CN109988290B - Preparation method of oligomeric metalloporphyrin complex and polycarbonate - Google Patents

Preparation method of oligomeric metalloporphyrin complex and polycarbonate Download PDF

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CN109988290B
CN109988290B CN201910324732.9A CN201910324732A CN109988290B CN 109988290 B CN109988290 B CN 109988290B CN 201910324732 A CN201910324732 A CN 201910324732A CN 109988290 B CN109988290 B CN 109988290B
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卓春伟
秦玉升
曹瀚
王献红
王佛松
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Changchun Institute of Applied Chemistry of CAS
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract

The invention provides a preparation method of an oligomeric multicenter metalloporphyrin complex and polycarbonate, wherein the complex has a structure shown in a formula I. The metalloporphyrin complex has a plurality of active centers and has higher catalytic activity when catalyzing the copolymerization of carbon dioxide and alkylene oxide. In addition, the catalyst also has higher product selectivity and high-temperature stability when catalyzing the copolymerization of carbon dioxide and alkylene oxide. The oligomeric multicenter metalloporphyrin complex is applied to synthesis of ether-rich polycarbonate, and the structure of a synthetic product contains a certain amount of ether segments, so that the brittleness problem of the conventional polycarbonate material is solved, the toughness of the material is enhanced, and the application space of the material is expanded. The conversion frequency TOF value of a system for catalyzing copolymerization of carbon dioxide and alkylene oxide is 34h‑1～8110h‑1(ii) a The by-products in the reaction product are less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 28-62%.

Description

Preparation method of oligomeric metalloporphyrin complex and polycarbonate
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of an oligomeric metalloporphyrin complex and polycarbonate.
Background
The carbon dioxide is abundant in reserves and low in price, is an ideal C1 resource, and has many industrial cases for synthesizing large small molecular compounds by taking the carbon dioxide as a raw material. The copolymerization reaction of carbon dioxide and epoxy compounds is a few reaction processes capable of consuming carbon dioxide, and meanwhile, biodegradable plastics can be generated, so that the copolymer is expected to become a substitute of traditional non-degradable polyolefin plastics, and the problem of increasingly serious white pollution is solved. Polycarbonate is a high molecular polymer containing carbonate groups in molecular chains, is a fully-degradable high molecular material, has good air permeability and oxygen and water barrier properties, and is applied to a plurality of fields of biodegradable pollution-free materials, novel liquid crystal materials, gas barrier materials, rubber material reinforcing agents, composite materials and the like.
The carbon dioxide and epoxide can generate copolymerization reaction to synthesize polycarbonate under the action of catalyst, and the common catalyst systems of the copolymerization reaction at present comprise a series of catalysts such as alkyl zinc-active hydrogen catalyst system, zinc carboxylate catalyst system, phenol zinc salt catalyst system, diimine zinc catalyst system, double metal cyanide catalyst system, rare earth ternary catalyst system, metalloporphyrin catalyst system and the like. In the existing catalyst, Salenco is a catalytic system with good comprehensive catalytic performance, but the toxicity of metallic cobalt is high, and particularly when the catalyst is used as biodegradable plastic, the composting process strictly limits the residue of cobalt, so the application of the catalyst is greatly limited. The active center of the aluminum porphyrin catalyst is environment-friendly metal aluminum, meets the use requirement of biodegradable plastics, and can effectively catalyze the copolymerization reaction of carbon dioxide and epoxide, so that the aluminum porphyrin complex is emphasized in the field of carbon dioxide and epoxide catalysts.
The first use of aluminum-based metalloporphyrins for catalyzing CO by professor Inoue of Japan since 19782Aluminum-based metalloporphyrin catalysts have attracted attention of researchers since the reaction of Propylene Oxide (PO) with propylene oxide to Produce Polycarbonate (PPC), but high-activity and high-selectivity aluminum-based porphyrin catalysts have been the research target in this field. Tetrabifunctional aluminum porphyrin complex catalytic systems appeared in 2014 show high reactivity and high selectivity, but the catalyst synthesis is complex, and the practical application of the catalyst is limited. Therefore, breaking through the conventional catalyst mode, designing and synthesizing a two-component porphyrin catalytic system with more excellent catalytic performance becomes a research focus.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of an oligomeric metalloporphyrin complex and polycarbonate, wherein the complex has adjustable active center number and high catalytic activity.
The invention provides an oligomeric metalloporphyrin complex, which has a structure shown in a formula I:
Figure BDA0002035919310000021
in the formula I, R isaIs selected from
Figure BDA0002035919310000022
The R isbIs selected from H or
Figure BDA0002035919310000023
The value of n is 2-50;
Figure BDA0002035919310000024
is a linking group;
the above-mentioned
Figure BDA0002035919310000025
Is a metalloporphyrin complex having the structure of formula II:
Figure BDA0002035919310000026
in the formula II, M is a metal element; 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, 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;
x is selected from halo, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoate, p-methylbenzenesulfonate, 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-bistrifluoromethylphenol oxyanion, or pentafluorophenol oxyanion.
Preferably, the
Figure BDA0002035919310000031
Has a structure of formula III or formula IV:
Figure BDA0002035919310000032
wherein the value of p is an integer of 1-16.
Preferably, the metallic element is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
Preferably, the oligomeric metalloporphyrin complex is specifically of formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106:
Figure BDA0002035919310000033
Figure BDA0002035919310000041
wherein Y is 2, 4-dinitrophenol oxyanion.
The invention provides a preparation method of polycarbonate, which comprises the following steps:
under the action of a cocatalyst and the oligomeric metalloporphyrin complex as a main catalyst, carrying out copolymerization reaction on carbon dioxide and epoxide to obtain polycarbonate;
the cocatalyst comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and organic base;
the mass ratio of the main catalyst to the cocatalyst is 1: 0.1-5.
Preferably, the mass ratio of the procatalyst and epoxide is 1: 2000 to 500000.
Preferably, the cocatalyst is selected from one or more of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphine nitramine, 1,5, 7-triazabicyclo [4.4.0] dec-5-en-4-dimethylaminopyridine and gamma-chloropropylmethyldimethoxysilane.
Preferably, the temperature of the copolymerization reaction is 10-150 ℃; the time of the copolymerization reaction is 0.5-12 h.
Preferably, the epoxide includes 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.
Preferably, the pressure of the carbon dioxide is 0.1MPa to 8 MPa.
The invention provides an oligomeric multicenter metalloporphyrin complex which has a structure shown in a formula I. The metalloporphyrin complex has a plurality of active centers and has higher catalytic activity when catalyzing the copolymerization of carbon dioxide and alkylene oxide. In addition, the catalyst also has higher product selectivity and high-temperature stability when catalyzing the copolymerization of carbon dioxide and alkylene oxide. The oligomeric multicenter metalloporphyrin complex is applied to synthesis of ether-rich polycarbonate, and the structure of the synthesized product contains a certain amount of ether segments, so that the brittleness problem of the conventional polycarbonate material can be solved, the toughness of the material is enhanced, and the application space of the material is expanded. The experimental results show that: the conversion frequency TOF value of a system for catalyzing copolymerization of carbon dioxide and alkylene oxide is 34h-1～8110h-1(ii) a The number average molecular weight of the copolymerization reaction product of the carbon dioxide and the alkylene oxide is 6800-46000 g/mol, and the molecular weight distribution is 1.21-1.28; the by-products in the reaction product are less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 28 to 62 percent.
Detailed Description
The invention provides an oligomeric metalloporphyrin complex, which has a structure shown in a formula I:
Figure BDA0002035919310000051
in the formula I, R isaIs selected from
Figure BDA0002035919310000052
The R isbIs selected from H or
Figure BDA0002035919310000053
The value of n is 2-50;
Figure BDA0002035919310000054
is a linking group;
the above-mentioned
Figure BDA0002035919310000055
Is a metalloporphyrin complex having the structure of formula II:
Figure BDA0002035919310000056
in the formula II, M is a metal element; 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, 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;
x is selected from halo, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoate, p-methylbenzenesulfonate, 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-bistrifluoromethylphenol oxyanion, or pentafluorophenol oxyanion.
In the present invention, the
Figure BDA0002035919310000061
Has a structure of formula III or formula IV:
Figure BDA0002035919310000062
wherein the value of p is an integer of 1-16.
In the present invention, p is specifically 1,2, 4 or 6.
In the present invention, the metal element is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; preferably selected from iron, cobalt or aluminium.
In the present invention, the oligomeric metalloporphyrin complex is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106:
Figure BDA0002035919310000063
Figure BDA0002035919310000071
Figure BDA0002035919310000072
wherein Y is 2, 4-dinitrophenol oxyanion.
The oligomeric metalloporphyrin complex provided by the invention is applied to the synthesis of ether-rich polycarbonate. The ether-rich polycarbonate has a certain amount of ether segments in the structure, so that the brittleness problem of polycarbonate materials in the prior art can be solved, the toughness of the materials is enhanced, and the application space of the materials is expanded.
In the invention, the preparation method of the oligomeric metalloporphyrin complex in the technical scheme comprises the following steps:
reacting a compound with a structure shown in a formula III with a metal coordination compound to obtain an oligomeric metalloporphyrin complex with a structure shown in a formula I;
Figure BDA0002035919310000073
in the formula III, Ra' selected from
Figure BDA0002035919310000081
The R isbSelected from H or
Figure BDA0002035919310000082
The value of n is 2-50;
Figure BDA0002035919310000083
is a linking group;
the above-mentioned
Figure BDA0002035919310000084
Is a porphyrin complex having the structure of formula IV:
Figure BDA0002035919310000085
in the formula IV, R is1～R19Independently selected from 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.
The invention is prepared by a ring-opening metathesis polymerization method, the number of active centers is adjustable, compared with the prior art, the scheme can rapidly prepare the porphyrin complex containing a plurality of active centers, and the porphyrin complex has high catalytic activity, product selectivity and high temperature stability when catalyzing the copolymerization of carbon dioxide and alkylene oxide.
In the present invention, the compound having the structure of formula iii may be selected from formula 201, formula 202, formula 203, or formula 204:
Figure BDA0002035919310000086
Figure BDA0002035919310000091
in a particular embodiment of the invention, the compound having the structure of formula iii is preferably prepared according to the following method:
contacting a compound having the structure of formula V with CHCl in the presence of a Grubbs III catalyst3Carrying out ring opening metathesis polymerization reaction to obtain a compound with a structure shown in a formula III;
Figure BDA0002035919310000092
in the formula V, R iscIs selected from
Figure BDA0002035919310000093
RdIs selected from H or
Figure BDA0002035919310000094
The value of n is 2-50; the above-mentioned
Figure BDA0002035919310000101
Is a linking group;
Figure BDA0002035919310000102
has a structure of formula III or formula IV:
Figure BDA0002035919310000103
wherein the value of p is an integer of 1-16;
the above-mentioned
Figure BDA0002035919310000104
Is a porphyrin complex having the structure of formula IV:
Figure BDA0002035919310000105
in the present invention, the compound having the structure of formula v may be selected from formula 301, formula 302, formula 303, or formula 304:
Figure BDA0002035919310000106
Figure BDA0002035919310000111
in a specific embodiment of the invention, the compound having the structure of formula v is prepared by:
Figure BDA0002035919310000112
reacting with 5-norbornene-2-acyl chloride or 5-norbornene-2, 3-diacid chloride to obtain a compound with a structure shown in a formula V;
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, 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; the R is20Selected from H or an aliphatic alcohol group;
the above-mentioned
Figure BDA0002035919310000121
Specifically formula 401, formula 402, or formula 403:
Figure BDA0002035919310000122
in the present invention, the metal complex is preferably selected from a divalent metal compound or a trivalent metal compound; the divalent metal compound is selected fromOne or more selected from zinc chloride, zinc acetate, manganese chloride, magnesium chloride, ferrous chloride and cobalt acetate; the trivalent metal compound is selected from diethylaluminum chloride (AlEt)2Cl)。
When the complex is a divalent complex, the metal complex reacts with a compound with a structure shown in a formula III, and then is coordinated with a phenol oxygen anion compound to obtain the oligomeric multicenter metalloporphyrin complex with the structure shown in the formula I.
When the complex is a trivalent complex, the metal complex reacts with a compound with a structure shown in a formula III to obtain the oligomeric multicenter metalloporphyrin complex with the structure shown in the formula I.
The invention provides a preparation method of polycarbonate, which comprises the following steps:
under the action of a cocatalyst and the oligomeric metalloporphyrin complex as a main catalyst, carrying out copolymerization reaction on carbon dioxide and epoxide to obtain polycarbonate;
the cocatalyst comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and organic base; more preferably, the cocatalyst comprises one or more of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, bistriphenylphosphine ammonium chloride (PPNCl), bistriphenylphosphine ammonium bromide, bistriphenylphosphamidoamine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene 4-dimethylaminopyridine and gamma-chloropropylmethyldimethoxysilane.
The mass ratio of the main catalyst to the cocatalyst is 1: 0.1-5. In the specific embodiment of the invention, the mass ratio of the main catalyst to the auxiliary catalyst is 1: 0.5; or 1: 0.83; or 1: 0.67.
In the present invention, the mass ratio of the main catalyst and the epoxide is 1: 2000 to 500000. In a specific embodiment of the present invention, the mass ratio of the procatalyst to the epoxide is 1: 5000; or 1: 100000; or 1: 25000.
In the present invention, the cocatalyst is selected from one or more of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphine nitramine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene-4-dimethylaminopyridine and gamma-chloropropylmethyldimethoxysilane.
In the invention, the temperature of the copolymerization reaction is 10-150 ℃; the time of the copolymerization reaction is 0.5-12 h. In a specific embodiment of the present invention, the temperature of the copolymerization reaction is specifically 10 ℃, 25 ℃, 40 ℃, 70 ℃, 110 ℃ or 90 ℃; the time is specifically 3h, 1h, 0.5h, 1h or 12 h.
In the invention, 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. In a particular embodiment of the invention, the epoxide is in particular propylene oxide or epichlorohydrin.
In the present invention, the pressure of the carbon dioxide is 0.1MPa to 8 MPa. In a specific embodiment of the invention, the pressure of the carbon dioxide is specifically 3MPa, 8MPa or 6 MPa.
In order to further illustrate the present invention, the following examples are provided to describe the preparation of oligomeric metalloporphyrin complexes and polycarbonates in detail, but they should not be construed as limiting the scope of the present invention.
Preparation example 1:
Figure BDA0002035919310000141
(1) adding 15g (120mmol) of 3-hydroxybenzaldehyde, 39g (370mmol) of benzaldehyde and 33g (490mmol) of pyrrole into 500mL of propionic acid, heating to 130 ℃, refluxing for 2h, cooling to room temperature after the reaction is finished, concentrating the reaction solution to 200mL, adding methanol, cooling in a refrigerator overnight, filtering to obtain a product, and performing silica gel column chromatography (CHCl)3/CH3OH) to obtain the product Por-A with the yield of about 10 percent.1H-NMR(CDCl3): 8.76,8.20,8.08,7.71,7.22, -2.93. High resolution electrospray mass spectrometryThe analysis result is [ C44H30N4O ]]：630.75，found：630.71。
(2) 3.15g (5mmol) of Por-A, 7.8g (50mmol) of 5-norbornene-2-yl chloride and 2ml of pyridine are added under argon to 100ml of dry dichloromethane and stirred at room temperature for 48 h. Washing with dilute hydrochloric acid solution, distilled water, saturated sodium bicarbonate, and distilled water for three times, vacuum removing solvent, and subjecting the obtained product to silica gel column Chromatography (CH)2Cl2Petroleum ether is 3: 7) purifying to obtain the product Por-B with the yield of about 50 percent.1H-NMR(CDCl3): 8.85,8.22,8.12,7.78,7.49,6.22,6.02,3.26,3.03,2.88,1.93,1.45,1.32, -2.79. The analysis result of the high-resolution electrospray mass spectrometry is [ C52H38N4O 2]]：750.30，found：750.30。
(3) The feeding molar ratio of the polymerized monomer Por-B to the Grubbs III catalyst is 50: 1. under argon, 0.3g (0.4mmol,50eq) of Por-B,71mg (8umol, 1eq) of Grubbs III catalyst, 15ml of CHCl3Adding the mixture into a 100ml single-neck flask, carrying out freeze drying by liquid nitrogen to remove oxygen, filling argon for three times, and reacting for 3 hours at 40 ℃. After the reaction is finished, 5ml of vinyl ether is added, stirring is continued for 15min, then ether is added to precipitate the product, and the solid polymer product Poly-Por-1 is collected by centrifugation, wherein the yield is about 80%.1H-NMR(CDCl3): 8.80,8.24,8.10,7.77,7.47,5.35,3.24,3.00,2.87,1.30,1.43,1.31, -2.76. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝12500,PDI＝1.24。
(4) Dissolving 0.5mmol of the oligomeric porphyrin ligand in 20ml of dry chloroform, and dropwise adding 0.5mmol of AlEt2And Cl, and stirring the mixture at room temperature for 6 hours. And purifying the obtained product by column chromatography, and drying to obtain the required complex Poly-Al-1.
Preparation example 2:
Figure BDA0002035919310000161
(1) the polymerized monomer Por-B synthesis is shown in "preparation 1". The feeding molar ratio of the polymerized monomer Por-B to the Grubbs III catalyst is 100: 1. under the protection of argon, 0.3g (0.4mmol,50eq) of Por-B,35mg (8umol, 1eq) Grubbs III catalyst, 15ml CHCl3Adding the mixture into a 100ml single-neck flask, carrying out freeze drying by liquid nitrogen to remove oxygen, filling argon for three times, and reacting for 3 hours at 40 ℃. After the reaction is finished, 5ml of vinyl ether is added, stirring is continued for 15min, then ether is added to precipitate the product, and the solid polymer product Poly-Por-2 is collected by centrifugation, wherein the yield is about 80%.1H-NMR(CDCl3): 8.81,8.25,8.12,7.79,7.46,5.33,3.25,3.01,2.88,1.31,1.40,1.29, -2.78. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝18000,PDI＝1.26。
(4) Dissolving 0.5mmol of the oligomeric porphyrin ligand in 20ml of dry chloroform, and dropwise adding 0.5mmol of AlEt2And Cl, and stirring the mixture at room temperature for 6 hours. And purifying the obtained product by column chromatography, and drying to obtain the required complex Poly-Al-2.
Preparation example 3:
Figure BDA0002035919310000171
(1) adding 15g (120mmol) of 3-hydroxybenzaldehyde, 69g (370mmol) of p-bromobenzaldehyde and 33g (490mmol) of pyrrole into 500mL of propionic acid, heating to 130 ℃ or so, refluxing for 2h, cooling to room temperature after the reaction is finished, concentrating the reaction solution to 200mL, adding methanol, cooling in a refrigerator overnight, filtering to obtain a product, and performing silica gel column chromatography (CHCl)3/CH3OH) to obtain the product Por-C with the yield of about 15 percent.1H-NMR(CDCl3): 8.86,8.27,8.15,7.75,7.54, -2.85. The analysis result of the high-resolution electrospray mass spectrometry is [ C44H27Br3N4O ]]：863.97，found：863.90。
(2) 4.32g (5mmol) of Por-C, 7.8g (50mmol) of 5-norbornene-2-yl chloride and 2ml of pyridine are added under argon to 100ml of dry dichloromethane and stirred at room temperature for 48 h. Washing with dilute hydrochloric acid solution, distilled water, saturated sodium bicarbonate, and distilled water for three times, vacuum removing solvent, and subjecting the obtained product to silica gel column Chromatography (CH)2Cl2Petroleum ether is 3: 7) purifying to obtain the product Por-D with the yield of about 50 percent.1H-NMR(CDCl3)：8.86,8.21,8.07,7.93,7.49,6.20,6.00,3.26,3.03,2.88,1.93,1.45,1.32, -2.81. The analysis result of the high-resolution electrospray mass spectrometry is [ C52H35Br3N4O 2]]：984.03，found：984.00。
(3) The feeding molar ratio of the polymerized monomer Por-D to the Grubbs III catalyst is 50: 1. under argon, 0.3936g (0.4mmol,50eq) of Por-B,71mg (8umol, 1eq) of Grubbs III catalyst, 15ml of CHCl3Adding the mixture into a 100ml single-neck flask, carrying out freeze drying by liquid nitrogen to remove oxygen for three times, filling argon, and reacting for 3 hours at 40 ℃. After the reaction is finished, 5ml of vinyl ether is added, stirring is continued for 15min, then ether is added to precipitate the product, and the solid polymer product Poly-Por-3 is collected by centrifugation, wherein the yield is about 80%.1H-NMR(CDCl3): 8.85,8.22,8.09,7.91,7.47,5.33,3.24,3.00,2.87,1.30,1.43,1.31, -2.77. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝12200,PDI＝1.28。
(4) Dissolving 0.5mmol of the oligomeric porphyrin ligand in 20ml of dry chloroform, and dropwise adding 0.5mmol of AlEt2And Cl, and stirring the mixture at room temperature for 6 hours. And purifying the obtained product by column chromatography, and drying to obtain the required complex Poly-Al-3.
Preparation example 4:
Figure BDA0002035919310000191
(1) the synthesis of the complex Por-A is shown in "preparation example 1". 0.63g (1mmol) of Por-A, 0.15mL (1.15mmol) of 6-chloro-1-hexanol and 0.14g of potassium carbonate were dissolved in 100mL of anhydrous DMF under nitrogen protection, and after stirring sufficiently, the mixture was heated under reflux for 12 h. After the reaction is finished, the product is dried and dissolved by dichloromethane, extracted and washed by water for 3 times, and the organic phase is dried by anhydrous magnesium sulfate and then dried by spinning. The solid product was purified by column chromatography on silica gel using methylene chloride as eluent to give about 0.68g of product Por-E. High resolution electrospray mass spectrometry analysis, the analysis result is [ C50H42N4O2 ]: 730.91, found: 730.88.
(2) 3.65g (5mmol) of Por-E, 7.8g (50mmol) of 5-norbornene-2-yl chloride and 2ml of pyridine are added under argon to 100ml of dry dichloromethane and stirred at room temperature for 48 h. After the reaction is finished, respectivelyWashing with dilute hydrochloric acid solution, distilled water, saturated sodium bicarbonate, and distilled water for three times, vacuum removing solvent, and subjecting the obtained product to silica gel column Chromatography (CH)2Cl2Petroleum ether is 3: 7) purifying to obtain the product Por-F with the yield of about 50 percent. The analysis result of the high-resolution electrospray mass spectrometry is [ C53H40N4O 2]]：780.31，found：780.30。
(3) The feeding molar ratio of the polymerized monomer Por-F to the Grubbs III catalyst is 50: 1. under argon, 0.3121g (0.4mmol,50eq) of Por-B,71mg (8umol, 1eq) of Grubbs III catalyst, 15ml of CHCl3Adding the mixture into a 100ml single-neck flask, carrying out freeze drying by liquid nitrogen to remove oxygen, filling argon for three times, and reacting for 3 hours at 40 ℃. After the reaction is finished, 5ml of vinyl ether is added, stirring is continued for 15min, then ether is added to precipitate the product, and the solid polymer product Poly-Por-4 is collected by centrifugation, wherein the yield is about 80%. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝13000,PDI＝1.26。
(4) Dissolving 0.5mmol of the oligomeric porphyrin ligand in 20ml of dry chloroform, and dropwise adding 0.5mmol of AlEt2And Cl, and stirring the mixture at room temperature for 6 hours. And purifying the obtained product by column chromatography, and drying to obtain the required complex Poly-Al-4.
Preparation example 5:
Figure BDA0002035919310000211
(1) 7.30g (10mmol) of Por-E, 2.1799g (2mmol) of 5-norbornene-2, 3-dicarboxylic acid dichloride and 0.5ml of pyridine are added to 100ml of dry dichloromethane under argon and stirred at room temperature for 48 h. Washing with dilute hydrochloric acid solution, distilled water, saturated sodium bicarbonate, and distilled water for three times, vacuum removing solvent, and subjecting the obtained product to silica gel column Chromatography (CH)2Cl2Petroleum ether is 3: 7) purifying to obtain the product Por-G with the yield of about 60 percent. The analysis result of the high-resolution electrospray mass spectrometry is [ C103H78N8O6 ]]：1522.60，found：1522.60。
(2) The feeding molar ratio of the polymerized monomer Por-G to the Grubbs III catalyst is 50: 1. under the protection of argon, 0.6090G (0.4mmol,50eq) of Por-G,71mg (8umol, 1 e)q) Grubbs III catalyst, 15ml CHCl3Adding the mixture into a 100ml single-neck flask, carrying out freeze drying by liquid nitrogen to remove oxygen, filling argon for three times, and reacting for 3 hours at 40 ℃. After the reaction is finished, 5ml of vinyl ether is added, stirring is continued for 15min, then ether is added to precipitate the product, and the solid polymer product Poly-Por-5 is collected by centrifugation, wherein the yield is about 75%. Gel permeation chromatography (GPC, CH)2Cl2):Mn＝8000,PDI＝1.30。
(3) Dissolving 0.5mmol of the oligomeric porphyrin ligand in 20ml of dry chloroform, and dropwise adding 0.5mmol of AlEt2And Cl, and stirring the mixture at room temperature for 6 hours. And purifying the obtained product by column chromatography, and drying to obtain the required complex Poly-Al-5.
Preparation example 6:
Figure BDA0002035919310000221
the ligand Poly-Por-1(320mg) was dissolved in 20mL of anhydrous DMF, and 180mg of cobalt acetate with crystal water removed was added thereto, followed by reaction with stirring at room temperature for 12 hours. 0.042g of anhydrous lithium chloride was added, and the reaction was continued for 12 hours with introduction of oxygen. The reaction was stopped, the solvent was removed under reduced pressure, and the residue was dissolved in 20mL of methylene chloride and washed three times with 70mL of a saturated sodium bicarbonate solution and 70mL of a saturated saline solution, respectively. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was dissolved in 20mL of dichloromethane, and 0.10g of silver tetrafluoroborate was added and reacted for 24 hours with exclusion of light. Insoluble matter was removed by filtration, and 0.20g of sodium 2, 4-dinitrophenolate was added to the filtrate to react at room temperature for 2 hours. Insoluble inorganic salts were removed by filtration and the solvent was removed under reduced pressure. The crude product was recrystallized from dichloromethane and n-hexane to give the complex Poly-Al-6 in about 85% yield.
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 oligomeric aluminum porphyrin complex Poly-Al-1,0.0075mmol of PPNCl and 75mmol of dried propylene oxide in preparation example 1 were added into 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, so that the pressure in the high-pressure reaction kettle reached 3MPa, and the temperature of the high-pressure reaction kettle was controlled at 25 ℃ for polymerization 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 28 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 665h-1(ii) a The polycarbonate obtained by the preparation had a number average molecular weight of 46000 and a molecular weight distribution of 1.23, 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 oligoaluminum-based porphyrin complex Poly-Al-1,0.0075mmol of PPNCl of preparation example 1 and 75mmol of dried propylene oxide were added to a 15ml autoclave after water removal and oxygen removal, and the autoclave was then removed from the glove boxThen the mixture is taken out, 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 40 ℃ for carrying out 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 33 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 1015h-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 32000 and a molecular weight distribution of 1.26.
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 of the oligomeric aluminum porphyrin complex Poly-Al-1,0.0075mmol of PPNCl and 150mmol of dried propylene oxide in preparation example 1 were added into 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 with a pressure adjustment function, so that the pressure in the autoclave reached 3MPa, and the temperature of 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 first reaction kettleTime sampling1H-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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 38 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 2985h through calculation-1(ii) a The number average molecular weight of the polycarbonate obtained was 27000 and the molecular weight distribution was 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 oligomeric aluminum porphyrin complex Poly-Al-1,0.0075mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 1 were added into a 50ml 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, so that the pressure in the high-pressure reaction kettle reached 3MPa, and the temperature of the high-pressure reaction kettle was controlled at 110 ℃ for polymerization for 0.5 h. 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 the examples showed that the polycarbonate had a carbonate unit content of 42% and a cyclic carbonate side productThe product content is less than 10%; the TOF value of the catalytic system is calculated to be 6549h-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 25000 and a molecular weight distribution of 1.26.
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 oligomeric aluminum porphyrin complex Poly-Al-2,0.0075mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 2 were added into a 50ml 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, so that the pressure in the high-pressure reaction kettle reached 3MPa, 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 40 percent, and the content of cyclic carbonate by-products is less than 10 percent; the TOF value of the catalytic system is calculated to be 5870h-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 21000 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 oligosaccharide porphyrin complex Poly-Al-2,0.0075mmol of PPNCl and 150mmol of dried propylene oxide in preparation example 2 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 with a pressure adjustment function, so that the pressure in the autoclave reached 3MPa, and the temperature of 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 34 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 2755h through calculation-1(ii) a The number average molecular weight of the polycarbonate obtained was 29000 as determined by GPC, and the molecular weight distribution was 1.28.
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 oligomeric aluminum porphyrin complex Poly-Al-3,0.0075mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 3 were added into a 50ml 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, so that the pressure in the high-pressure reaction kettle reached 3MPa, and the temperature of the high-pressure reaction kettle was controlled at 110 ℃ for polymerization for 0.5 h. 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 40 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 8110h-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 25000 and a molecular weight distribution of 1.24.
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 oligomeric aluminum porphyrin complex Poly-Al-3,0.0075mmol of PPNCl in preparation example 3 and 150mmol of dried propylene oxide were added into a 25ml autoclave after water removal and oxygen removal, and then the autoclave was taken out from the glove box and passed through a pressure regulating function IIThe carbon dioxide supply line is filled with carbon dioxide into the high-pressure reaction kettle, the pressure in the high-pressure reaction kettle reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 70 ℃ to carry out polymerization reaction for 1 h. 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 35 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 4530h-1(ii) a The polycarbonate thus obtained had a number average molecular weight of 28000 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 oligomeric aluminum porphyrin complex Poly-Al-3,0.0075mmol of PPNCl and 75mmol of dried epichlorohydrin in preparation example 3 are added into a 15ml high-pressure reaction kettle after water removal and oxygen removal processes, then the high-pressure reaction kettle is taken out from 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 12 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. At 25 ℃ under vacuumAnd pumping out unreacted propylene oxide in the drying oven to obtain the polycarbonate.
By passing1H-NMR nuclear magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the carbonate unit content in the polycarbonate is 42 percent, and the content of the cyclic carbonate by-product is less than 10 percent; the TOF value of the catalytic system is 34h through calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 6800 and a molecular weight distribution of 1.26 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 oligomeric aluminum porphyrin complex Poly-Al-4,0.0075mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 4 were added into a 50ml 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, so that the pressure in the high-pressure reaction kettle reached 3MPa, 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 44 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 6758h by calculation-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 31000 and a molecular weight distribution of 1.22.
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 oligomeric aluminum porphyrin complex Poly-Al-4,0.01 mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 4 were added into a 50ml high-pressure reaction kettle after water 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 6MPa, and the temperature of the high-pressure reaction kettle was controlled at 90 ℃ 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 62 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 5200h by calculation-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 42000 and a molecular weight distribution of 1.21.
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 oligomeric aluminum porphyrin complex Poly-Al-4,0.0125mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 4 were added to a 50ml high-pressure reaction kettle after water 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, so that the pressure in the high-pressure reaction kettle reached 8MPa, and the temperature of the high-pressure reaction kettle was controlled at 90 ℃ 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 60 percent, and the content of cyclic carbonate by-products is less than 0.03 percent; the TOF value of the catalytic system is 5350h by calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 40100 and a molecular weight distribution of 1.22, as determined by GPC.
Example 13
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 boxIn the preparation method, 0.015mmol of the oligomeric aluminum porphyrin complex Poly-Al-4,0.0075mmol of PPNCl and 150mmol of dried propylene oxide in preparation example 4 are added into a 25ml high-pressure reaction kettle after water removal and oxygen removal, then the high-pressure reaction kettle is taken out from a 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 70 ℃ for polymerization reaction for 1 h. 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the carbonate unit content in the polycarbonate is 39 percent, and the content of the cyclic carbonate by-product is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 3987h-1(ii) a The polycarbonate obtained by GPC had a number average molecular weight of 22000 and a molecular weight distribution of 1.27.
Example 14
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 oligosaccharide porphyrin complex Poly-Al-5,0.0075mmol of PPNCl and 375mmol of dried propylene oxide in preparation example 5 were added to a 50ml autoclave after water 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, and the inside of the autoclave was allowed to contain carbon dioxideThe pressure reaches 3MPa, and the temperature of the high-pressure reaction kettle is controlled at 110 ℃ for polymerization reaction for 1 h. 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 32 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is calculated to be 7758h-1(ii) a The polycarbonate obtained by GPC was found to have a number average molecular weight of 24000 and a molecular weight distribution of 1.23.
Example 15
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 oligosaccharide porphyrin complex Poly-Al-5,0.0075mmol of PPNCl and 150mmol of dried propylene oxide in preparation example 5 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 adjustment function, so that the pressure in the autoclave reached 3MPa, and the temperature of the autoclave was controlled at 70 ℃ for 1 hour of polymerization. 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. Pumping out unreacted propylene oxide in a vacuum drying oven at 25 deg.CAnd (5) alkane to obtain the polycarbonate.
By passing1H-NMR nuclear magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 38 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 3370h through calculation-1(ii) a The polycarbonate obtained had a number average molecular weight of 30000 and a molecular weight distribution of 1.26 as determined by GPC.
Example 16
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 oligosaccharide porphyrin complex Poly-Al-6, 0.0075mmol of PPNCl and 75mmol of dried propylene oxide in preparation example 6 were added to a 15ml 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 adjustment function, so that the pressure in the autoclave reached 3MPa, and the temperature of the autoclave 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 magnetism is used for detecting the polycarbonate prepared in the example, and the result shows that the content of carbonate units in the polycarbonate is 52 percent, and the content of cyclic carbonate by-products is less than 0.01 percent; the TOF value of the catalytic system is 560h by calculation-1(ii) a The number average molecular weight of the polycarbonate obtained was 32000, measured by GPC, and the molecule was found to beThe amount distribution was 1.23.
As can be seen from the above examples, the present invention provides an oligomeric multicenter metalloporphyrin complex having the structure of formula I. The metalloporphyrin complex has a plurality of active centers and has higher catalytic activity when catalyzing the copolymerization of carbon dioxide and alkylene oxide. In addition, the catalyst also has higher product selectivity and high-temperature stability when catalyzing the copolymerization of carbon dioxide and alkylene oxide. The oligomeric multicenter metalloporphyrin complex is applied to synthesis of ether-rich polycarbonate, and the structure of the synthesized product contains a certain amount of ether segments, so that the brittleness problem of the conventional polycarbonate material can be solved, the toughness of the material is enhanced, and the application space of the material is expanded. The experimental results show that: the conversion frequency TOF value of a system for catalyzing copolymerization of carbon dioxide and alkylene oxide is 34h-1～8110h-1(ii) a The number average molecular weight of the copolymerization reaction product of the carbon dioxide and the alkylene oxide is 6800-46000 g/mol, and the molecular weight distribution is 1.21-1.28; the by-products in the reaction product are less than 10 percent, even less than 0.01 percent; the content of carbonate units in the polymer reaches 28 to 62 percent.
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. An oligomeric metalloporphyrin complex having the structure of formula i:
Figure FDA0003011417430000011
in the formula I, R isaIs selected from
Figure FDA0003011417430000012
The R isbIs selected from H or
Figure FDA0003011417430000013
The value of n is 2-50;
Figure FDA0003011417430000014
is a linking group;
the above-mentioned
Figure FDA0003011417430000015
Is a metalloporphyrin complex having the structure of formula II:
Figure FDA0003011417430000016
in the formula II, M is a metal element; 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, 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;
x is selected from halo, -NO3、CH3COO-、CCl3COO-、CF3COO-、ClO4-、BF4-、BPh4-、-CN、-N3P-methylbenzoate, p-methylbenzenesulfonate, 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-bistrifluoromethylphenol oxyanion, or pentafluorophenol oxyanion.
2. The oligomeric metalloporphyrin complex of claim 1, wherein the metalloporphyrin complex is conjugated to a pharmaceutically acceptable carrier
Figure FDA0003011417430000021
Has a structure of formula III or formula IV:
Figure FDA0003011417430000022
wherein the value of p is an integer of 1-16.
3. The oligomeric metalloporphyrin complex according to claim 1, wherein the metallic element is selected from magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
4. The oligomeric metalloporphyrin complex according to claim 1, wherein the oligomeric metalloporphyrin complex is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106:
Figure FDA0003011417430000023
Figure FDA0003011417430000031
Figure FDA0003011417430000032
wherein Y is 2, 4-dinitrophenol oxyanion.
5. A method of making a polycarbonate comprising the steps of:
under the action of a cocatalyst and the oligomeric metalloporphyrin complex as the main catalyst, carrying out copolymerization reaction on carbon dioxide and epoxide to obtain polycarbonate;
the cocatalyst comprises one or more of quaternary ammonium salt, quaternary phosphonium salt and organic base;
the mass ratio of the main catalyst to the cocatalyst is 1: 0.1-5.
6. The method of claim 5, wherein the mass ratio of the procatalyst to the epoxide is 1: 2000 to 500000.
7. The method according to claim 5, wherein the co-catalyst is one or more selected from the group consisting of tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, bistriphenylphosphine ammonium chloride, bistriphenylphosphine ammonium bromide, bistriphenylphosphine nitramine, 1,5, 7-triazabicyclo [4.4.0] dec-5-en-4-dimethylaminopyridine and γ -chloropropylmethyldimethoxysilane.
8. The method according to claim 5, wherein the temperature of the copolymerization reaction is 10 ℃ to 150 ℃; the time of the copolymerization reaction is 0.5-12 h.
9. The preparation method according to claim 5, 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.
10. The production method according to claim 5, wherein the pressure of the carbon dioxide is 0.1 to 8 MPa.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2352449A (en) * 1999-04-29 2001-01-31 Secr Defence Synthesis of polycarbonates
CN102731766A (en) * 2012-07-24 2012-10-17 中国科学院长春应用化学研究所 Preparation method of aliphatic polycarbonate polyol
CN105111426A (en) * 2015-09-16 2015-12-02 武汉理工大学 Quaternary ammonium salt functionalized porphyrin catalyst and preparation method thereof
CN106957415A (en) * 2015-09-16 2017-07-18 武汉理工大学 It is a kind of for composite catalyst of carbon dioxide, expoxy propane and lactide ternary polymerization and preparation method thereof
CN108409954A (en) * 2018-02-06 2018-08-17 浙江大学 A kind of synthetic method of carbon dioxide-base polycarbonate block copolymer
JP2018184555A (en) * 2017-04-26 2018-11-22 学校法人東京理科大学 Method for producing aliphatic polycarbonate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2352449A (en) * 1999-04-29 2001-01-31 Secr Defence Synthesis of polycarbonates
CN102731766A (en) * 2012-07-24 2012-10-17 中国科学院长春应用化学研究所 Preparation method of aliphatic polycarbonate polyol
CN105111426A (en) * 2015-09-16 2015-12-02 武汉理工大学 Quaternary ammonium salt functionalized porphyrin catalyst and preparation method thereof
CN106957415A (en) * 2015-09-16 2017-07-18 武汉理工大学 It is a kind of for composite catalyst of carbon dioxide, expoxy propane and lactide ternary polymerization and preparation method thereof
JP2018184555A (en) * 2017-04-26 2018-11-22 学校法人東京理科大学 Method for producing aliphatic polycarbonate
CN108409954A (en) * 2018-02-06 2018-08-17 浙江大学 A kind of synthetic method of carbon dioxide-base polycarbonate block copolymer

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