argon atmosphere, and adding a magnetic stirrer and a closed cock to the polymerization tube to obtain a second compound (75. mu. mol, 25equiv) having a structure represented by formula (9) and a second compound represented by formula (11)Dissolving a fourth compound (75 mu mol, 25equiv) with the structure in dried chloroform (5m L), adding a Grubbs III catalyst (3 mu mol, 1equiv), wherein the molar ratio of a polymerization monomer to the catalyst is 50:1, carrying out freeze-drying for three times, removing oxygen, then sealing a polymerization tube, carrying out stirring reaction for 3 hours at 40 ℃, adding vinyl ethyl ether (3m L) for quenching after the polymerization is finished, then dropwise adding ethyl ether (30m L) under the stirring state, dissolving the polymerization monomer in the ethyl ether, precipitating an oligomeric porphyrin target product, collecting a solid product by centrifugation, washing the solid product for three times by using the ethyl ether, carrying out vacuum drying, and obtaining a fifth compound (x: y, the value of which is 1:1) shown in the formula (12), a deep red solid target product, and carrying out gel permeation chromatography (GPC, CH2Cl2):Mn＝11800，PDI＝1.21。
And d1) in an argon atmosphere glove box, adding a fifth compound (2.0mmol, wherein the component of the fourth compound is 1.0mmol) shown in the formula (12) into dry dichloromethane (20m L), stirring and dissolving, adding diethyl aluminum chloride (1.05mmol, 1 mol/L n-hexane solution), stirring the reaction solution at room temperature for 3h, after the reaction is finished, filtering the reaction solution by using a filtering sand core paved with a layer of neutral alumina (200 meshes and 300 meshes), washing the neutral alumina by using a dry dichloromethane/methanol (10/1, V/V) mixed solution, collecting the filtrate, concentrating and drying to obtain the sixth compound with the structure shown in the formula (13).
Step e1), adding a sixth compound (2mmol) with a structure shown in formula (13) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, condensing and refluxing for 48h, and after the reaction is finished, removing the solvent and redundant amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorAl-01 shown in formula (14), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000111
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Preparation example 2
Step a2) and step b2) the experimental procedures were the same as in step a1) and step b1) of preparation example 1, and a second compound having a structure represented by formula (9) and a fourth compound having a structure represented by formula (11) were obtained.
Step c2), in a glove box under argon atmosphere, drying a polymerization tube (15m L), matching with a magnetic stirrer and a closed cock, dissolving a second compound (50 mu mol, 16.6equiv) with a structure shown in formula (9) and a fourth compound (100 mu mol, 33.3equiv) with a structure shown in formula (11) in dry chloroform (5m L), adding Grubbs III catalyst (3 mu mol, 1equiv), wherein the molar ratio of the polymerization monomer to the catalyst is 50:1, carrying out three times of freeze-drying and oxygen removal on the solution, closing the polymerization tube, carrying out stirring reaction at 40 ℃ for 3h, after the polymerization is finished, adding vinyl ethyl ether (3m L) for quenching, then adding ethyl ether (30m L) under the stirring state, dissolving the polymerization monomer in the ethyl ether, precipitating the oligomeric porphyrin target product, collecting a solid product by centrifugation, washing three times by using the ethyl ether, and carrying out vacuum drying to obtain a Gel (GPC) gel (CH 2) with a penetration value of the fifth compound (x: y) shown in formula (15)2Cl2):Mn＝12500，PDI＝1.25。
And d2) in an argon atmosphere glove box, adding a fifth compound (1.5mmol, wherein the component of the fourth compound is 1.0mmol) shown in the formula (15) into dry dichloromethane (20m L), stirring and dissolving, adding diethyl aluminum chloride (1.05mmol, 1 mol/L n-hexane solution), stirring the reaction solution at room temperature for 3h, after the reaction is finished, filtering the reaction solution by using a filtering sand core paved with a layer of neutral alumina (200 meshes and 300 meshes), washing the neutral alumina by using a dry dichloromethane/methanol (10/1, V/V) mixed solution, collecting the filtrate, concentrating and drying to obtain the sixth compound with the structure shown in the formula (16).
Figure BDA0002493333740000121
Step e2), adding a sixth compound (1.5mmol) with the structure shown in the formula (16) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, carrying out condensation reflux for 48h, and after the reaction is finished, removing the solvent and excessive amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorAl-02 shown in the formula (17), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000122
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Preparation example 3:
step a3), adding 5-norbornene-2-carboxylic acid (3.62mmol, 1equiv) and dichloromethane (30m L) into a dry single-neck flask (100m L), stirring and dissolving, adding dicyclohexylcarbodiimide (DCC, 3.62mmol, 1equiv), a first compound (3.62mmol, 1equiv.) having a structure shown in formula (18), 4-dimethylaminopyridine (catalyst equivalent) into the reaction solution, stirring and dissolving under the protection of argon, heating and refluxing for 16H, diluting the reaction solution with dichloromethane after the reaction is finished, filtering, drying the filtrate with anhydrous magnesium sulfate, and removing the solvent in vacuum, and collecting an oily product.
Figure BDA0002493333740000131
Step b3) experimental procedure the same as in step b1) of preparation example 1, a fourth compound having a structure represented by formula (11) was obtained.
Step c3),Dissolving a second compound (50 mu mol, 16.6equiv) with a structure shown in a formula (19) and a fourth compound (100 mu mol, 33.3equiv) with a structure shown in a formula (11) in dry chloroform (5m L) in a glove box under an argon atmosphere by using a magnetic stirrer and a closed cock, adding a Grubbs III catalyst (3 mu mol, 1equiv), wherein the molar ratio of a polymerization monomer to the catalyst is 50:1, freeze-drying the solution for three times, deoxidizing, closing the polymerization tube, stirring and reacting for 3 hours at 40 ℃, quenching by adding vinyl ether (3m L) after polymerization is finished, dropwise adding ether (30m L) under a stirring state, dissolving the polymerization monomer in the ether, precipitating a target product of oligomeric porphyrin, collecting a solid product by centrifugation, washing the solid product for three times by using the ether, and drying in vacuum to obtain a fifth compound (x: y) with a value of 1:2, and performing Gel Permeation Chromatography (GPC) (CH 20)2Cl2):Mn＝13000，PDI＝1.29。
And d3) in an argon atmosphere glove box, adding a fifth compound (1.5mmol, wherein the component of the fourth compound is 1.0mmol) shown in the formula (20) into dry dichloromethane (20m L), stirring and dissolving, adding diethyl aluminum chloride (1.05mmol, 1 mol/L n-hexane solution), stirring the reaction solution at room temperature for 3h, after the reaction is finished, filtering the reaction solution by using a filtering sand core paved with a layer of neutral alumina (200 meshes and 300 meshes), washing the neutral alumina by using a dry dichloromethane/methanol (10/1, V/V) mixed solution, collecting the filtrate, concentrating and drying to obtain the sixth compound with the structure shown in the formula (21).
Figure BDA0002493333740000132
Step e2), adding a sixth compound (1.5mmol) with the structure shown in the formula (21) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, condensing and refluxing for 48h, and after the reaction is finished, removing the solvent and the excessive amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorAl-03 shown in the formula (22), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000141
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Preparation example 4
Step a4) experimental procedure the same as in step a3) of preparation example 3, a second compound having a structure represented by formula (19).
Step b4), adding 5-norbornene-2-carboxylic acid (12mmol) into a 250m L three-neck flask filled with dry tetrahydrofuran (150m L) under the protection of argon, placing the system in an ice-water bath at 0 ℃, dropwise adding oxalyl chloride (60mmol), adding N, N-dimethylformamide (DMF, 0.2m L) after the completion of the reaction, stirring for 30min, recovering to room temperature, and stirring for reaction for 6 h.
Under the protection of argon, a third compound (6mmol) with a structure shown in a formula (23) is added into a 250m L three-neck flask, dried dichloromethane (100m L) is stirred and dissolved by magnetic force, a purple reaction liquid is cooled to 0 ℃, synthesized 5-norbornene-2-acyl chloride (12mmol) is dissolved by dried dichloromethane (10m L), then the obtained solution is dropwise added into a reaction system, pyridine (2m L) is added into the reaction system by a syringe, the reaction system is stirred for 30min and then is stirred at room temperature for 24H, after the reaction is finished, the reaction system is washed by a dilute hydrochloric acid solution, after removing a pyridine component, saturated sodium bicarbonate, saturated sodium chloride and water are respectively used for three times, an organic layer is collected, the obtained organic layer is dried by anhydrous sodium sulfate, a purple filtrate is collected by filtration, and a crude product is obtained by concentration, a silica gel column chromatography is used for separation and purification (dichloromethane/petroleum ether is 1/1, V/V), a first component is collected, and a fourth atomized compound with a structure shown in a formula (24) is obtained, and analysis result of high electron spray mass spectrometry is analyzed by [ C52H35Br3N4O2, 984.03.
Figure BDA0002493333740000151
Step c4), in a glove box under argon atmosphere, drying a polymerization tube (15m L), adding a magnetic stirrer and a closed cock, dissolving a second compound (50 mu mol, 16.6equiv) with a structure shown in formula (19) and a fourth compound (100 mu mol, 33.3equiv) with a structure shown in formula (24) in dry chloroform (5m L), adding Grubbs III catalyst (3 mu mol, 1equiv), wherein the molar ratio of the polymerization monomer to the catalyst is 50:1, carrying out three times of freeze-drying and oxygen removal on the solution, closing the polymerization tube, carrying out stirring reaction at 40 ℃ for 3h, after the polymerization is finished, adding vinyl ethyl ether (3m L) for quenching, then adding ethyl ether (30m L) under the stirring state, dissolving the polymerization monomer in ethyl ether, precipitating an oligomeric porphyrin target product, collecting a solid product by centrifugation, washing three times by using ethyl ether, carrying out vacuum drying, and obtaining a fifth compound (x: y) with a value of 1:2), a red permeation chromatography product (CH, a GPC target product, and a GPC product2Cl2):Mn＝11300，PDI＝1.22。
And d4) in an argon atmosphere glove box, adding a fifth compound (1.5mmol, wherein the component of the fourth compound is 1.0mmol) shown in the formula (25) into dry dichloromethane (20m L), stirring and dissolving, adding diethyl aluminum chloride (1.05mmol, 1 mol/L n-hexane solution), stirring the reaction solution at room temperature for 3h, after the reaction is finished, filtering the reaction solution by using a filtering sand core paved with a layer of neutral alumina (200 meshes and 300 meshes), washing the neutral alumina by using a dry dichloromethane/methanol (10/1, V/V) mixed solution, collecting the filtrate, concentrating and drying to obtain the sixth compound with the structure shown in the formula (26).
Figure BDA0002493333740000152
Step e4), adding a sixth compound (1.5mmol) with the structure shown in the formula (26) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, condensing and refluxing for 48h, and after the reaction is finished, removing the solvent and the excessive amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorAl-04 shown in the formula (27), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000161
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Preparation example 5
Step a5) experimental procedure the same as in step a3) of preparation example 3, a second compound having a structure represented by formula (19).
Step b5), adding a second compound (15.8mmol, 2.5equiv.) having a structure shown in formula (19), anhydrous potassium carbonate (15.8mmol, 2.5equiv.), N-dimethylformamide (DMF, 50m L) into a magnetically stirred round-bottom flask (250m L), stirring to dissolve, dissolving a third compound (6.33mmol, 1equiv) having a structure shown in formula (23) into dry N, N-dimethylformamide (DMF, 30m L), slowly adding the system at room temperature, continuing to stir to dissolve for 30min, after the completion of the addition, raising the reaction temperature to 60 ℃, continuing to stir for 48H, after the reaction is completed, removing the solvent in vacuum, adding dichloromethane (200m L) and water (200m L) into the system, separating the organic layer, extracting the aqueous phase with dichloromethane (2 × m L), combining the organic phases, drying with anhydrous water, concentrating by filtration to obtain a crude product, separating the crude product by using a purple chromatography (200m L) and collecting the eluate by N-hexane chromatography (3625V) and analyzing the crude product by electrospray analysis, and collecting the crude product having a structure of N-dimethylformamide (DMF, N-dimethylformamide (3655) and acetic acid).
Step c5), drying the polymerization tube (15m L) in a glove box under argon atmosphere, and mixing the second compound (50 mu mol) with the structure shown in the formula (19) by a magnetic stirrer and a closed cock16.6equiv) and a fourth compound (100. mu. mol, 33.3equiv) having a structure represented by formula (28) were dissolved in dry chloroform (5m L), Grubbs III catalyst (3. mu. mol, 1equiv) was added, the molar ratio of the polymerized monomer to the catalyst was 50:1, the solution was lyophilized three times to remove oxygen, the polymerization tube was sealed, the reaction was stirred at 40 ℃ for 3 hours, after the polymerization was completed, vinyl ethyl ether (3m L) was added to quench, then ethyl ether (30m L) was added dropwise with stirring, the polymerized monomer was dissolved in ethyl ether, the target product of oligomeric porphyrin was precipitated, the solid product was collected by centrifugation, washed three times with ethyl ether, and after vacuum drying, the fifth compound (x: y value of 1:2) represented by formula (29) was obtained, the target product of dark red solid was obtained, gel permeation chromatography (GPC, CH, and2Cl2):Mn＝13100，PDI＝1.25。
Figure BDA0002493333740000171
and d5) in an argon atmosphere glove box, adding a fifth compound (1.5mmol, wherein the component of the fourth compound is 1.0mmol) shown in the formula (29) into dry dichloromethane (20m L), stirring and dissolving, adding diethyl aluminum chloride (1.05mmol, 1 mol/L n-hexane solution), stirring the reaction solution at room temperature for 3h, after the reaction is finished, filtering the reaction solution by using a filtering sand core paved with a layer of neutral alumina (200 meshes and 300 meshes), washing the neutral alumina by using a dry dichloromethane/methanol (10/1, V/V) mixed solution, collecting the filtrate, concentrating and drying to obtain the sixth compound with the structure shown in the formula (30).
Step e5), adding a sixth compound (1.5mmol) with the structure shown in the formula (31) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, condensing and refluxing for 48h, and after the reaction is finished, removing the solvent and the excessive amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorAl-05 shown in the formula (31), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000181
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Preparation example 6
Step a6), step b6), step c6) the experimental procedures were the same as in step a5), step b5), step c5) of preparation example 5, respectively, to obtain a fifth compound having the structure represented by formula (29).
Step d6), dissolving the fifth compound (1.5mmol, wherein the fourth compound component is 1.0mmol) shown in formula (29) in 20m L anhydrous DMF, adding cobalt acetate (180mg) with crystal water removed, stirring at room temperature for reaction for 12h, adding 0.042g anhydrous lithium chloride, introducing oxygen, continuing to react for 12h, stopping the reaction, removing the solvent under reduced pressure, dissolving the residue in 20m L in dichloromethane, washing with 70m L saturated sodium bicarbonate solution and 70m L saturated saline solution respectively for three times, drying the organic phase with anhydrous sodium sulfate, removing the solvent under reduced pressure, dissolving the residue in 20m L in dichloromethane, adding 0.01g silver tetrafluoroborate, reacting away from light for 24h, filtering to remove insoluble substances, adding 0.20g 2, 4-dinitrophenol sodium to the filtrate, reacting at room temperature for 2h, filtering to remove inorganic salts, removing the solvent under reduced pressure, and recrystallizing the crude product with dichloromethane and n-hexane to obtain the sixth compound shown in formula (32).
Step e6), adding a sixth compound (1.5mmol) with a structure shown in formula (32) and tributylamine (50mmol) into a mixed solvent of 10m L dry tetrahydrofuran and acetonitrile solution, carrying out condensation reflux for 48h, and after the reaction is finished, removing the solvent and excessive amine compound in vacuum to obtain the bifunctional metalloporphyrin complex PorCo-01 shown in formula (33), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1: 1.
Figure BDA0002493333740000191
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuum-pumping drying treatment, a vacuum oil pump is used for continuously pumping for 12 hours at the temperature of 50 ℃, high-purity argon is used for ventilation once every 30min in the pumping process, and the metalloporphyrin complex after being pumped is placed into a glove box for storage.
Example 1
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-01 of preparation example 1 and 75mmol of dried propylene oxide were added to a 15ml high-pressure reaction kettle after water removal and oxygen removal, the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was charged into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle was made to reach 4MPa, and the temperature of the high-pressure reaction kettle was controlled at 25 ℃ for a polymerization reaction for 3 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 1 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 78%, and the product selectivity is 99.9%; the catalytic activity (TOF value) of the catalytic system is calculated to be 1580h-1(ii) a The polycarbonate obtained had a number average molecular weight of 45000 and a molecular weight distribution of 1.21 as determined by GPC.
Example 2
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-01 of preparation example 1 and 75mmol of dried propylene oxide were added to a 15ml high-pressure reaction kettle after water removal and oxygen removal, the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was charged into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle was made to reach 4MPa, and the temperature of the high-pressure reaction kettle was controlled at 40 ℃ for a polymerization reaction for 3 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 2 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 95% and the product selectivity is 99.9%; the catalytic activity (TOF value) of the catalytic system is 3655h by calculation-1(ii) a The polycarbonate obtained by the preparation had a number average molecular weight of 52000 and a molecular weight distribution of 1.26 as determined by GPC.
Example 3
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol was preparedThe aluminum porphyrin complex PolyAl-02 and 150mmol of dry propylene oxide in example 2 were added to a dehydrated and deoxygenated 25ml autoclave, which was then taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line with a pressure adjusting function so that the pressure in the autoclave reached 3MPa, and the autoclave was controlled at 70 ℃ for polymerization for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 3 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 89%, and the product selectivity is 99.9%; the catalytic activity (TOF value) of the catalytic system is calculated to be 5880h-1(ii) a The polycarbonate obtained had a number average molecular weight of 49000 and a molecular weight distribution of 1.24 as determined by GPC.
Example 4
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-02 of preparation example 2 and 375mmol of dry propylene oxide were added into a 50ml high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was charged into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle was made to reach 5MPa, and the temperature of the high-pressure reaction kettle was controlled at 110 ℃ for polymerization reaction for 0.5 h. The polymerization reactionAfter the reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 4 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 82%, and the product selectivity is 97%; the catalytic activity (TOF value) of the catalytic system is 14549h by calculation-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 95000 and a molecular weight distribution of 1.31.
Example 5
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-03 of preparation example 3 and 375mmol of dried propylene oxide were added to a 50ml autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 5MPa, and the temperature of the autoclave was controlled at 110 ℃ to perform a polymerization reaction for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR Nuclear magnetic resonance examination of the polycarbonate obtained in example 5, results are shown in the TableMeanwhile, the chemical structure selectivity (carbonate unit content) of the polycarbonate is 78 percent, and the product selectivity is 97 percent; the catalytic activity (TOF value) of the catalytic system is 11580h by calculation-1(ii) a The polycarbonate obtained by GPC was found to have a number average molecular weight of 75000 and a molecular weight distribution of 1.24.
Example 6
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-03 of preparation example 3 and 150mmol of dried propylene oxide were added to a 25ml autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 4MPa, and the temperature of the autoclave was controlled at 70 ℃ to perform a polymerization reaction for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 6 shows that the polycarbonate contains 89% carbonate units and less than 0.01% cyclic carbonate by-products; the TOF value of the catalytic system is 6755h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 59000 and a molecular weight distribution of 1.28 as determined by GPC.
By passing1The polycarbonate obtained in example 6 was examined by H-NMR nuclear magnetic resonance, and the results showed that the polycarbonate was esterifiedThe chemical structure selectivity (carbonate unit content) was 89%, and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalytic system is 6755h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 59000 and a molecular weight distribution of 1.28 as determined by GPC.
Example 7
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-04 of preparation example 4 and 375mmol of dried propylene oxide were added into a 50ml high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was charged into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle was made to reach 3MPa, and the temperature of the high-pressure reaction kettle was controlled at 110 ℃ for polymerization reaction for 1.5 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 7 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 82%, and the product selectivity is 99.9%; the catalytic activity (TOF value) of the catalytic system is calculated to be 15110h-1(ii) a The polycarbonate obtained had a number average molecular weight of 95000 and a molecular weight distribution of 1.24 as determined by GPC.
Example 8
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-05 of preparation example 5 and 150mmol of dried propylene oxide were added to a 25ml autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 3MPa, and the temperature of the autoclave was controlled at 70 ℃ to perform a polymerization reaction for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 8 shows that the chemical structure selectivity (carbonate unit content) of the polycarbonate is 79%, and the product selectivity is 99.9%; the catalytic activity (TOF value) of the catalytic system is calculated to be 7530h-1(ii) a The polycarbonate obtained had a number average molecular weight of 58000 and a molecular weight distribution of 1.27 as determined by GPC.
Example 9
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-05 and 375mmol of dried propylene oxide of preparation example 5 were added to a 50ml autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 5MPa, and the temperature of the autoclave was controlled at 110 ℃ to perform a polymerization reaction for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance analysis of the polycarbonate prepared in example 9 showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 88% and the product selectivity was 98%; the catalytic activity (TOF value) of the catalytic system is 13770h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 54000 and a molecular weight distribution of 1.23 as determined by GPC.
Example 10
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyAl-05 of preparation example 5 and 150mmol of dried propylene oxide were added to a 25ml autoclave after water removal and oxygen removal, the autoclave was taken out of the glove box, carbon dioxide was charged into the autoclave through a carbon dioxide supply line having a pressure adjusting function, the pressure in the autoclave was made to be 4MPa, and the temperature of the autoclave was controlled to be within a range ofThe polymerization was carried out at 25 ℃ for 3 h. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 10 revealed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 81% and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalytic system is calculated to be 1560h-1(ii) a The number average molecular weight of the polycarbonate obtained by the preparation was 39000 and the molecular weight distribution was 1.23, as determined by GPC.
Example 11
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyCo-01 prepared in preparation example 6 and 75mmol of dried epichlorohydrin are added into a 15ml high-pressure reaction kettle after water and oxygen removal, then the high-pressure reaction kettle is taken out of the glove box, carbon dioxide is filled into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 10 ℃ for carrying out polymerization reaction for 8 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1The polycarbonate obtained in example 11 was examined by H-NMR nuclear magnetic resonance, and the results showed that the polycarbonate was esterifiedThe chemical structure selectivity (carbonate unit content) was 96%, and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalytic system is 540h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 77000 and a molecular weight distribution of 1.26 as determined by GPC.
Example 12
In the invention, carbon dioxide and epoxide are polymerized in a high-pressure reaction kettle, and before the polymerization reaction, the high-pressure reaction kettle is subjected to water removal and oxygen removal treatment, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to pressure reduction and argon replacement treatment in a vacuum oven at the temperature of 80 ℃, the pressure reduction and argon replacement operation is repeated once an hour for three times to achieve the purposes of removing water and oxygen from the high-pressure reaction kettle, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex PolyCo-01 prepared in preparation example 6 and 375mmol of dried propylene oxide were added into a 50ml high-pressure reaction kettle after water and oxygen removal, then the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was charged into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure adjusting function, the pressure in the high-pressure reaction kettle was made to reach 5MPa, and the temperature of the high-pressure reaction kettle was controlled at 110 ℃ for polymerization reaction for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time1H-NMR nuclear magnetic samples, and nuclear magnetic measurement is carried out. And pumping out the unreacted propylene oxide in a vacuum drying oven at 25 ℃ to obtain the polycarbonate.
By passing1H-NMR nuclear magnetic resonance detection of the polycarbonate prepared in example 12 revealed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 77% and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalytic system is 10600h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 81000 and a molecular weight distribution of 1.22 as determined by GPC.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A bifunctional oligomeric metalloporphyrin complex having the structure of formula (I):
Figure FDA0002493333730000011
wherein x is an integer of 1-25; y is an integer of 1-25, and the value of x: y is 1 (1-10);
the above-mentioned
Figure FDA0002493333730000012
Is a linking group; the Ra is one of a quaternary ammonium salt functional group and a quaternary phosphonium salt functional group; the Rb is a metalloporphyrin complex with a structure of a formula (II):
Figure FDA0002493333730000013
wherein M is a metal element;
x is independently selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3One or more of p-methylbenzoyl, p-methylbenzenesulfonic, o-nitrophenol oxy, p-nitrophenol oxy, m-nitrophenol oxy, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-bis-trifluoromethylphenol oxy or pentafluorophenol oxy anions;
the R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Independently selected from one of hydrogen, halogen, aliphatic groups of C1-C5, substituted aliphatic groups of C1-C5, aryl groups with 1-3 benzene rings or substituted aryl groups with 1-3 benzene rings.
2. The complex of claim 1, wherein Ra is one of a quaternary ammonium salt functional group having a structure of formula (iii) and a quaternary phosphonium salt functional group having a structure of formula (iv):
Figure FDA0002493333730000021
wherein n, m and k are independently selected from integers of 1-6;
Y1 -and Y2 -Independently selected from halogen anion, NO3 -、CH3COO-、CCl3COO-、CF3COO-、ClO4 -、BF4 -One or more of p-methyl benzenesulfonic acid group, p-methyl benzoate group, 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-bis-trifluoromethylphenol oxyanion and pentafluorophenol oxyanion.
3. The complex of claim 1, wherein the linker group has the structure of formula (VII) or formula (VIII):
Figure FDA0002493333730000022
wherein: p is an integer of 1 to 10.
4. The complex of claim 1, wherein M is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium.
5. The complex of claim 1, wherein the metalloporphyrin complex is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106;
Figure FDA0002493333730000023
Figure FDA0002493333730000031
Figure FDA0002493333730000041
6. a method for preparing a bifunctional oligomeric metalloporphyrin complex, comprising:
polymerizing the compound shown as the formula (i-2) and the compound shown as the formula (i-4) by using a Grubbs III catalyst to obtain a compound shown as the formula (i-5);
reacting the compound shown in the formula (i-5) with a metal salt compound to obtain a compound shown in a formula (i-6);
reacting a tertiary amine compound shown as a formula (I-6) to obtain a compound shown as a formula (I);
Figure FDA0002493333730000051
wherein p is an integer of 1-10; x is an integer of 1-25; y is an integer of 1-25, and the value of x: y is 1 (1-10);
the above-mentioned
Figure FDA0002493333730000052
Is a linking group; one of the Ra quaternary ammonium salt functional group and the quaternary phosphonium salt functional group; the Rb is a metalloporphyrin complex with a structure of a formula (II): x is independently selected from halogen, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3One or more of p-methylbenzoyl, p-methylbenzenesulfonic, o-nitrophenol oxy, p-nitrophenol oxy, m-nitrophenol oxy, 2, 4-dinitrophenol oxy, 3, 5-dinitrophenol oxy, 2,4, 6-trinitrophenol oxy, 3, 5-dichlorophenol oxy, 3, 5-difluorophenol oxy, 3, 5-bis-trifluoromethylphenol oxy or pentafluorophenol oxy anions;
the R is1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18And R19Independently selected from one of hydrogen, halogen, aliphatic groups of C1-C5, substituted aliphatic groups of C1-C5, aryl groups with 1-3 benzene rings or substituted aryl groups with 1-3 benzene rings.
7. The complex of claim 1, wherein the tertiary amine compound is one of trimethylamine, tributylamine, and trihexylamine; the metal in the metal salt compound is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
8. A method of producing a polycarbonate, comprising:
taking the metalloporphyrin complex as defined in any one of claims 1 to 5 or the metalloporphyrin complex prepared by the method as defined in any one of claims 6 to 7 as a catalyst, and carrying out copolymerization reaction on carbon dioxide and epoxide to obtain the polycarbonate.
9. The preparation method of claim 8, wherein the molar ratio of the metalloporphyrin complex to the epoxide is 1 (2000-500000); the pressure of the carbon dioxide is 0.1-8.0 MPa; the temperature of the copolymerization reaction is 0-150 ℃; the time of the copolymerization reaction is 0.5 h-48 h.
10. The preparation method according to claim 8, wherein the epoxide comprises one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
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