Method for preparing dicarboxylic ester from biomass
The preparation of dicarboxylic acid ester from fructose through the biomass route solves the problem of non-biodegradation of existing materials and achieves efficient and selective preparation of biodegradable materials.
Patent Information
- Application Number
- CN202510233027.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-28
- Publication Date
- 2025-06-17
AI Technical Summary
The existing dicarboxylate polymeric materials are not biodegradable, resulting in environmental pollution.
Through the biomass route, dicarboxylic acid esters are prepared from fructose through three-step catalytic conversion, including the formation of 2,5-furan diformaldehyde, long-chain precursors with furan ring structure, and hydrogenation reaction under the action of metal catalysts or metal catalysts and solid acid catalysts to produce furan ring dicarboxylic acid esters, tetrahydrofuran ring dicarboxylic acid esters or dimethyl sebacate.
The preparation of dicarboxylic acid ester from a biomass source is achieved, with high yield and selectivity, and three different dicarboxylic acid esters can be obtained, solving the problem of non-biodegradation of traditional materials.
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Figure CN120157579A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organic synthesis, and particularly relates to a method for preparing dicarboxylic acid esters from biomass. Background Art
[0002] As important industrial raw materials and widely used fine organic chemical products, dicarboxylic acid esters are widely used in industries such as solvents, plasticizers, resins, coatings, fragrances, flavors, pharmaceuticals, rubber, and plastics. At the same time, it is also an important intermediate for the separation of dicarboxylic acids and the hydrogenation of dicarboxylic acids to produce fine chemicals such as diols.
[0003] Currently, polyethylene terephthalate (PET) commonly produced by the polycondensation of terephthalic acid (PTA) and ethylene glycol (EG) can be processed into fibers, films, and plastic products, which have advantages such as high strength and good dimensional stability. However, PET materials are not biodegradable, and the outflow of a large amount of PET materials will cause environmental pollution. Therefore, studying a new synthesis technology for dicarboxylic acid esters is of great practical significance in solving the problem that current dicarboxylic acid ester polymer materials are not biodegradable. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for preparing dicarboxylic acid esters from biomass, which has simple steps, high yield, and can produce several different dicarboxylic acid esters.
[0005] To achieve the above purpose, the technical solution adopted by the present invention is:
[0006] A method for preparing dicarboxylic acid esters from biomass, the specific steps are as follows:
[0007] S1. Fructose reacts with additive potassium bromide and dimethyl sulfoxide under the catalysis of an acid catalyst to generate 2,5-furandicarboxaldehyde.
[0008] S2. The 2,5-furandicarboxaldehyde prepared in step S1 is added to N,N-dimethylformamide and reacts with methyl hydrogen malonate to generate a long-chain precursor with a furan ring structure; the structural formula of the long-chain precursor with a furan ring structure is
[0009] S3. The long-chain precursor with a furan ring structure prepared in step S2 is added to a solvent under the catalysis of a metal catalyst or a metal catalyst and a solid acid catalyst, and the reaction is carried out to prepare a dicarboxylic acid ester; the dicarboxylic acid ester is one of a furan ring dicarboxylic acid ester, a tetrahydrofuran ring dicarboxylic acid ester, and dimethyl sebacate; when only catalyzed by a metal catalyst, hydrogenation outside the ring gives a furan ring dicarboxylic acid ester, and its structural formula is When only catalyzed by a metal catalyst, full hydrogenation gives a tetrahydrofuran ring dicarboxylic acid ester, and its structural formula is When a metal catalyst and a solid acid catalyst are co-catalyzed, dimethyl sebacate is obtained by hydrodeoxygenation.
[0010] Preferably, in step S1, the acid catalyst is one of ion exchange resin CD250, ion exchange resin CD750, and ion exchange resin AIRC 120H; the mass ratio between the acid catalyst and fructose is (0.01 - 0.5):1.
[0011] Preferably, in step S1, the mass ratio between the additive potassium bromide and fructose is (0.1 - 0.5):1; the ratio of the volume of dimethyl sulfoxide to the mass of fructose is (0.5 - 5) mL:100 mg.
[0012] Preferably, in step S1, the hydrolysis reaction temperature is 80 - 150 °C, and the reaction time is 8 - 16 h.
[0013] Preferably, in step S2, the molar ratio between 2,5-furandicarboxaldehyde and hydrogen methylmalonate is 1:(1 - 3); the reaction temperature is 50 - 120 °C, and the reaction time is 10 - 16 h.
[0014] Further, in step S2, one or more of the catalysts ion exchange resin IRA-402, ion exchange resin A26, ion exchange resin A21, magnesium-aluminum hydrotalcite, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane are added; among them, the 4-dimethylaminopyridine and 1,4-diazabicyclo[2.2.2]octane are 10% of the molar amount of 2,5-furandicarboxaldehyde; the ion exchange resin IRA-402, ion exchange resin A26, ion exchange resin A21, and magnesium-aluminum hydrotalcite are 10% of the mass of 2,5-furandicarboxaldehyde.
[0015] Preferably, in step S2, the concentration of 2,5-furandicarboxaldehyde is 0.1 - 2 mol / L.
[0016] Preferably, in step S3, the reaction is carried out in a batch reactor; the reaction temperature is 30 - 230 °C, the reaction time is 12 - 36 h, and the hydrogen pressure is 2 - 3 MPa.
[0017] Preferably, in step S3, the metal catalyst is selected from one of Raney nickel, Pt / C, Pd / C, Ru / C, and Rh / C, where the active metal loading of Pt / C, Pd / C, Ru / C, and Rh / C is 3 - 10 wt%; the acidic catalyst is H-Y or phosphotungstic acid; when only the metal catalyst is present, the metal catalyst is 10% of the mass of the long-chain precursor with a furan ring structure; when both the metal catalyst and the acidic catalyst are present, the metal catalyst and the acidic catalyst are 10% and 20% of the mass of the long-chain precursor with a furan ring structure, respectively.
[0018] Preferably, in step S3, the solvent used is one or more of 1,4-dioxane, n-octane, methanol, tetrahydrofuran, and ethyl acetate, and the concentration of the long-chain precursor with a furan ring structure is 0.01 - 5 mol / L.
[0019] Compared with the prior art, the present invention has the following beneficial effects:
[0020] The present invention selects a biomass route to catalytically convert fructose into dicarboxylic acid esters in three steps, with a green raw material source; by regulating the hydrogenation depth, three different dicarboxylic acid esters are selectively obtained. Description of the Drawings
[0021] Figure 1 GC spectrum of 2,5-furandicarboxaldehyde prepared by hydrolysis and oxidation of fructose as the raw material in step S1 of Example 1;
[0022] Figure 2 MS spectrum of 2,5-furandicarboxaldehyde prepared by hydrolysis and oxidation of fructose as the raw material in step S1 of Example 1;
[0023] Figure 3 For 2,5-furandicarboxaldehyde prepared by hydrolysis and oxidation of fructose as the raw material in step S1 of Example 1 1 1H-NMR spectrum;
[0024] Figure 4 For 2,5-furandicarboxaldehyde prepared by hydrolysis and oxidation of fructose as the raw material in step S1 of Example 1 13 13C-NMR spectrum;
[0025] Figure 5 GC spectrum of the long-chain precursor with a furan ring structure prepared by reacting 2,5-furandicarboxaldehyde and methylhydrogen malonate as the raw materials in step S2 of Example 1;
[0026] Figure 6 MS spectrum of the long-chain precursor with a furan ring structure prepared by reacting 2,5-furandicarboxaldehyde and methylhydrogen malonate as the raw materials in step S2 of Example 1;
[0027] Figure 7 For the long-chain precursor with a furan ring structure prepared by reacting 2,5-furandicarboxaldehyde and methylhydrogen malonate as the raw materials in step S2 of Example 1 1 1H-NMR spectrum;
[0028] Figure 8 For the long-chain precursor with a furan ring structure prepared by reacting 2,5-furandicarboxaldehyde and methylhydrogen malonate as the raw materials in step S2 of Example 1 13 13C-NMR spectrum;
[0029] Figure 9 The GC spectrum of the furan ring dicarboxylic acid ester prepared in step S3 of Example 1;
[0030] Figure 10 The MS spectrum of the furan ring dicarboxylic acid ester prepared in step S3 of Example 1;
[0031] Figure 11 The 1 1H-NMR spectrum of the furan ring dicarboxylic acid ester prepared in step S3 of Example 1;
[0032] Figure 12 The 13 13C-NMR spectrum of the furan ring dicarboxylic acid ester prepared in step S3 of Example 1;
[0033] Figure 13 The 1 1H-NMR spectrum of the tetrahydrofuran ring dicarboxylic acid ester prepared in step S3 of Example 2;
[0034] Figure 14 The 13 13C-NMR spectrum of the tetrahydrofuran ring dicarboxylic acid ester prepared in step S3 of Example 2;
[0035] Figure 15 The GC spectrum of dimethyl sebacate prepared in step S3 of Example 3;
[0036] Figure 16 The MS spectrum of dimethyl sebacate prepared in step S3 of Example 3;
[0037] Figure 17 The 1 1H-NMR spectrum of dimethyl sebacate prepared in step S3 of Example 3;
[0038] Figure 18 The 13 13C-NMR spectrum of dimethyl sebacate prepared in step S3 of Example 3. Detailed implementation manners
[0039] The present invention will be further described in detail below with reference to the examples.
[0040] In the following examples, unless otherwise specified, the reagents used can be obtained through commercial purchase or in the manner reported in known literature.
[0041] Example 1
[0042] S1. Fructose (0.56 mmol, 100 mg) was added under the catalysis of ion exchange resin CD250 (25 mg) to (0.28 mmol, 33 mg) KBr and dimethyl sulfoxide (2 mL) to undergo an oxidative hydrolysis reaction to form 2,5-furandicarboxaldehyde. The reaction temperature was 130 °C and the reaction time was 12 h. The mixture obtained after the reaction was extracted to remove the catalyst and additives, and the organic layer was taken and added with internal standard n-tridecane for detection. After gas chromatography analysis, as Figure 1 shown, the yield of 2,5-furandicarboxaldehyde was 55%;
[0043] The MS spectrum of the 2,5-furandicarboxaldehyde prepared in this step was as Figure 2 shown, 1 the 1H-NMR spectrum and 13 the 13C-NMR spectrum were as Figure 3 and Figure 4 shown. The structural characterization data was as follows:
[0044] 1 1H NMR (400 MHz, CDCl3) δ 9.87 (s, 2H), 7.34 (s, 2H); 13 13C NMR (101 MHz, CDCl3) δ 179.18, 154.23, 119.17.
[0045] S2. (62.05 mg, 0.5 mmol) 2,5-Furandicarboxaldehyde prepared in step S1 was added under (6.1 mg, 0.05 mmol) 4-dimethylaminopyridine DMAP to (0.5 mL) N,N-dimethylformamide and (130 mg, 1.1 mmol) hydrogen methylmalonate and reacted at 80 °C for 15 h to form a long-chain precursor with a furan ring structure; the structural formula of the long-chain precursor with a furan ring structure was The mixture obtained after the reaction was extracted to remove the solvent and catalyst, and the organic layer was taken and added with internal standard n-tridecane for detection. After gas chromatography analysis, as Figure 5 shown, the yield of the furan ring long-chain precursor was 94%;
[0046] The MS spectrum of the furan ring long-chain precursor prepared in this step was as Figure 6 shown, 1 the 1H-NMR spectrum and 13 the 13C-NMR spectrum were as Figure 7 and Figure 8 shown. The structural characterization data was as follows:
[0047] 11H NMR (600 MHz, CDCl3) δ 7.46–7.37 (m, 2H), 6.72–6.65 (m, 2H), 6.44 (ddd, J = 15.7, 4.6, 2.1 Hz, 2H), 3.86–3.80 (m, 6H); 13 13C NMR (151 MHz, CDCl3) δ 167.08, 152.44, 130.27, 117.57, 116.75, 51.83.
[0048] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6 mg, 10 wt%) of Raney nickel to (2 mL) of methanol in a high-pressure reactor. React at 70 °C and (2 MPa) of H2 for 12 h to form a furan ring dicarboxylate; the structural formula of the furan ring dicarboxylate is After the reaction, the resulting mixture was filtered to remove the catalyst, and internal standard tridecane was added. After gas chromatography analysis, as Figure 9 shown, the yield of the furan ring dicarboxylate was 95%;
[0049] The MS spectrum of the furan ring dicarboxylate prepared in this step is as Figure 10 shown, 1 The 1H-NMR spectrum and 13 the 13C-NMR spectrum are as Figure 11 , Figure 12 shown, and the structure characterization data are as follows:
[0050] 1 1H NMR (600 MHz, CDCl3) δ 5.88 (s, 2H), 3.67 (s, 6H), 2.90 (dd, J = 8.5, 6.8 Hz, 4H), 2.62 (dd, J = 8.4, 6.9 Hz, 4H); 13 13C NMR (151 MHz, CDCl3) δ 173.00, 152.70, 105.79, 51.67, 32.49, 23.46.
[0051] Example 2
[0052] S1. Replace "ion exchange resin CD250" in Example 1 with "ion exchange resin CD750", and keep other processes the same as in Example 1. The yield of the furan ring long-chain precursor obtained is 53%.
[0053] S2. Replace "4-dimethylaminopyridine DMAP" in Example 1 with "(5.6 mg, 0.05 mmol) 1,4-diazabicyclo[2.2.2]octane DABCO", and keep other processes the same as in Example 1. The yield of the furan ring long-chain precursor is 92%.
[0054] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6 mg, 10 wt%) Pd / C to (2 mL) of methanol. React in a high-pressure reactor at 90 °C and (2 MPa) H2 for 12 h to form a tetrahydrofuran ring dicarboxylate ester; the structural formula of the tetrahydrofuran ring dicarboxylate ester is The mixture obtained after the reaction is filtered to remove the catalyst, and internal standard tridecane is added. After gas chromatography analysis, the yield of the furan ring dicarboxylate ester is 98%.
[0055] The 1H-NMR spectrum of the tetrahydrofuran ring dicarboxylate ester prepared in this step 1 and the 13C-NMR spectrum are as 13 shown in Figure 13 、 Figure 14 and the structural characterization data are as follows:
[0056] 1H NMR (600 MHz, CDCl3) δ 3.77–3.71 (m, 1H), 3.56 (s, 3H), 2.31–2.22 (m, 2H), 1.87 (t, J = 6.4 Hz, 1H), 1.78–1.73 (m, 1H), 1.72–1.66 (m, 2H); 13 13C NMR (151 MHz, CDCl3) δ 174.23, 51.38, 34.00, 28.99, 24.85.
[0057] Example 3
[0058] S1. Replace "ion exchange resin CD250" in Example 1 with "ion exchange resin AIRC 120H", and keep other processes the same as in Example 1. The yield of the furan ring long-chain precursor is 54%.
[0059] S2. Replace "4-dimethylaminopyridine DMAP" in Example 1 with "(6.2 mg, 10 wt%) ion exchange resin IRA-402", and keep other processes the same as in Example 1. The yield of the furan ring long-chain precursor is 88%.
[0060] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6
[0061] (47.2 mg, 20 wt%) Pd / C and (47.2 mg, 20 wt%) H-Y were added to (2 mL) n-octane. In a high-pressure reactor,
[0062] The reaction was carried out at 230 °C and (3 MPa) H2 for 36 h to produce dimethyl sebacate. After the reaction, the obtained mixture was filtered to remove the catalyst, internal standard tridecane was added, and gas chromatography analysis was performed as Figure 15 shown. The yield of dimethyl sebacate was 92%;
[0063] The MS spectrum of the dimethyl sebacate prepared in this step is as Figure 16 shown, 1 The 1H-NMR spectrum and 13 The 13C-NMR spectrum are as Figure 17 , Figure 18 shown. The structural characterization data are as follows: 1 1H NMR (600 MHz, CDCl 3 3) δ 3.63 (s, 1H), 2.27 (t, J = 7.6 Hz, 1H), 1.58 (t, J = 7.5 Hz, 1H), 1.27 (s, 2H); 13 13C NMR (151 MHz, CDCl3) δ 174.23, 51.38, 34.00, 28.99, 24.85.
[0064] Example 4
[0065] S1: The same as in Example 1;
[0066] S2: "Ion exchange resin A26" was used instead of "ion exchange resin IRA-402" in Example 3, and other processes were kept the same as in Example 3. The yield of the furan ring long-chain precursor was 86%;
[0067] S3: (236.22 mg, 1 mmol) The long-chain precursor with a furan ring structure prepared in step S2 was added to (2 mL) ethyl acetate in the presence of (23.6 mg, 10 wt%) Raney nickel. In a high-pressure reactor, the reaction was carried out at 70 °C and (2 MPa) H2 for 12 h to produce a furan ring dicarboxylate; the structural formula of the furan ring dicarboxylate is After the reaction, the obtained mixture was filtered to remove the catalyst, internal standard tridecane was added, and gas chromatography analysis was performed. The yield of the furan ring dicarboxylate was 93%.
[0068] Example 5
[0069] S1: The same as in Example 1;
[0070] S2. Replace "ion exchange resin IRA-402" in Example 3 with "ion exchange resin A21", and keep other processes the same as in Example 3. The yield of the furan ring long-chain precursor is 84%;
[0071] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6 mg, 10 wt%) Pt / C to (2 mL) of methanol in a high-pressure reactor. React at 90 °C and (2 MPa) H2 for 12 h to form a tetrahydrofuran ring dicarboxylate ester; the structural formula of the tetrahydrofuran ring dicarboxylate ester is After the reaction, the resulting mixture is filtered to remove the catalyst, and internal standard tridecane is added. After gas chromatography analysis, the yield of the furan ring dicarboxylate ester is 94%.
[0072] Example 6
[0073] S1. The same as in Example 1;
[0074] S2. Replace "ion exchange resin IRA-402" in Example 3 with "magnesium-aluminum hydrotalcite", and keep other processes the same as in Example 3. The yield of the furan ring long-chain precursor is 84%;
[0075] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6 mg, 10 wt%) Ph / C (47.2 mg, 20 wt%) H-Y to (2 mL) of n-octane in a high-pressure reactor. React at 230 °C and (3 MPa) H2 for 36 h to form dimethyl sebacate. After the reaction, the resulting mixture is filtered to remove the catalyst, and internal standard tridecane is added. After gas chromatography analysis, the yield of dimethyl sebacate is 86%.
[0076] Example 7
[0077] S1. The same as in Example 1;
[0078] S2. No catalyst is added in this step, and other processes are the same as in Example 1. The yield of the furan ring long-chain precursor is 88%;
[0079] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 and (23.6 mg, 10 wt%) Raney nickel to (2 mL) of 1,4-dioxane in a high-pressure reactor. React at 70 °C and (2 MPa) H2 for 12 h to form a furan ring dicarboxylate ester; the structural formula of the furan ring dicarboxylate ester is The mixture obtained after the reaction was filtered to remove the catalyst, and internal standard tridecane was added. After gas chromatography analysis, the yield of the furan ring dicarboxylate was 86%.
[0080] Example 8
[0081] S1. It is the same as Example 1;
[0082] S2. Preparation of the long-chain precursor of the furan ring;
[0083] S2-1. (62.05 mg, 0.5 mmol) 2,5-furandicarboxaldehyde prepared in step S1 was added under (6.2 mg, 10 wt%) ion exchange resin IRA-402 to (0.5 mL) N,N-dimethylformamide and (130 mg, 1.1 mmol) hydrogen methylmalonate, and reacted at 80 °C for 15 h to form a long-chain precursor with a furan ring structure; the structural formula of the long-chain precursor with a furan ring structure is After the reaction, the upper-layer reaction solution was taken out, internal standard n-tridecane was added for detection, and after gas chromatography analysis, the yield of the long-chain precursor of the furan ring was 88%;
[0084] S2-2. (1 mL) N-N dimethylformamide was added to the high-pressure reaction tube of the upper-layer reaction solution to wash the lower-layer ion exchange resin IRA-402. After washing three times, step S2-1 was repeated, internal standard tridecane was added, and after gas chromatography analysis, the yield of the long-chain precursor of the furan ring was 87%;
[0085] S2-3. Step S2-2 was repeated, and after gas chromatography analysis, the yield of the long-chain precursor of the furan ring was 84%;
[0086] S2-4. Step S2-2 was repeated, and after gas chromatography analysis, the yield of the long-chain precursor of the furan ring was 86%;
[0087] It can be seen from the above steps that the catalyst IRA-402 can be recycled 3 times with no obvious change in yield.
[0088] S3. (236.22 mg, 1 mmol) The long-chain precursor with a furan ring structure prepared in step S2 was added under (23.6 mg, 10 wt%) Raney nickel to (2 mL) tetrahydrofuran, and reacted in a high-pressure reactor at 70 °C and (2 MPa) H2 for 12 h to form a furan ring dicarboxylate; the structural formula of the furan ring dicarboxylate is The mixture obtained after the reaction was filtered to remove the catalyst, internal standard tridecane was added, and after gas chromatography analysis, the yield of the furan ring dicarboxylate was 80%.
[0089] Example 9
[0090] S1. It is the same as that in Example 1;
[0091] S2. (62.05 mg, 0.5 mmol) 2,5-Furandicarboxaldehyde prepared in step S1 was added under (6.2 mg, 10 wt%) ion exchange resin IRA-402 to (0.5 mL) N,N-dimethylformamide and (130 mg, 1.1 mmol) hydrogen methylmalonate. An internal standard tridecane was added, and the reaction was carried out at 80 °C for 16 h. Samples were taken every 2 h starting from 8 h to generate a long-chain precursor with a furan ring structure; the structural formula of the long-chain precursor with a furan ring structure is After 8 h, a drop of the reaction solution was taken out, diluted, and detected. After gas chromatography analysis, the yield of the furan ring long-chain precursor was 50%; after 10 h, a drop of the reaction solution was taken out, diluted, and detected. After gas chromatography analysis, the yield of the furan ring long-chain precursor was 80%; after 12 h, a drop of the reaction solution was taken out, diluted, and detected. After gas chromatography analysis, the yield of the furan ring long-chain precursor was 88%; after 14 h, a drop of the reaction solution was taken out, diluted, and detected. After gas chromatography analysis, the yield of the furan ring long-chain precursor was 88%; after 16 h, a drop of the reaction solution was taken out, diluted, and detected. After gas chromatography analysis, the yield of the furan ring long-chain precursor was 87%.
[0092] S3. (236.22 mg, 1 mmol) The long-chain precursor with a furan ring structure prepared in step S2 was added under (23.6 mg, 10 wt%) Raney nickel to (2 mL) methanol. In a high-pressure reaction kettle, the reaction was carried out at 30 °C and (2 MPa) H2 for 12 h to generate furan ring dicarboxylate; the structural formula of the furan ring dicarboxylate is The mixture obtained after the reaction was filtered to remove the catalyst, an internal standard tridecane was added, and after gas chromatography analysis, the yield of the furan ring dicarboxylate was 85%.
[0093] Example 10
[0094] In step S3 of this example, the temperature was 50 °C, and other steps were all kept the same as those in Example 1; after gas chromatography analysis, the yield of the furan ring dicarboxylate was 88%.
[0095] Example 11
[0096] In step S3 of this example, the temperature was 90 °C, and other steps were all kept the same as those in Example 1; after gas chromatography analysis, the yield of the furan ring dicarboxylate was 85%.
[0097] Example 12
[0098] Replace "Pd / C" in Step 3 of Example 2 with "Ru / C", and keep the other steps the same as those in Example 2; after gas chromatography analysis, the yield of the tetrahydrofuran ring dicarboxylate is 86%.
[0099] Example 13
[0100] Replace "Pd / C" in Step 3 of Example 2 with "Rh / C", and keep the other steps the same as those in Example 2; after gas chromatography analysis, the yield of the tetrahydrofuran ring long-chain precursor is 88%.
[0101] Example 14
[0102] Replace "methanol" in Step 3 of Example 2 with "ethyl acetate", and keep the other processes the same as those in Example 2. The yield of the tetrahydrofuran ring dicarboxylate obtained is 90%.
[0103] Example 15
[0104] Replace "methanol" in Step 3 of Example 2 with "1,4-dioxane", and keep the other processes the same as those in Example 2. The yield of the tetrahydrofuran ring dicarboxylate obtained is 88%.
[0105] Example 16
[0106] Replace "methanol" in Step 3 of Example 2 with "tetrahydrofuran", and keep the other processes the same as those in Example 2. The yield of the tetrahydrofuran ring dicarboxylate obtained is 89%.
[0107] Example 17
[0108] S1. The same as that in Example 1;
[0109] S2. The same as that in Example 1;
[0110] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in Step S2 and (23.6 mg, 10 wt%) of Pd / C to (2 mL) of methanol in a high-pressure reactor, and react at 30 °C and (2 MPa) of H2 for 12 h to produce the tetrahydrofuran ring dicarboxylate; the structural formula of the tetrahydrofuran ring dicarboxylate is After the reaction, the obtained mixture is filtered to remove the catalyst, internal standard tridecane is added, and after gas chromatography analysis, the yield of the tetrahydrofuran ring dicarboxylate is 83%.
[0111] Example 18
[0112] Change the condition of 30 °C in Step S3 to 50 °C, and keep the other processes the same as those in Example 17. The yield of the tetrahydrofuran ring dicarboxylate obtained is 89%.
[0113] Example 19
[0114] In step S3, change the condition of 30 °C to 110 °C, and keep other processes the same as in Example 17. The yield of the tetrahydrofuran ring dicarboxylic acid ester obtained is 98%.
[0115] Example 20
[0116] S1. The same as in Example 1;
[0117] S2. The same as in Example 1;
[0118] S3. Add (236.22 mg, 1 mmol) of the long-chain precursor with a furan ring structure prepared in step S2 to (2 mL) of n-octane under (23.6 mg, 10 wt%) Pd / C and (47.2 mg, 20 wt%) phosphotungstic acid in a high-pressure reactor, and react at 230 °C and (3 MPa) H2 for 36 h to generate dimethyl sebacate. After the reaction, the obtained mixture is filtered to remove the catalyst, add the internal standard tridecane, and through gas chromatography analysis, the yield of dimethyl sebacate is 80%.
Claims
1. A method for preparing dicarboxylic acid esters from biomass, characterized in that: The specific steps are: S1. Adding potassium bromide as an additive to fructose under the catalysis of an acid catalyst and reacting with dimethyl sulfoxide to produce 2,5-furandicarboxaldehyde; S2, adding N,N-dimethylformamide to the 2,5-furandicarboxaldehyde prepared in step S1 to react with methylmalonic acid hydrogen to generate a long-chain precursor having a furan ring structure; the structural formula of the long-chain precursor having a furan ring structure is S3, adding a solvent to the long-chain precursor with a furan ring structure prepared in step S2 under the catalysis of a metal catalyst or a metal catalyst and a solid acid catalyst, and reacting to prepare a dicarboxylic acid ester; the dicarboxylic acid ester is one of a furan ring dicarboxylic acid ester, a tetrahydrofuran ring dicarboxylic acid ester, and dimethyl sebacate; when only the metal catalyst is used for catalysis, exocyclic hydrogenation is performed to obtain a furan ring dicarboxylic acid ester, and the structural formula thereof is When only metal catalyst is used for catalysis, full hydrogenation is performed to obtain tetrahydrofuran cyclic dicarboxylic acid ester, the structural formula of which is When the metal catalyst and the solid acid catalyst are used together for catalysis, dimethyl sebacate is obtained by hydrodeoxygenation.
2. A method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S1, the acid catalyst is one of ion exchange resin CD250, ion exchange resin CD570, and ion exchange resin AIRC 120H; the mass ratio between the acid catalyst and fructose is (0.01-0.5):
1.
3. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S1, the mass ratio of the additive potassium bromide to fructose is (0.1-0.5):1; the ratio of the volume of dimethyl sulfoxide to the mass of fructose is (0.5-5) mL:100 mg.
4. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S1, the reaction temperature is 80-150° C. and the reaction time is 8-16 h.
5. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S2, the molar ratio of 2,5-furandicarboxaldehyde to methylmalonic acid hydrogen is 1:(1-3); the reaction temperature is 50-120° C., and the reaction time is 10-16 h.
6. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S2, a catalyst selected from the group consisting of ion exchange resin IRA-402, ion exchange resin A26, ion exchange resin A21, magnesium-aluminum hydrotalcite, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane is added; wherein the 4-dimethylaminopyridine and 1,4-diazabicyclo[2.2.2]octane are 10% of the molar amount of 2,5-furandicarboxaldehyde; and the ion exchange resin IRA-402, ion exchange resin A26, ion exchange resin A21, and magnesium-aluminum hydrotalcite are 10% of the mass of 2,5-furandicarboxaldehyde.
7. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S2, the concentration of 2,5-furandicarboxaldehyde is 0.1-2 mol / L.
8. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S3, the reaction is carried out in a tank reactor; the reaction temperature is 30-230° C., the reaction time is 12-36 h, and the hydrogen pressure is 2-3 MPa.
9. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S3, the metal catalyst is selected from one of ryning nickel, Pt / C, Pd / C, Ru / C, and Rh / C, wherein the active metal loading of Pt / C, Pd / C, Ru / C, and Rh / C is 3-10wt%; the acidic catalyst is HY or phosphotungstic acid; when there is only a metal catalyst, the metal catalyst is 10% of the mass of the long-chain precursor with a furan ring structure; when the metal catalyst and the acidic catalyst exist at the same time, the metal catalyst and the acidic catalyst are 10% and 20% of the mass of the long-chain precursor with a furan ring structure, respectively.
10. The method for preparing dicarboxylic acid esters from biomass according to claim 1, characterized in that: In step S3, the solvent used is one of 1,4-dioxane, n-octane, methanol, tetrahydrofuran, and ethyl acetate, and the concentration of the long-chain precursor having a furan ring structure is 0.01-5 mol / L.