CN113582934A - Preparation method and application of Pentane metal-free homogeneous catalyst - Google Patents

Preparation method and application of Pentane metal-free homogeneous catalyst Download PDF

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CN113582934A
CN113582934A CN202110882658.XA CN202110882658A CN113582934A CN 113582934 A CN113582934 A CN 113582934A CN 202110882658 A CN202110882658 A CN 202110882658A CN 113582934 A CN113582934 A CN 113582934A
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pentane
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epoxy compound
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CN113582934B (en
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支云飞
邹冉
王鹏飞
陕绍云
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Kunming University of Science and Technology
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/08—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
    • C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
    • C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
    • C07D243/12—1,5-Benzodiazepines; Hydrogenated 1,5-benzodiazepines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/26—Polythioesters

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Abstract

The invention discloses a preparation method of a Pentane metal-free homogeneous catalyst, which takes acetylacetone (2, 4-pentanedione) and organic amine salt as raw materials to obtain the Pentane metal-free homogeneous catalyst by a one-step method; the prepared catalyst can be used for catalyzing the cycloaddition reaction of an epoxy compound and carbon dioxide to prepare cyclic carbonate and can also be used for catalyzing the copolymerization reaction of the epoxy compound and sulfur dioxide to prepare the polysulfite; the preparation method of the invention has the advantages of simple and easily obtained raw materials, simple preparation method, economy and environmental protection. The catalyst has the advantages of small dosage, high activity, mild reaction conditions, convenience for large-scale production and important industrial application prospect.

Description

Preparation method and application of Pentane metal-free homogeneous catalyst
Technical Field
The invention relates to a preparation technology and application of a Pentane metal-free homogeneous catalyst, in particular to a preparation method of the Pentane metal-free homogeneous catalyst, a method for catalyzing copolymerization of sulfur dioxide and an epoxy compound and a method for cycloaddition reaction of carbon dioxide and the epoxy compound.
Background
Sulfur dioxide (SO)2) As a product of fossil combustion, is a toxic, odorous gaseous pollutant; with SO2The discharge of (2) can generate acid rain and photochemical smog, and seriously endanger human health and ecological environment. In recent years, researchers have discovered that epoxy compounds can be used with SO2Copolymerization reaction is carried out, and sulfuryl (-SO) can be introduced into the product2-) to impart excellent mechanical properties, chemical resistance, as well as good permeability and biocompatibility, etc. Can be applied to the fields of electrode composite materials, thermosetting adhesives, drug transportation, sewage purification and the like. However, in the copolymerization, the presence of the monomer is difficult to react with SO2Low selectivity of the polymerized or produced poly sulfite, resulting in SO2The copolymerization is difficult to realize industrialization. Over the past decades, researchers have developed a variety of catalysts to catalyze SO2And epoxy compound, including organic metal catalyst, peroxide catalyst, Lewis acid/base catalyst, inorganic salt catalyst, etc. However, these catalysts still have problems of containing metal ions, difficult separation, complicated preparation method, poor catalytic effect, and the like. Therefore, it is urgent to find a metal-free catalyst with environmental protection and high efficiency.
Carbon dioxide (CO)2) Is a main greenhouse gas, and is a non-toxic, low-cost and rich renewable carbon source. Vigorous development of CO2The green utilization technology improves the added value of the product and has important economic and environmental significance. CO 22Can obtain cyclic carbonate through cycloaddition reaction with epoxy compound, and has wide application prospect in the fields of plastic raw materials, pharmacy, fine chemicals and the like. However, due to CO2Thus, there is a need to develop a high performance catalyst for CO promotion2Ring-opening addition reaction of (1). Researchers developed catalysts such as metal complexes, organic bases, and alkali halides to catalyze CO2Cycloaddition reaction with epoxy compound. But also has metal ion pollution and goldThe method has the problems of high cost, complex operation and the like, so that a green, efficient and low-cost catalyst needs to be researched and developed.
In recent years, nonmetal catalysts are widely researched by researchers by virtue of the characteristics of low price, high activity, mild reaction conditions and the like. The catalyst contains-OH and-NH2Hydrogen bond donors such as-COOH, etc., which can form hydrogen bonds with oxygen atoms of epoxy groups, polarize C-O bonds in the epoxide, weaken the electron cloud density thereof, effectively replace metal ions and halides, and avoid the problems of catalyst poisoning, halide corrosion on stainless steel reaction kettles, etc. caused by the falling of the metal ions.
Disclosure of Invention
The invention provides a preparation method of a Pentane metal-free homogeneous catalyst, aiming at the problems that the copolymerization reaction conditions of sulfur dioxide and epoxy compounds and the cycloaddition reaction conditions of carbon dioxide and epoxy compounds are harsh, the catalytic activity of the traditional catalyst is low, the traditional catalyst is not environment-friendly and the like.
The organic ammonium salt can be one of tetraethylenepentamine, ethylenediamine, o-phenylenediamine, 1, 8-diaminonaphthalene and 2, 3-diaminotoluene; the molar ratio of the acetylacetone to the organic amine salt is 2: 1-5: 1.
The invention also aims to apply the Pentane metal-free homogeneous catalyst prepared by the method to the preparation of the polysulfite by catalyzing the copolymerization reaction of sulfur dioxide and an epoxy compound, and specifically, the epoxy compound and the Pentane metal-free homogeneous catalyst are sequentially added into a high-pressure reaction kettle; and introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing sulfur dioxide with the purity of 99%, wherein the pressure of the sulfur dioxide is 0.2MPa, the reaction temperature is set to be 50-90 ℃, reacting for 4-24 hours, then cooling, dissolving a reaction product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate by using methanol for 3-4 times, and vacuum drying the washed precipitate at 40 ℃ for 24 hours to obtain a copolymer of the sulfur dioxide and an epoxy compound, namely the poly sulfite.
In the copolymerization reaction of sulfur dioxide and an epoxy compound, the molar ratio of the Pentane metal-free homogeneous catalyst to the epoxy compound is 1: 100-1: 1000.
The invention also aims to apply the Pentane metal-free homogeneous catalyst prepared by the method in the cycloaddition reaction of carbon dioxide and an epoxy compound, and specifically, the epoxy compound and the Pentane metal-free homogeneous catalyst are sequentially added into a high-pressure reaction kettle; and introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing carbon dioxide with the purity of 99%, setting the pressure of the carbon dioxide to be 0.5-4 MPa, setting the reaction temperature to be 70-110 ℃, cooling after reacting for 3-7 hours, and obtaining the product, namely the cyclic carbonate after the reaction is finished.
In the cycloaddition reaction of carbon dioxide and an epoxy compound, the molar ratio of the Pentane metal-free homogeneous catalyst to the epoxy compound is 1: 100-1: 1000.
The epoxy compound is one of epoxy cyclohexane, epoxy propane, 1, 2-epoxybutane, styrene oxide and epoxy chloropropane.
Compared with the prior art, the invention has the following advantages:
(1) the Pentane metal-free homogeneous catalyst is prepared by using acetylacetone and organic amine salt through a one-step method for the first time, and the catalyst can be used for catalyzing the cycloaddition reaction of an epoxy compound and carbon dioxide to prepare cyclic carbonate and catalyzing the copolymerization reaction of the epoxy compound and sulfur dioxide to prepare polysulfite;
(2) the catalyst of the invention has the advantages of simple preparation method, easy operation, less catalyst consumption, low cost, high yield and easy realization of green industrial production.
Drawings
FIG. 1 is a Fourier transform Infrared Spectroscopy (FTIR) plot of the Pentane-based metal-free homogeneous catalyst prepared in example 1;
FIG. 2 is a Fourier transform infrared spectroscopy (FTIR) plot of the polysulfite prepared in example 2;
FIG. 3 is prepared as in example 3Cyclic carbonic acid esters of (2)1H NMR spectrum;
FIG. 4 is the polysulfite prepared in example 41H NMR spectrum.
Detailed Description
The invention is explained in more detail below with reference to examples and figures, without limiting the scope of the invention.
Example 1:
(1) sequentially adding 8.23mL of acetylacetone and 70mL of anhydrous ethanol into a 50mL three-neck flask, dropwise adding 7.57mL of tetraethylenepentamine, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 75 ℃ for 24 hours after dropwise adding;
(2) after the reaction is finished, transferring the reacted solution into a single-neck flask, carrying out rotary evaporation on an ethanol solution at 60 ℃, then drying the solution in a vacuum drying oven at 50 ℃ for 12 hours, and characterizing the obtained product by Fourier transform infrared spectroscopy (FTIR), wherein the FTIR is shown in figure 1; as can be seen from FIG. 1, at 3352cm-1And 1708cm-1No reactant-NH-found therein2Characteristic peak with C = O, instead of 1623cm-1The stretching vibration of the C = N bond, which appears here, initially proves the successful synthesis of the catalyst.
(3) Adding 5mL of epoxy cyclohexane and 0.034g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle in sequence according to the molar ratio of 500: 1; then introducing nitrogen with the purity of 99.99 percent into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and then introducing sulfur dioxide with the purity of 99 percent into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 80 ℃ and the reaction time at 6 h; dissolving a reaction product by using dichloromethane, then adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 3 times by using methanol, placing the washed precipitate in a vacuum drying oven, and drying in vacuum at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound. Wherein the conversion rate of the epoxy cyclohexane is 93 percent, and the selectivity of the polysulfite is 88 percent.
(4) Sequentially adding 5mL of epoxy chloropropane and 0.089g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the mol ratio of 250:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 100 ℃, the carbon dioxide pressure at 1MPa and the reaction time at 6 h; cooling to obtain the cycloaddition product of carbon dioxide and epoxy compound, wherein the yield of the product is 98%, and the selectivity can reach 99%.
Example 2:
(1) sequentially adding 8.23mL of acetylacetone and 60mL of anhydrous ethanol into a 50mL three-neck flask, dropwise adding 2.67mL of ethylenediamine, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 60 ℃ for 12h after dropwise adding;
(2) after the reaction is finished, the solution after the reaction is transferred to a single-neck flask, the ethanol solution is evaporated in a rotary manner at the temperature of 60 ℃, and then the solution is dried in a vacuum drying oven for 12 hours at the temperature of 50 ℃.
(3) Adding 5mL of epoxy cyclohexane and 0.110g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle in sequence according to the molar ratio of 100: 1; then introducing nitrogen with the purity of 99.99 percent into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and then introducing sulfur dioxide with the purity of 99 percent into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 50 ℃ and the reaction time at 4 h; dissolving a reaction product by using dichloromethane, then adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 3 times by using methanol, placing the washed precipitate in a vacuum drying oven, and drying in vacuum at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound. The resulting product was characterized by Fourier transform Infrared Spectroscopy (FTIR), as can be found in FIG. 2 at 1202cm-1And 725cm-1Vibration peaks related to S = O and S-O appear at the parts respectively, and the existence of sulfur dioxide on the main chain is confirmed; wherein the conversion rate of the epoxy cyclohexane is 96 percent, and the selectivity of the poly sulfite is 73 percent;
(4) sequentially adding 5mL of epoxy chloropropane and 0.143g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 100:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 70 ℃, the pressure of carbon dioxide at 0.5MPa and the reaction time at 3 h; cooling to obtain the cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound, wherein the yield of the product is 89%, and the selectivity can reach 94%.
Example 3:
(1) sequentially adding 20.57mL of acetylacetone and 80mL of anhydrous ethanol into a 50mL three-neck flask, dropwise adding 7.57mL of tetraethylenepentamine, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 90 ℃ for 24 hours after dropwise adding;
(2) after the reaction is finished, the solution after the reaction is transferred to a single-neck flask, the ethanol solution is evaporated in a rotary manner at the temperature of 60 ℃, and then the solution is dried in a vacuum drying oven for 12 hours at the temperature of 50 ℃.
(3) Adding 5mL of epoxy cyclohexane and 0.017g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle in sequence according to the molar ratio of 1000: 1; then introducing nitrogen with the purity of 99.99 percent into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99 percent into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 90 ℃ and the reaction time at 24 h; dissolving a reaction product by using dichloromethane, then adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 4 times by using methanol, placing the washed precipitate in a vacuum drying oven, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain a copolymer of sulfur dioxide and an epoxy compound; the epoxycyclohexane conversion was 97% and the polysulfite selectivity was 74%.
(4) Sequentially adding 5mL of epoxy chloropropane and 0.023g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 1000:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 3 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 110 ℃, the carbon dioxide pressure at 4MPa and the reaction time at 7 h; cooling to obtain carbon dioxideCycloaddition products with epoxy compounds cyclic carbonates. By using1The resulting product was characterized by H NMR spectrum as shown in FIG. 3; the product yield is 82%, and the selectivity can reach 98%.
Example 4:
(1) sequentially adding 8.23mL of acetylacetone and 80mL of absolute ethyl alcohol into a 50mL three-neck flask, dropwise adding 4.2mL of o-phenylenediamine, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 90 ℃ for 12 hours after dropwise adding;
(2) after the reaction is finished, transferring the reacted solution into a single-mouth flask, carrying out rotary evaporation at 60 ℃ to obtain an ethanol solution, and drying in a vacuum drying oven at 50 ℃ for 12 hours;
(3) adding 5mL of propylene oxide and 0.039g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle in sequence according to the molar ratio of 500: 1; then introducing nitrogen with the purity of 99.99 percent into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99 percent into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 110 ℃ and the reaction time at 4 h; dissolving a reaction product by using dichloromethane, then adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 4 times by using methanol, placing the washed precipitate in a vacuum drying oven, and drying in vacuum at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound. By using1The resulting product was characterized by H NMR spectrum, as in fig. 4; the epoxycyclohexane conversion was 99% and the polysulfite selectivity was 65%.
(4) Sequentially adding 5mL of propylene oxide and 0.078g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the mol ratio of 250:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 110 ℃, the carbon dioxide pressure at 1MPa and the reaction time at 5 h; cooling to obtain a cycloaddition product of carbon dioxide and an epoxy compound, namely cyclic carbonate; the yield of the product is 80 percent, and the selectivity can reach 95 percent.
Example 5:
(1) sequentially adding 8.23mL of acetylacetone and 75mL of absolute ethyl alcohol into a 50mL three-neck flask, dropwise adding 5.61mL of 1, 8-diaminonaphthalene, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 75 ℃ for 18h after dropwise adding;
(2) after the reaction is finished, transferring the reacted solution into a single-mouth flask, carrying out rotary evaporation at 60 ℃ to obtain an ethanol solution, and drying in a vacuum drying oven at 50 ℃ for 12 hours;
(3) sequentially adding 5mL of epoxy chloropropane and 0.0451g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 3 times, and introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 90 ℃ and the reaction time at 9 h; dissolving a product obtained by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 3 times by using methanol, placing the washed precipitate in a vacuum drying oven, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound, wherein the conversion rate of epoxy chloropropane is 90%, and the selectivity of the poly sulfite is 60%.
(4) Sequentially adding 5mL of epoxy chloropropane and 0.0451g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 80 ℃, the pressure of carbon dioxide at 2MPa and the reaction time at 20 h; cooling to obtain the cycloaddition product of carbon dioxide and epoxy compound, wherein the yield of the product is 83 percent, and the selectivity can reach 99 percent.
Example 6:
(1) sequentially adding 8.34mL of acetylacetone and 75mL of absolute ethyl alcohol into a 50mL three-neck flask, adding 4.89g of 2, 3-diaminotoluene, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 65 ℃ for 20 hours;
(2) after the reaction is finished, transferring the reacted solution into a single-mouth flask, carrying out rotary evaporation at 60 ℃ to obtain an ethanol solution, and drying in a vacuum drying oven at 50 ℃ for 12 hours;
(3) sequentially adding 5mL of 1, 2-butylene oxide and 0.033g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 3 times, and introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.5 MPa; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 90 ℃ and the reaction time at 9 h; dissolving the obtained product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate for 3 times by using methanol, placing the washed precipitate in a vacuum drying oven, and carrying out vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound, wherein the conversion rate of epoxy chloropropane is 87%, and the selectivity of the poly sulfite is 60%.
(4) Sequentially adding 5mL of styrene oxide and 0.051g of Pentane metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the mol ratio of 250:1, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing the nitrogen for 2 times, and introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction is finished, closing the inlet and outlet valves, setting the rotating speed at 280r/min, the temperature at 80 ℃, the pressure of carbon dioxide at 2MPa and the reaction time at 20 h; cooling to obtain the cycloaddition product of carbon dioxide and epoxy compound, wherein the yield of the product is 64%, and the selectivity can reach 97%.

Claims (7)

1. A preparation method of a Pentane metal-free homogeneous catalyst is characterized by comprising the following steps: dissolving acetylacetone and organic amine salt in 60-80 mL of absolute ethanol, reacting at 60-90 ℃ for 12-24 h, removing ethanol from a reaction product by rotary evaporation, and drying to obtain the Pentane metal-free homogeneous catalyst.
2. The method of preparing a Pentane-based metal-free homogeneous catalyst of claim 1, wherein: the organic ammonium salt is one of tetraethylenepentamine, ethylenediamine, o-phenylenediamine, 1, 8-diaminonaphthalene and 2, 3-diaminotoluene; the molar ratio of the acetylacetone to the organic amine salt is 2: 1-5: 1.
3. The use of the Pentane-based metal-free homogeneous catalyst prepared by the method of claim 1 for catalyzing the copolymerization of sulfur dioxide and an epoxy compound, wherein: sequentially adding an epoxy compound and a Pentane metal-free homogeneous catalyst into a high-pressure reaction kettle, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing sulfur dioxide gas with the purity of 99%, wherein the pressure of the sulfur dioxide is 0.2MPa, reacting at 50-90 ℃ for 4-24 hours, cooling, dissolving a reaction product by using dichloromethane, adding methanol for precipitation, filtering, collecting the precipitate, washing the precipitate for 3-4 times by using methanol, and drying to obtain a copolymer of the sulfur dioxide and the epoxy compound, namely the poly-sulfite.
4. The use of the Pentane-based metal-free homogeneous catalyst prepared by the method of claim 1 for catalyzing the addition reaction of carbon dioxide and an epoxy compound, wherein: sequentially adding an epoxy compound and a Pentane metal-free homogeneous catalyst into a high-pressure reaction kettle, introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing carbon dioxide with the purity of 99%, reacting at 70-110 ℃ for 3-7 hours under the pressure of 0.5-4 MPa, cooling, and obtaining a product, namely the cyclic carbonate after the reaction is finished.
5. Use according to claim 3, characterized in that: the molar ratio of the Pentane metal-free homogeneous catalyst to the epoxy compound is 1: 100-1: 1000.
6. Use according to claim 4, characterized in that: the molar ratio of the Pentane metal-free homogeneous catalyst to the epoxy compound is 1: 100-1: 1000.
7. Use according to claim 3 or 4, characterized in that: the epoxy compound is one of epoxy cyclohexane, epoxy propane, 1, 2-epoxybutane, styrene oxide and epoxy chloropropane.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536803A (en) * 2022-10-27 2022-12-30 大连理工大学 Preparation method of sulfur dioxide-based Polyurethane (PES)
CN116354807A (en) * 2023-03-23 2023-06-30 昆明理工大学 Solvent-free synthesis method of nonmetal catalyst and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102356086A (en) * 2009-03-18 2012-02-15 泰恩河畔纽卡斯尔大学 Aluminum complexes and their use in the synthesis of cyclic carbonates
CN102580775A (en) * 2011-12-30 2012-07-18 河北工业大学 Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol
CN103030557A (en) * 2013-01-09 2013-04-10 四川大学 Method for generating phenylacetate by acetophenone in one step
CN107827764A (en) * 2017-11-27 2018-03-23 上海应用技术大学 A kind of preparation method of double β amino ketones or double β amino esters

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102356086A (en) * 2009-03-18 2012-02-15 泰恩河畔纽卡斯尔大学 Aluminum complexes and their use in the synthesis of cyclic carbonates
CN102580775A (en) * 2011-12-30 2012-07-18 河北工业大学 Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol
CN103030557A (en) * 2013-01-09 2013-04-10 四川大学 Method for generating phenylacetate by acetophenone in one step
CN107827764A (en) * 2017-11-27 2018-03-23 上海应用技术大学 A kind of preparation method of double β amino ketones or double β amino esters

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李珍 等: ""催化剂催化二氧化硫共聚的研究进展"", 《高分子材料科学与工程》, vol. 36, no. 6, pages 184 - 190 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536803A (en) * 2022-10-27 2022-12-30 大连理工大学 Preparation method of sulfur dioxide-based Polyurethane (PES)
CN115536803B (en) * 2022-10-27 2023-07-11 大连理工大学 Preparation method of sulfur dioxide-based polysulfate polyurethane
CN116354807A (en) * 2023-03-23 2023-06-30 昆明理工大学 Solvent-free synthesis method of nonmetal catalyst and application thereof
CN116354807B (en) * 2023-03-23 2024-04-12 昆明理工大学 Solvent-free synthesis method of nonmetal catalyst and application thereof

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