CN111892562B - Method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride - Google Patents
Method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The invention belongs to the technical field of bio-based chemicals, and particularly relates to a method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride. The invention relates to a preparation method for generating phthalic anhydride by catalyzing furan and maleic anhydride, which is characterized in that furan and maleic anhydride are used as raw materials, and Diels-Alder reaction and dehydration steps are adopted to produce phthalic anhydride, wherein the furan and the maleic anhydride are obtained from biomass-converted furfural. The method is green, economical and renewable, reduces the use of non-renewable traditional resources, provides advanced technical support for the industrial production of the bio-based phthalic anhydride, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of bio-based chemicals, and particularly relates to a method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride.
Background
Phthalic anhydride, abbreviated as phthalic anhydride. The main application of the compound is to further derive dibutyl phthalate, and the compound is used as a plasticizer of PVC and the like; and also widely used for producing unsaturated polyester resins, alkyd resins, fuels and pigments.
Patent CN101130535A reports that phthalic anhydride is prepared by catalytic reaction of o-xylene and/or naphthalene as raw material with gas phase oxygen containing molecular oxygen. The production of phthalic anhydride on the market at present is based on non-renewable fossil resources as raw materials, wherein the ortho-method proportion is 64 percent, and the naphthalene method proportion is 36 percent. With the reduction of fossil resource reserves and the improvement of environmental requirements, nonrenewable fossil resources can not meet the requirements of human beings, and biomass resources become the most promising renewable energy sources due to the characteristics of wide distribution, rich carbon content and environmental friendliness, so that the biomass resources have very good commercial prospect as substitutes of fossil fuels to produce renewable high-value chemicals from the perspective of biomass.
Under the premise of developing green and sustainable chemistry, the heterogeneous catalyst attracts wide attention in the aspect of replacing the homogeneous catalyst due to the advantages of easy separation, small equipment corrosion and reusability in recent years. Therefore, from the perspective of biomass conversion, it is very meaningful to find a green, cheap and efficient solid acid catalyst, which generates high yield of phthalic anhydride under mild conditions, for reducing the use of traditional resources and for industrialization of chemicals.
Disclosure of Invention
The invention aims to solve the technical problems that non-renewable fossil resources and homogeneous catalysts are difficult to separate and corrode equipment and cannot be recycled, and provides a method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride comprises the steps of firstly preparing a cycloaddition intermediate product from furan and maleic anhydride serving as raw materials through a Diels-Alder reaction, and then dehydrating the cycloaddition intermediate product under the action of a solid catalyst to prepare phthalic anhydride.
Furthermore, a cocatalyst is also required to be added in the preparation of the phthalic anhydride by dehydrating the cycloaddition intermediate product under the solid catalyst.
Still further, the cocatalyst comprises one or a mixture of more of acetic acid, acetic anhydride, trifluoroacetic anhydride, maleic anhydride and methane sulfonic anhydride in any proportion.
Further, the solvent for preparing the cycloaddition intermediate product by taking furan and maleic anhydride as raw materials through Diels-Alder reaction comprises one or a mixture of several of tetrahydrofuran, acetone, ethanol and glycol in any proportion.
Further, the mass mixing ratio of the maleic anhydride and the solvent is 4:3
Further, the solid catalyst is a solid acid catalyst.
Still further, the solid acid catalyst comprises one or a mixture of several of phosphotungstic acid, 732 resin, Amberlyst-15 resin, dodecylbenzene sulfonic acid, Amberlyst-35 resin and Amberlyst-36 resin in any proportion.
Furthermore, the molar ratio of the furan to the maleic anhydride is (1-3): 1.
Further, the mass ratio of the cycloaddition intermediate product, the solid acid catalyst and the cocatalyst is 0.05: (0.75-1.5) 1.
Further, the reaction temperature of the Diels-Alder reaction is 15-40 ℃; and/or the reaction time is 1-24 h.
Further, the reaction temperature of the Diels-Alder reaction is 20-30 ℃; and/or the reaction time is 3-5 h.
Further, the reaction temperature for preparing the phthalic anhydride by dehydrating the cycloaddition intermediate product under the solid catalyst is two stages: the first section is 15-35 ℃; and/or the reaction time is 1-3 h; the second section is 70-95 ℃; and/or the reaction time is 0.5-8 h.
Compared with the prior art, the invention has the following advantages:
aiming at the current situations that non-renewable fossil resources and homogeneous catalysts are difficult to separate and corrode equipment and cannot be recycled, the invention searches for a proper solid catalyst and fully exerts the catalytic activity of the solid catalyst to generate the bio-based phthalic anhydride under mild conditions; the method has the advantages of simple operation, mild condition, low energy consumption, cyclic utilization and easy large-scale preparation, provides advanced technical support for the industrial production of the bio-based phthalic anhydride, and has wide application prospect.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
figure 1 shows the reaction pathway for the preparation of phthalic anhydride from bio-based furan and maleic anhydride in a two-step process.
FIG. 2 shows a nuclear magnetic hydrogen spectrum of a cycloaddition intermediate product produced from a bio-based furan and maleic anhydride by a Diels-Alder reaction.
FIG. 3 shows nuclear magnetic hydrogen spectra for the dehydration of the cycloaddition intermediate to produce phthalic anhydride.
Detailed Description
The present invention will be specifically described below with reference to specific examples. The experimental methods described below are, unless otherwise specified, all routine laboratory procedures. The experimental materials described below, unless otherwise specified, are commercially available.
Example 1
In this example, the reaction operation steps for synthesizing the bio-based phthalic anhydride are as follows:
the method comprises the following steps: 1.3600g of furan, 2.0057g of maleic anhydride and 1.5280g of acetone are added into a 50mL centrifuge tube and reacted for 24h at 15 ℃ to prepare the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product is 83% according to the formula (1);
in formula (1): a. the (5.35ppm) The peak area of the cycloaddition intermediate product at the chemical shift of 5.35 ppm;
A (MA) the peak area of the nuclear magnetic shift of the maleic anhydride is 7.48 ppm;
A (maleic acid) the peak area was shifted by nuclear magnetism for maleic acid at 6.23 ppm.
Step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
Taking 0.5500g of the treated Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product, putting the intermediate product into a 50mL centrifuge tube, placing the centrifuge tube in a water bath, reacting for 3h at 15 ℃ and reacting for 0.5h at 95 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 70.2 percent.
A (PA) The peak area of nuclear magnetic shift of phthalic anhydride is 8.01 ppm;
A (std) peak area at 2.99ppm for nuclear magnetic shift for internal standard sulfolane;
w (CI) mass of the intermediate product of cycloaddition;
w (std) mass of sulfolane is internal standard;
MW (PA) 、MW (std) 、MW (CI) relative atomic masses of phthalic anhydride, sulfolane, and cycloaddition intermediate products, respectively;
M (CI) is the molar mass of the cycloaddition intermediate product;
P (std) 、P (PA) respectively the purities of internal standard sulfolane and phthalic anhydride;
nH (std) proton number of internal standard sulfolane;
nH (PA) is the number of protons in the phthalic anhydride.
A PA The peak area of nuclear magnetic shift of phthalic anhydride is 8.01 ppm;
A internal standard Peak area at 2.99ppm for nuclear magnetic shift for internal standard sulfolane;
m 0 CI mass of the cycloaddition intermediate added;
M CI is the molar mass of the cycloaddition intermediate.
Example 2
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in example 1, and the specific operation steps are as follows:
the method comprises the following steps: 4.0844g of furan, 2.0081g of maleic anhydride and 1.5280g of acetone are added into a 50mL centrifuge tube and reacted for 24h at 15 ℃ to prepare the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product is 85 percent according to the calculation of the formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
0.6002g of the treated Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 30 ℃ and for 8h at 80 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 62.1 percent.
Example 3
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5210g of acetone are added into a 50mL centrifuge tube and reacted for 1h at 40 ℃ to prepare the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product was 67.5% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
0.3012g of the above processed Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard, and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 25 ℃ and 1.5h at 80 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): and 76 percent.
Example 4
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in example 1, and the specific operation steps are as follows:
the method comprises the following steps: 1.3624g of furan, 2.0081g of maleic anhydride and 1.5080g of acetone are added into a 50mL centrifuge tube and reacted for 1h at 40 ℃ to prepare the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product is 64 percent according to the calculation of the formula (1);
step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
0.4100g of the above processed Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 3h at 35 ℃ and 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 65.5 percent.
Example 5
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 4.0806g of furan, 2.0081g of maleic anhydride and 1.5010g of n-heptane are added into a 50mL centrifuge tube and reacted for 4h at 25 ℃ to obtain the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product was 86.5% as calculated according to equation (1);
step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
Taking Amberlyst-35 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-35, drying and waiting for standby.
0.5012g of the treated Amberlyst-35, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0206g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and placed into a water bath kettle to react for 1h at normal temperature and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 86.7 percent.
Example 6
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7241g of furan, 2.0083g of maleic anhydride and 1.5103g of ethanol were added into a 50mL centrifuge tube and reacted at room temperature for 24 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 64.6% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
Taking 0.5500g of the treated Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product into a 50mL centrifuge tube, placing the centrifuge tube into a water bath, and reacting at 26 ℃ for 2h and 70 ℃ for 1.5 h.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 70.6 percent.
Example 7
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5009g of ethylene glycol were added to a 50mL centrifuge tube and reacted at room temperature for 5 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 69.5% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
Taking 0.5500g of the treated Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product, putting the intermediate product into a 50mL centrifuge tube, placing the centrifuge tube in a water bath, reacting for 2h at 26 ℃ and reacting for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 84 percent.
Example 8
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5004g of tetrahydrofuran were added to a 50mL centrifuge tube and reacted at room temperature for 24 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 70.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
1.3049g of phosphotungstic acid, 1.3422g of acetic anhydride and 0.0517g of sulfolane are taken as internal standards, 0.0224g of purified cycloaddition intermediate product is put into a 50mL centrifuge tube and placed into a water bath kettle to react for 2h at 25 ℃ and react for 4h at 80 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 62.2 percent.
Example 9
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5002g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
0.6001g of the treated Amberlyst-15, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 30 ℃ and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 84 percent.
Example 10
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5010g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
Taking Amberlyst-36 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-36, drying and waiting for standby.
Taking 0.5001g of the treated Amberlyst-36, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard, and 0.0204g of the purified cycloaddition intermediate product into a 50mL centrifuge tube, placing the centrifuge tube into a water bath, reacting for 2h at 28 ℃ and reacting for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 85 percent.
Example 11
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5101g of acetone are added into a 50mL centrifuge tube and reacted for 4h at room temperature to obtain the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-36 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-36, drying and waiting for standby.
0.4701g of the treated Amberlyst-36, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 28 ℃ and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 89 percent.
Example 12
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5001g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product is 83.1 percent according to the formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
0.5001g of dodecylbenzenesulfonic acid, 0.4000g of acetic anhydride and 0.0202g of sulfolane are taken as internal standards, 0.0204g of the purified cycloaddition intermediate product is placed in a 50mL centrifuge tube and is placed in a water bath for reaction for 2 hours at the temperature of 28 ℃, and is reacted for 1 hour at the temperature of 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 60 percent.
Example 13
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5006g of acetone are added into a 50mL centrifuge tube and reacted for 4h at room temperature to obtain the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
And putting 732 hydrogen type resin into a beaker, adding acetic anhydride until the resin is immersed for 3 hours, filtering, collecting 732 resin, drying and waiting for later use.
0.8001g of the treated Amberlyst-36, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 25 ℃ and for 4h at 80 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 60 percent.
Example 14
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5008g of acetone are added into a 50mL centrifuge tube and reacted for 4h at room temperature to obtain the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product is 83.1 percent according to the formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-36 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-36, drying and waiting for standby.
0.4601g of the treated Amberlyst-36, 0.4000g of trifluoroacetic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 28 ℃ and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 86 percent.
Example 15
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5021g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
And (2) putting Amberlyst-35 resin into a beaker, adding acetic anhydride until the resin is immersed for 3 hours, filtering, collecting Amberlyst-35, drying and waiting for standby.
0.5001g of the treated Amberlyst-35, 0.4000g of acetic acid, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 28 ℃ and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 60.3 percent.
Example 16
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5102g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-36 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-36, drying and waiting for standby.
0.4703g of the treated Amberlyst-36, 0.4000g of maleic anhydride, 0.0202g of sulfolane as an internal standard and 0.0204g of the purified cycloaddition intermediate product are put into a 50mL centrifuge tube and put into a water bath to react for 2h at 27 ℃ and for 1h at 90 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): and (3.2).
Example 17
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in the example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5010g of acetone were added to a 50mL centrifuge tube and reacted at room temperature for 4 hours to obtain a cycloaddition intermediate.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned intermediate product of cycloaddition and diethyl ether are mixed and frozen in a refrigerator overnight, and then filtered by filter paper for purification.
Taking Amberlyst-15 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-15, drying and waiting for standby.
0.5501g of the above treated Amberlyst-15, 0.4000g of methanesulfonic anhydride, 0.0202g of sulfolane as an internal standard, and 0.0204g of the purified cycloaddition intermediate product were put in a 50mL centrifuge tube, and placed in a water bath to react at 28 ℃ for 2h and at 90 ℃ for 1 h.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 60.1 percent.
Example 18
The method for synthesizing the bio-based phthalic anhydride is basically the same as the method in example 1, and the specific operation steps are as follows:
the method comprises the following steps: 2.7244g of furan, 2.0081g of maleic anhydride and 1.5009g of acetone are added into a 50mL centrifuge tube and reacted for 4h at room temperature to obtain the cycloaddition intermediate product.
The yield of the cycloaddition intermediate product was 83.1% as calculated according to formula (1);
step two: the above-mentioned cycloaddition intermediate product and ethyl ether are mixed, frozen in a refrigerator overnight, filtered by filter paper and purified.
Taking Amberlyst-36 resin, adding acetic anhydride until the resin is soaked for 3 hours, filtering, collecting Amberlyst-36, drying and waiting for standby.
Taking 0.5001g of the treated Amberlyst-36, 0.4000g of acetic anhydride, 0.0202g of sulfolane as an internal standard, and 0.0204g of the purified cycloaddition intermediate product into a 50mL centrifuge tube, placing the centrifuge tube into a water bath, reacting for 2h at 28 ℃, and reacting for 8h at 70 ℃.
The yield of the bio-based phthalic anhydride is calculated according to the formulas (2) and (3): 72.1 percent.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (9)
1. A method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride is characterized by comprising the following steps: firstly, preparing a cycloaddition intermediate product by taking furan and maleic anhydride as raw materials through a Diels-Alder reaction, and then dehydrating the cycloaddition intermediate product under a solid catalyst to prepare phthalic anhydride; the solvent for preparing the cycloaddition intermediate product by taking furan and maleic anhydride as raw materials through a Diels-Alder reaction comprises one or a mixture of more of tetrahydrofuran, acetone, ethanol and glycol in any proportion; the solid catalyst is a solid acid catalyst; the solid acid catalyst comprises one or a mixture of more of phosphotungstic acid, 732 resin, Amberlyst-15 resin, Amberlyst-35 resin and Amberlyst-36 resin in any proportion;
the method comprises the specific steps of adding acetic anhydride into a resin solid acid catalyst to immerse the resin solid acid catalyst, collecting the immersed resin solid acid catalyst, and drying the resin solid acid catalyst for later use.
2. The process of claim 1 for the catalytic synthesis of phthalic anhydride from furan and maleic anhydride, wherein: the preparation of phthalic anhydride by dehydrating the cycloaddition intermediate product under the solid catalyst also needs to add a cocatalyst.
3. The method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride according to claim 2, wherein: the cocatalyst comprises one or a mixture of more of acetic acid, acetic anhydride, trifluoroacetic anhydride, maleic anhydride and methane sulfonic anhydride in any proportion.
4. The method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride according to claim 1, wherein: the mass ratio of the maleic anhydride to the solvent is 4: 3.
5. The method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride according to claim 1, wherein: the molar ratio of furan to maleic anhydride is 1-3: 1.
6. The process of claim 1 for the catalytic synthesis of phthalic anhydride from furan and maleic anhydride, wherein: the mass ratio of the cycloaddition intermediate product to the solid acid catalyst to the cocatalyst is 0.05: 0.75-1.5: 1.
7. The process of claim 1 for the catalytic synthesis of phthalic anhydride from furan and maleic anhydride, wherein: the reaction temperature of the Diels-Alder reaction is 15-40 ℃; and/or the reaction time is 1-24 h.
8. The method for catalyzing furan and cis-anhydride to synthesize phthalic anhydride according to claim 7, wherein: the reaction temperature of the Diels-Alder reaction is 20-30 ℃; and/or the reaction time is 3-5 h.
9. The method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride according to claim 1, wherein: the reaction temperature for preparing the phthalic anhydride by dehydrating the cycloaddition intermediate product under the solid catalyst is two stages: the first section is 15-35 ℃; and/or the reaction time is 1-3 h; the second section is 70-95 ℃; and/or the reaction time is 0.5-8 h.
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| US4560772A (en) * | 1984-10-22 | 1985-12-24 | Stauffer Chemical Company | Preparation of substituted phthalic anhydrides |
| CN110128438A (en) * | 2019-05-29 | 2019-08-16 | 西南林业大学 | A kind of method and its application of photocatalysis biology base furans Diels-Alder reaction |
| WO2020046124A1 (en) * | 2018-08-29 | 2020-03-05 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Diels-alder reaction with furanics to obtain aromatics |
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| CA2991207A1 (en) * | 2015-07-01 | 2017-01-05 | Novomer, Inc. | Methods for production of terephthalic acid from ethylene oxide |
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| US4560772A (en) * | 1984-10-22 | 1985-12-24 | Stauffer Chemical Company | Preparation of substituted phthalic anhydrides |
| WO2020046124A1 (en) * | 2018-08-29 | 2020-03-05 | Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno | Diels-alder reaction with furanics to obtain aromatics |
| CN110128438A (en) * | 2019-05-29 | 2019-08-16 | 西南林业大学 | A kind of method and its application of photocatalysis biology base furans Diels-Alder reaction |
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