CN113336932B - Metal coordination catalyst for synthesizing carbon dioxide-based biodegradable material and application thereof - Google Patents
Metal coordination catalyst for synthesizing carbon dioxide-based biodegradable material and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
Abstract
The invention discloses a metal coordination catalyst for synthesizing a carbon dioxide-based biodegradable material and application thereof, wherein the metal coordination catalyst is used for catalyzing copolymerization reaction of carbon dioxide and a compound to prepare the carbon dioxide-based biodegradable materialThe catalyst, the ligand of the coordination catalyst has the following general formula
Description
Technical Field
The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a metal coordination catalyst for synthesizing a carbon dioxide-based biodegradable material and application thereof.
Background
Carbon dioxide is an inexhaustible carbon resource on the earth, and the reserve is extremely rich, and the content of the carbon dioxide in the atmosphere reaches 2.75 multiplied by 10 12 Ton. In recent years, due to the decreasing of petroleum resources, ecological and environmental problems caused by a large amount of carbon dioxide in the air, and the like, all countries around the world have paid great attention to the development and utilization of carbon dioxide in solving the problems of energy shortage, resource shortage, serious public nuisance, and the like. Carbon dioxide chemistry is also gradually paid attention by scientists in China as a branch of C1 chemistry.
In the active research on activation of carbon dioxide, the synthesis of polymer materials using carbon dioxide has become a very attractive issue. Since the first synthesis of high molecular weight alternating copolymers by using carbon dioxide and propylene oxide in Inoue in 1969, the reaction of carbon dioxide and many substances with different properties for synthesizing high molecules has been successfully carried out. Among them, the copolymerization of carbon dioxide with epoxy compounds has attracted attention.
The carbon dioxide and the epoxy compound are cheap and easy to obtain, and compared with traditional synthetic methods such as phosgene/diol polycondensation and cyclic carbonate ring-opening copolymerization, the method has remarkable green chemical characteristics. No organic solvent is required to be added in the reaction process; the produced polycarbonate can be degraded into harmless organic micromolecules under natural conditions, so that secondary pollution to the environment is effectively avoided. Aliphatic polycarbonates, such as polypropylene carbonate and polycyclohexene carbonate, are potentially useful in many applications, such as biomedical materials, packaging materials, engineering resin synthesis, pyrotechnic manufacturing, safety glass, and the like. The aliphatic polycarbonate can be completely degraded into harmless diol in a living body, has good biocompatibility, is a very important medical material, and receives more and more attention in the fields of surgical sutures, bone fixation materials, drug release systems and the like. The catalyst used in the synthesis process has great influence on the production economy and the performance of the obtained aliphatic polycarbonate, and the existing catalyst has low activity, low catalytic selectivity and long polymerization time, and needs to be developed with better effect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a metal coordination catalyst for synthesizing a carbon dioxide-based biodegradable material and application thereof, and the metal coordination catalyst has the advantages of high catalytic efficiency, good selectivity and simple operation.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention relates to a metal coordination catalyst for the copolymerization reaction of carbon dioxide and epoxy compound to synthesize carbon dioxide-based biodegradable material, wherein the general formula of the ligand is as follows:
wherein, in the ligand used by the coordination catalyst, A and B groups are aromatic heterocyclic compounds;
specifically, A and B groups in a ligand used by the coordination catalyst are pyridine, furan or thiophene.
When the A group in the ligand used by the coordination catalyst is pyridine, furan or thiophene, the two-CH = N groups connected on the aromatic heterocyclic ring can be in ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
When the B group in the ligand used by the coordination catalyst is pyridine, furan or thiophene, the two-NH groups connected on the aromatic heterocyclic ring can be in ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
The C, D, E and F groups in the ligand used by the coordination catalyst are one or two of alkyl, hydrogen, alkoxy, carboxyl, substituted aryl or substituted heteroaryl.
When the B group in the ligand used by the coordination catalyst is pyridine, furan or thiophene, the C, D, E and F groups can be in ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
The coordination center metal elements used by the coordination catalyst are zinc, aluminum, manganese and magnesium; preferably, the coordination center metal is zinc.
The metal coordination catalyst is used for the copolymerization reaction of carbon dioxide and epoxy compounds to synthesize the carbon dioxide-based biodegradable material.
Preferably, the epoxy compound is one of ethylene oxide, propylene oxide, cyclohexene oxide, 1, 2-butylene oxide and 2, 3-butylene oxide.
Examples of applications are as follows:
the method for catalyzing the copolymerization reaction of carbon dioxide and epoxy compounds by using the 2, 5-di (6-carboxyl-2-imine pyridine) furan condensed 2, 6-diethylaniline zinc complex catalyst comprises the following steps:
vacuumizing an autoclave for 1h at the temperature higher than 100 ℃, replacing carbon dioxide for 2-3 times, cooling to room temperature, adding a 2, 5-bis (6-carboxyl-2-imine pyridine) furan condensation 2, 6-diethylaniline zinc complex catalyst and an epoxy compound into the autoclave, heating, charging carbon dioxide, opening and stirring, reacting for a period of time, cooling to room temperature, dissolving the polymer out of the autoclave by using dichloromethane, adopting methanol as a precipitator, slowly dropwise adding a dichloromethane solution of the polymer into the methanol, precipitating a solid, filtering and collecting the solid, and drying in vacuum to obtain a copolymerization product polycarbonate.
The mass ratio of the catalyst to the epoxy compound is 1.
Preferably, the copolymerization temperature is from 80 to 150 ℃.
Preferably, the copolymerization pressure is between 1 and 5MPa.
Preferably, the copolymerization reaction time is 10 to 40 hours.
Under the reaction conditions, the aliphatic polycarbonate product can be obtained. The catalyst has multiple coordination types, can play a synergistic effect, and has the advantages of high catalytic efficiency, good selectivity and simple operation.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Example 1
The preparation method of the 2, 5-di (6-amino-2-imine pyridine) thiophene condensed 5-methyl-2-furancarboxylic acid zinc catalyst comprises the following steps:
(1) Weighing 7g (0.05 mol) of 2, 5-dialdehyde thiophene and 10.9g (0.1 mol) of 2, 6-diaminopyridine, respectively dissolving in 100mL of dimethyl sulfoxide, slowly dripping the 2, 6-diaminopyridine solution into the 2, 5-dialdehyde thiophene solution under stirring, heating and refluxing, reacting for 3h, and separating out the product to obtain the 2, 5-bis (6-amino-2-imine pyridine) thiophene. After 16.1g (0.05 mol) of 2, 5-bis (6-amino-2-iminopyridine) thiophene and 12.6g (0.1 mol) of 5-methyl-2-furancarboxylic acid were dissolved in toluene, the resulting solution was mixed, heated under reflux, stirred for 2 hours, and the product was separated to obtain 2, 5-bis (6-amino-2-iminopyridine) thiophene condensed 5-methyl-2-furancarboxylic acid. The product was subjected to structural analysis, 1H NMR (400MHz, CDCl3): δ 2.2 (s, 6H, -CH 3), 6.32 to 7.45 (m, 12H, aromatic), 8.36 (s, 2H, -CH = N), 10.8 (s, 2H, -NH);
(2) Taking 5.39g (0.01 mol) of 2, 5-bis (6-amino-2-imine pyridine) thiophene condensed 5-methyl-2-furancarboxylic acid ligand in a flask, vacuumizing, charging nitrogen for three times, replacing air and water in the flask, cooling by using a cold salt bath, adding 1.51g (0.012 mol) diethyl zinc under the protection of nitrogen, reacting for 0.5h, heating to room temperature, and continuing to react for 1.5h to obtain the 2, 5-bis (6-amino-2-imine pyridine) thiophene condensed 5-methyl-2-furancarboxylic acid zinc complex catalyst.
Example 2
The preparation method of the 2, 5-di (6-amino-2 imine pyridine) furan condensed 6-methyl-2-pyridine formic acid zinc complex catalyst comprises the following steps:
(1) Weighing 1.24g (0.01 mol) of 2, 5-dialdehyde furan and 2.18g (0.02 mol) of 2, 6-diaminopyridine, respectively dissolving in dimethyl sulfoxide, slowly dripping the 2, 6-diaminopyridine solution into the 2, 5-dialdehyde thiophene solution under stirring, heating to 130 ℃, reacting for 2h, and separating out the product to obtain the 2, 5-bis (6-amino-2 imine pyridine) furan. After 3.06g (0.01 mol) of 2, 5-bis (6-amino-2-iminopyridine) furan and 3.014g (0.022 mol) of 6-methyl-2-pyridinecarboxylic acid were dissolved in toluene, they were mixed and refluxed with heating, and stirred for 2 hours, and the product was separated to obtain 2, 5-bis (6-amino-2-iminopyridine) furan condensed 6-methyl-2-pyridinecarboxylic acid. The product was subjected to structural analysis, 1H NMR (400MHz, CDCl3): δ 2.5 to 2.6 (s, 6H, -CH 3), 6.3 to 8.1 (m, 14H, aromatic H), 8.2 (s, 2H, -CH = N), 10.6 (s, 2H, -NH);
(2) Taking 5.45g (0.01 mol) of 2, 5-bis (6-amino-2 imine pyridine) thiophene condensed 5-methyl-2-furancarboxylic acid ligand in a flask, vacuumizing and filling nitrogen for three times, replacing air and water in the flask, cooling by using a cold salt bath, adding 1.51g (0.012 mol) of diethyl zinc under the protection of nitrogen, reacting for 1h, heating to 60 ℃, and continuing to react for 1h to obtain the 2, 5-bis (6-amino-2 imine pyridine) furan condensed 6-methyl-2-pyridinecarboxylic acid zinc complex catalyst.
Example 3
The preparation method of the 2, 5-di (6-amino-2 imine pyridine) furan condensed 5-methyl-2-thiophene formic acid zinc complex catalyst comprises the following steps:
(1) Weighing 2.18g (0.02 mol) of 2, 6-diaminopyridine and 1.24g (0.01 mol) of 2, 5-dialdehyde furan, respectively dissolving in dimethyl sulfoxide, slowly dripping the 2, 6-diaminopyridine solution into the 2, 5-dialdehyde furan solution under stirring, heating and refluxing, reacting for 3h, and separating out the product to obtain the 2, 5-bis (6-amino-2-imine pyridine) furan. After 3.06g (0.01 mol) of 2, 5-bis (6-amino-2-iminopyridine) furan and 2.84g (0.02 mol) of 5-methyl-2-thiophenecarboxylic acid were dissolved in toluene, respectively, the mixture was heated under reflux, stirred for 2 hours, and the product was separated to obtain 2, 5-bis (6-amino-2-iminopyridine) furan condensed 5-methyl-2-thiophenecarboxylic acid ligand. The product was subjected to structural analysis, 1H NMR (400MHz, CDCl3): delta 2.5 (s, 6H, -CH 3), 6.5 to 7.7 (m, 12H, aromatic H), 8.4 (s, 2H, -CH = N), 10.8 (s, 2H, -NH);
(2) Taking 5.54g (0.01 mol) of 2, 5-bis (6-amino-2 imine pyridine) furan condensation 5-methyl-2-thiophene formic acid ligand in a flask, vacuumizing and filling nitrogen for three times, replacing air and water in the flask, cooling by using a cold salt bath, adding 1.51g (0.012 mol) diethyl zinc under the protection of nitrogen, reacting for 1h, heating to 60 ℃, and continuing to react for 1h to obtain the 2, 5-bis (6-amino-2 imine pyridine) furan condensation 5-methyl-2-thiophene formic acid zinc complex catalyst.
Example 4
The preparation method of the 2, 6-di (6-amino-2-imine pyridine) pyridine condensed 5-methyl-2-thiophene formic acid zinc complex catalyst comprises the following steps:
(1) Weighing 1.35g (0.01 mol) of 2, 6-dialdehyde pyridine and 2.4g (0.022 mol) of 2, 6-diaminopyridine, respectively dissolving in dimethyl sulfoxide, slowly dripping the 2, 6-diaminopyridine solution into the 2, 6-dialdehyde pyridine solution under stirring, heating and refluxing, reacting for 2h, and separating out the product to obtain the 2, 6-bis (6-amino-2 imine pyridine) pyridine. After 3.17g (0.01 mol) of 2, 6-bis (6-amino-2-iminopyridine) pyridine and 2.84g (0.02 mol) of 5-methyl-2-thiophenecarboxylic acid were dissolved in toluene, the solutions were mixed, heated under reflux, stirred for 3 hours, and the product was separated to obtain 2, 6-bis (6-amino-2-iminopyridine) pyridine-condensed 5-methyl-2-thiophenecarboxylic acid ligand. The product was subjected to structural analysis, 1H NMR (400MHz, CDCl3): δ 2.38 (s, 6H, -CH 3), 6.1 to 8.1 (m, 13H, aromatic H), 8.6 (s, 2H, -CH = N), 11.1 (s, 2H, -NH);
(2) Taking 5.66g (0.01 mol) of 2, 6-bis (6-amino-2 imine pyridine) pyridine-condensed 5-methyl-2-thiophene formic acid ligand in a flask, vacuumizing and charging nitrogen for three times, replacing air and water in the flask, cooling by using a cold salt bath, adding 1.51g (1.2 mol) diethyl zinc under the protection of nitrogen, reacting for 0.5h, heating to 50 ℃ and reacting for 1h to obtain the 2, 6-bis (6-amino-2 imine pyridine) pyridine-condensed 5-methyl-2-thiophene formic acid zinc complex catalyst.
Example 5
The method for catalyzing the copolymerization reaction of carbon dioxide and propylene oxide by using the 2, 5-bis (6-amino-2-imine pyridine) thiophene condensed 5-methyl-2-furancarboxylic acid zinc complex catalyst comprises the following steps:
vacuumizing an autoclave at 105 ℃ for 1h to replace carbon dioxide for 3 times, cooling to room temperature, adding 0.1g of 2, 5-bis (6-amino-2-imine pyridine) thiophene-condensed 5-methyl-2-furancarboxylic acid zinc complex catalyst and 50g of propylene oxide into the autoclave, heating to 90 ℃, introducing carbon dioxide to keep the pressure at 5MPa, opening and stirring, reacting for 30h, cooling to room temperature, dissolving the polymer out of the autoclave by using dichloromethane, slowly dropwise adding a dichloromethane solution of the polymer into methanol by using methanol as a precipitator, filtering and collecting precipitated solids, and drying in vacuum to obtain 32.7g of a copolymerization product, wherein the molar content of carbonate chain links is 95% by nuclear magnetic hydrogen spectroscopy.
Example 6
The method for catalyzing the copolymerization reaction of carbon dioxide and cyclohexene oxide by using the 2, 5-bis (6-amino-2 imine pyridine) furan condensed 6-methyl-2-pyridine formic acid zinc complex catalyst comprises the following steps:
vacuumizing an autoclave at 105 ℃ for 1h to replace carbon dioxide for 3 times, cooling to room temperature, adding 0.1g of 2, 5-bis (6-amino-2 imine pyridine) furan shrinkage 6-methyl-2-pyridine formic acid zinc complex catalyst and 30g of cyclohexene oxide into the autoclave, heating to 120 ℃, introducing carbon dioxide to keep the pressure at 4MPa, opening and stirring, reacting for 20h, cooling to room temperature, dissolving the polymer out of the autoclave by using dichloromethane, slowly dropwise adding a dichloromethane solution of the polymer into methanol, filtering and collecting precipitated solids, and drying in vacuum to obtain 23.6g of a copolymerization product, wherein the molar content of carbonate chain links is 94% by nuclear magnetic hydrogen spectrometry.
Example 7
The method for catalyzing the copolymerization reaction of carbon dioxide and 1, 2-butylene oxide by using the 2, 5-di (6-amino-2 imine pyridine) furan condensed 5-methyl-2-thiophene formic acid zinc complex catalyst comprises the following steps:
vacuumizing an autoclave at 105 ℃ for 1h to replace carbon dioxide for 3 times, cooling to room temperature, adding 0.1g2, 5-bis (6-amino-2 iminopyridine) furan shrinkage 5-methyl-2-thiophene zinc formate complex catalyst and 20g1, 2-epoxybutane into the autoclave, heating to 90 ℃, filling carbon dioxide to keep the pressure at 2MPa, opening and stirring, reacting for 10h, cooling to room temperature, dissolving the polymer out of the autoclave by using dichloromethane, slowly dropwise adding a dichloromethane solution of the polymer into methanol by using methanol as a precipitator, filtering and collecting precipitated solids, and drying in vacuum to obtain 15.7g of a copolymerization product, wherein the molar content of carbonate chain links is 90% by nuclear magnetic hydrogen spectrometry.
Example 8
The method for catalyzing the copolymerization reaction of carbon dioxide and cyclohexene oxide by using the 2, 6-di (6-amino-2-imine pyridine) pyridine condensed 5-methyl-2-thiophene zinc formate complex catalyst comprises the following steps:
vacuumizing an autoclave at 105 ℃ for 1h to replace carbon dioxide for 3 times, cooling to room temperature, adding 0.1g of 2, 6-bis (6-amino-2-imine pyridine) pyridine-condensed 5-methyl-2-thiophene zinc formate complex catalyst and 20g of epoxy cyclohexane into the autoclave, heating to 110 ℃, introducing carbon dioxide to keep the pressure at 1MPa, opening and stirring, reacting for 20h, cooling to room temperature, dissolving the polymer out of the autoclave by using dichloromethane, slowly dropwise adding a dichloromethane solution of the polymer into methanol by using methanol as a precipitator, filtering and collecting precipitated solids, and drying in vacuum to obtain 5.8g of a copolymerization product, wherein the molar content of carbonate chain links is 89% by nuclear magnetic hydrogen spectroscopy.
Claims (8)
1. A metal coordination catalyst for synthesizing carbon dioxide-based biodegradable materials is characterized in that: the ligand of the coordination catalyst has the following general formula
A and B groups in a ligand used by the metal coordination catalyst are pyridine, furan or thiophene; the C, D, E and F groups in the ligand used by the metal coordination catalyst are respectively and independently selected from alkyl, hydrogen, alkoxy, carboxyl, substituted aryl or substituted heteroaryl;
the metal element of the coordination center used by the metal coordination catalyst is zinc.
2. The metal complex catalyst according to claim 1, characterized in that: when the A group in the ligand used by the metal coordination catalyst is pyridine, furan or thiophene, the two-CH = N groups connected on the aromatic heterocycle are at ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
3. The metal-complex catalyst according to claim 1, characterized in that: when the B group in the ligand used by the metal coordination catalyst is pyridine, furan or thiophene, the two-NH groups connected on the aromatic heterocycle are at ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
4. The metal complex catalyst according to claim 1, characterized in that: when the B group in the ligand used by the metal coordination catalyst is pyridine, furan or thiophene, the C, D, E and F groups are in ortho-position, meta-position or para-position of the nitrogen atom of the pyridine, the oxygen atom of the furan or the sulfur atom of the thiophene.
5. Use of the metal complex catalyst according to any one of claims 1 to 4 in the synthesis of carbon dioxide-based biodegradable materials by copolymerization of carbon dioxide with epoxy compounds.
6. Use according to claim 5, characterized in that: the epoxy compound is one of ethylene oxide, propylene oxide, cyclohexene oxide, 1, 2-butylene oxide and 2, 3-butylene oxide.
7. Use according to claim 5, characterized in that: the mass ratio of the catalyst to the epoxy compound is 1.
8. Use according to claim 5, characterized in that: the copolymerization reaction temperature is 80-150 ℃, the copolymerization reaction pressure is 1-5 MPa, and the copolymerization reaction time is 10-40 h.
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