Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments in order to further explain the technical contents of the present invention.
N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, methanol, ethanol, cyclohexyl acetate, sodium 4-vinylbenzenesulfonate, azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, azobisisobutyramidine hydrochloride are all analytical reagents and purchased from Annagi chemical or Shanghai province. Amberlyst-15 (acid content, 4.6mmol/g) was purchased from Afaha. (4-vinylbenzyl) tris (4-vinylphenyl) phosphonium chloride was prepared using literature methods (j. mater. chem.a,2015,3,23871). Contact angle measurements were made on a Dataphysics OCA20 contact angle measuring instrument. N is a radical of 2 A gas washing desorption isotherm is under the condition of 77K, and a Micrometrics ASAP 2020 instrumentThe above is completed. Scanning electron microscopy was performed at TESCAN MIRA3, and projection electron microscopy was performed at Tecnai G2F 30. An X-ray photoelectron spectrometer was performed on a VG multilab 2000. 13 C and 31 p solid nmr spectra were tested on bruker avance III 600.
Example 1: preparation of organic porous Polymer solid acid catalyst (APOA-1)
Dissolving 1.11g (5.38mmol) of 4-vinylbenzene sulfonic acid sodium and 0.89g (1.80mmol) of (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride in 20mLN, N-dimethylformamide, stirring at room temperature for 2 hours, transferring the solution to a reaction kettle, adding 0.05g of azobisisobutyronitrile into the kettle, raising the temperature of the reaction kettle to 100 ℃ under the protection of nitrogen, reacting for 24 hours, filtering the obtained product, washing with ethanol for 3 times, and drying in vacuum to obtain the sodium benzenesulfonate functionalized organic porous polymer carrier;
adding 1.0g of the prepared sodium benzenesulfonate functionalized organic porous polymer carrier into 100mL of 1mol/L sulfuric acid aqueous solution, stirring for 24 hours at room temperature, filtering, repeating the exchange for 2 times (total exchange for 3 times), washing the precipitate for 4 times with water, and drying in vacuum to obtain the amphiphilic organic porous polymer solid acid catalyst, which is marked as APOA-1.
The amphipathy of the prepared APOA-1 is tested by adopting a contact angle measuring instrument, the contact angle of water and the APOA-1 is shown in figure 1, a water drop is absorbed by the APOA-1, and the contact angle is marked as 0 degrees, which indicates that the prepared APOA-1 has excellent hydrophilic performance; the contact angle of the cyclohexyl acetate and the APOA-1 is shown in figure 2, the cyclohexyl acetate liquid drop is absorbed by the APOA-1, the contact angle is recorded as 0 degrees, and the prepared APOA-1 has excellent oleophylic property; the contact angle measurement results of combining the graph 1 and the graph 2 show that the prepared APOA-1 has excellent amphiphilic performance.
The acid content of the APOA-1 is measured by acid-base titration by adopting 1mol/L NaOH solution, and the acid content of the APOA-1 is 3.57 mmol/g.
Using solid nuclear magnetism 13 The spectrum C was characterized for APOA-1, as shown in FIG. 3, and 127.4 to 144.3ppm were assigned to the aromatic ring carbon and 41.4ppm were assigned to the carbon atom on the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum was analyzed for the characterization of APOA-1, and as shown in FIG. 4, the chemical shift of P was 21ppm, indicating that P has a chemical environment and is a quaternary phosphonium salt.
APOA-1 was analyzed by X-ray photoelectron spectroscopy, and the spectra are shown in FIGS. 5 and 6, in which C, P, S, O is present and S has-SO 3 H and HSO 4 - Two forms are provided.
The shape and size of the APOA-1 are detected by using a field emission scanning electron microscope and a transmission electron microscope (FIGS. 7 and 8), and it can be seen that the APOA-1 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
APOA-1 was analyzed for specific surface area and pore size using a specific surface area and pore size analyzer (FIG. 9). The specific surface area of APOA-1 was found to be 228m 2 Per g, pore volume of 0.55cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 2: preparation of organic porous Polymer solid acid catalyst (APOA-2)
This example was carried out in accordance with the preparation process of example 1, except that the mass of the monomer sodium 4-vinylbenzenesulfonate was 0.59g (2.86mmol) and the mass of the monomer (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride was 1.41g (2.86mmol), and the other operations were exactly the same as in example 1, to give the catalyst APOA-2.
The APOA-2 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-2 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-2, the contact angle is 0 degrees, which indicates that the prepared APOA-2 has excellent amphipathy.
The acid content of the APOA-2 is measured by acid-base titration by adopting 1mol/L NaOH solution, and the acid content of the APOA-2 is 2.62 mmol/g.
Using solid nuclear magnetism 13 The spectrum C of APOA-2 is characterized and analyzed, and 127.5-144.4ppm belongs to the aromatic ring carbon, 41ppm belongs to the carbon atom of the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed on APOA-2, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-2 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The appearance and the size of the APOA-2 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-2 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-2 by using a specific surface area and pore size analyzer. The specific surface area of APOA-2 was measured to be 412m 2 Per g, pore volume of 0.73cm 3 ·g -1 The pore size distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 3: preparation of organic porous Polymer solid acid catalyst (APOA-3)
This example was carried out in accordance with the preparation process of example 1, except that the mass of the monomer sodium 4-vinylbenzenesulfonate was 1.25g (6.08mmol) and the mass of the monomer (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride was 0.75g (1.52mmol), and the other operations were exactly the same as in example 1, to give the catalyst APOA-3.
The APOA-3 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-3 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-3, the contact angle is 0 degrees, which indicates that the prepared APOA-3 has excellent amphipathy.
The acid content of the APOA-3 is measured by acid-base titration by adopting 1mol/L NaOH solution, and the acid content of the APOA-3 is 3.78 mmol/g.
Using solid state nuclear magnetism 13 The spectrum C is used for characterizing and analyzing APOA-3, and 127.5-144.5ppm belongs to the aromatic ring carbon41ppm belongs to the carbon atom of the polymerized vinyl group.
Using solid state nuclear magnetism 31 The P spectrum is characterized and analyzed for APOA-3, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-3 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The appearance and the size of the APOA-3 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-3 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-3 by using a specific surface area and pore size analyzer. The specific surface area of APOA-3 was found to be 139m 2 Per g, pore volume of 0.48cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 4: preparation of organic porous Polymer solid acid catalyst (APOA-4)
This example was carried out in accordance with the preparation process of example 1, except that the mass of the monomer sodium 4-vinylbenzenesulfonate was 1.35g (6.54mmol) and the mass of the monomer (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride was 0.65g (1.31mmol), and the other operations were exactly the same as in example 1, giving the catalyst denoted as APOA-4.
The APOA-4 prepared was characterized and analyzed as in example 1 as follows:
the amphipathy of the prepared APOA-4 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-4, the contact angle is 0 degrees, which indicates that the prepared APOA-4 has excellent amphipathy.
The acid content of the APOA-4 is measured by acid-base titration by adopting 1mol/L NaOH solution, and the acid content of the APOA-4 is 3.82 mmol/g.
Using solid nuclear magnetism 13 The spectrum C is used for characterizing and analyzing APOA-4, and 127.2-144.5ppm belongs to aromatic ringsCarbon, 41.5ppm belongs to the carbon atom of the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed by APOA-4, the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-4 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The appearance and the size of the APOA-4 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-4 is formed by stacking irregular nano particles and is in a loose state, and a small amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-4 by using a specific surface area and pore size analyzer. The specific surface area of APOA-4 was found to be 89m 2 Per g, pore volume of 0.32cm 3 ·g -1 The pore diameter distribution curve shows that the material has a certain amount of micropores and mesopores and a small amount of macropores.
Example 5: preparation of organic porous Polymer solid acid catalyst (APOA-5)
This example was carried out in accordance with the preparation of example 1, except that 0.02g of azobisisobutyronitrile as a free-radical initiator was used, and otherwise exactly the same operation as in example 1 gave the catalyst which was designated APOA-5.
The APOA-5 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-5 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-5, the contact angle is 0 degrees, which indicates that the prepared APOA-5 has excellent amphipathy.
The acid content of APOA-5 is measured by acid-base titration by adopting 1mol/LNaOH solution, and the acid content of APOA-5 is 3.47 mmol/g.
Using solid state nuclear magnetism 13 The spectrum C was characterized and analyzed for APOA-5, and 127.4 to 144.5ppm were assigned to the aromatic ring carbon and 41.2ppm were assigned to the carbon atom on the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed by APOA-5, the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-5 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The morphology and the size of APOA-5 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-5 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-5 by using a specific surface area and pore size analyzer. The specific surface area of APOA-5 was found to be 185m 2 Per g, pore volume of 0.51cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 6: preparation of organic porous Polymer solid acid catalyst (APOA-6)
This example was carried out in accordance with the preparation of example 1, except that 0.06g of azobisisobutyronitrile as a free-radical initiator was used, and otherwise exactly the same operation as in example 1 gave the catalyst which was designated APOA-6.
The APOA-6 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-6 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-6, the contact angle is 0 degrees, which indicates that the prepared APOA-6 has excellent amphipathy.
The acid content of APOA-6 is determined by acid-base titration with 1mol/LNaOH solution, and the acid content of APOA-6 is 3.52 mmol/g.
Using solid nuclear magnetism 13 The spectrum C was characterized and analyzed for APOA-6, and 127.2 to 144.4ppm were assigned to the aromatic ring carbon and 41.3ppm were assigned to the carbon atom on the polymerized vinyl group.
Using solid state nuclear magnetism 31 The P spectrum is used for carrying out characterization analysis on the APOA-6,the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The APOA-6 is analyzed by an X-ray photoelectron spectrometer, and the result shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The morphology and the size of the APOA-6 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-6 is formed by stacking irregular nano particles and is in a loose shape, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-6 by using a specific surface area and pore size analyzer. The specific surface area of APOA-6 was found to be 216m 2 Per g, pore volume of 0.54cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 7: preparation of organic porous Polymer solid acid catalyst (APOA-7)
This example was carried out in accordance with the preparation of example 1, except that 0.05g of azobisisoheptonitrile was used as the free-radical initiator, and exactly the same procedure as in example 1 was used, the catalyst obtained was designated APOA-7.
The APOA-7 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-7 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-7, the contact angle is 0 degrees, which indicates that the prepared APOA-7 has excellent amphipathy.
The acid content of APOA-7 is determined by acid-base titration by using 1mol/LNaOH solution, and the acid content of APOA-7 is 3.50 mmol/g.
Using solid nuclear magnetism 13 The spectrum C was characterized and analyzed for APOA-7, and 127.2 to 144.3ppm were assigned to the aromatic ring carbon and 41.5ppm were assigned to the carbon atom on the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed for APOA-7, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-7 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO 3 H and HSO 4 Two forms are provided.
The morphology and the size of the APOA-7 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-7 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-7 by using a specific surface area and pore size analyzer. The specific surface area of APOA-7 was found to be 207m 2 Per g, pore volume 0.53cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 8: preparation of organic porous Polymer solid acid catalyst (APOA-8)
This example was carried out in accordance with the preparation of example 3, except that the polymerization solvent used was N, N-dimethylacetamide and otherwise exactly the same as in example 3, giving the catalyst APOA-8.
The APOA-8 thus prepared was characterized, as in example 3, as follows:
the amphipathy of the prepared APOA-8 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-8, the contact angle is 0 degrees, which indicates that the prepared APOA-8 has excellent amphipathy.
The acid content of the APOA-8 is measured by acid-base titration by adopting 1mol/L NaOH solution, and the acid content of the APOA-8 is 3.79 mmol/g.
Using solid state nuclear magnetism 13 The spectrum C was characterized and analyzed for APOA-8, and 127.4 to 144.5ppm were assigned to the aromatic ring carbon and 41.2ppm were assigned to the carbon atom on the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed on APOA-8, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
APOA-8 is analyzed by an X-ray photoelectron spectrometer,the results indicated the presence of C, P, S, O elements, and S has an-SO 3 H and HSO 4 Two forms are provided.
The appearance and the size of the APOA-8 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-8 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And analyzing the specific surface area and the pore diameter of the APOA-8 by using a specific surface area and pore diameter analyzer. The specific surface area of APOA-8 was found to be 149m 2 Per g, pore volume of 0.47cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 9: preparation of organic porous Polymer solid acid catalyst (APOA-9)
This example was carried out in accordance with the preparation of example 1, except that the acid used was a 2mol/L nitric acid solution, the other operations were exactly the same as in example 1, and the catalyst was finally obtained and designated APOA-9.
The APOA-9 prepared is characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-9 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-9, the contact angle is 0 degrees, which indicates that the prepared APOA-9 has excellent amphipathy.
The acid content of APOA-9 was determined by acid-base titration using 1mol/LNaOH solution, with the acid content of APOA-9 being 2.68 mmol/g.
Using solid state nuclear magnetism 13 The spectrum C was characterized and analyzed for APOA-9, and 127.0 to 144.2ppm were assigned to the aromatic ring carbon and 41.1ppm to the carbon atom on the polymerized vinyl group.
Using solid nuclear magnetism 31 The P spectrum is characterized and analyzed on APOA-9, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The APOA-9 is analyzed by an X-ray photoelectron spectrometer, and the result shows that C, P, S, O, N element exists and S only has-SO 3 The H form.
The morphology and the size of APOA-9 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-9 is formed by stacking irregular nano particles and is in a loose shape, and a certain amount of mesopores exist among the stacked particles.
And (3) carrying out specific surface area and pore size analysis on the APOA-9 by using a specific surface area and pore size analyzer. The specific surface area of APOA-9 was found to be 236m 2 Per g, pore volume of 0.58cm 3 ·g -1 The pore size distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 10: preparation of organic porous Polymer solid acid catalyst (APOA-10)
This example was carried out in accordance with the preparation process of example 9, except that the nitric acid solution was used at a concentration of 0.5mol/L and the ion exchange time was 12 hours, and the operation was otherwise exactly the same as in example 9, and the catalyst obtained was designated as APOA-10.
The APOA-10 thus prepared was characterized and analyzed as in example 1, as follows:
the amphipathy of the prepared APOA-10 is tested by adopting a contact angle measuring instrument, and the result shows that water and cyclohexyl acetate are absorbed by the APOA-10, the contact angle is 0 degrees, which indicates that the prepared APOA-10 has excellent amphipathy.
The acid content of APOA-10 is determined by acid-base titration with 1mol/LNaOH solution, and the acid content of APOA-10 is 2.67 mmol/g.
Using solid nuclear magnetism 13 The spectrum C was analyzed for the characterization of APOA-10, and 127.3 to 144.3ppm were assigned to the aromatic ring carbon and 41.4ppm to the carbon atom on the polymerized vinyl group.
Using solid state nuclear magnetism 31 The P spectrum is characterized and analyzed on APOA-10, and the chemical shift of P is 21ppm, which indicates that P has a chemical environment and is a quaternary phosphonium salt.
The result of the analysis of APOA-10 by an X-ray photoelectron spectrometer shows that C, P, S, O, N element exists and S only has-SO 3 The H form.
The appearance and the size of the APOA-10 are detected by adopting a field emission scanning electron microscope and a transmission electron microscope, so that the APOA-10 is formed by stacking irregular nano particles and is in a loose state, and a certain amount of mesopores exist among the stacked particles.
And analyzing the specific surface area and the pore diameter of the APOA-10 by using a specific surface area and pore diameter analyzer. The specific surface area of APOA-10 was found to be 242m 2 Per g, pore volume of 0.58cm 3 ·g -1 The pore diameter distribution curve shows that the material has a large amount of micropores and mesopores and a small amount of macropores.
Example 11: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added into a 10mL glass reaction flask with a cock, and then the mixture was reacted at 120 ℃ for 2 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 92.2%, the selectivity of cyclohexanol was 95.6%, and the yield of cyclohexanol was 88.1%.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-2 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 65.9 percent, the selectivity of the cyclohexanol is 95.5 percent, and the yield of the cyclohexanol is 62.9 percent.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-3 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 86.7%, the selectivity of the cyclohexanol is 95.6%, and the yield of the cyclohexanol is 82.8%.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-4 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 79.3 percent, the selectivity of the cyclohexanol is 94.3 percent, and the yield of the cyclohexanol is 74.8 percent.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-5 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 86.5 percent, the selectivity of the cyclohexanol is 95.7 percent, and the yield of the cyclohexanol is 82.8 percent.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-6 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 90.9 percent, the selectivity of the cyclohexanol is 95.6 percent, and the yield of the cyclohexanol is 86.9 percent.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-7 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 89.3%, the selectivity of the cyclohexanol is 95.7%, and the yield of the cyclohexanol is 85.5%.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-8 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 85.4%, the selectivity of the cyclohexanol is 95.7%, and the yield of the cyclohexanol is 81.7%.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-9 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 88.2 percent, the selectivity of the cyclohexanol is 92.7 percent, and the yield of the cyclohexanol is 81.8 percent.
0.1g of APOA-1 catalyst is replaced by 0.1g of APOA-10 catalyst, the other conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 87.5 percent, the selectivity of the cyclohexanol is 92.9 percent, and the yield of the cyclohexanol is 81.3 percent.
0.1g of APOA-1 catalyst was replaced with 0.1g of Amberlyst-15 catalyst, the remaining conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 44.3%, the selectivity of cyclohexanol was 94.5%, and the yield of cyclohexanol was 41.9%.
0.1g of APOA-1 (acid content, 0.357mmol) catalyst was replaced with 5.6mg of benzenesulfonic acid (acid content, 0.357mmol), the remaining conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 69.1%, the selectivity of cyclohexanol was 90.5%, and the yield of cyclohexanol was 62.5%.
0.1g of APOA-1 (acid content, 0.357mmol) catalyst was replaced with 0.71mL of a 0.25mol/L sulfuric acid aqueous solution (acid content based on hydrogen ion, 0.357mmol), and the other conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 22.6%, the selectivity of cyclohexanol was 85.3%, and the yield of cyclohexanol was 19.3%.
Example 12: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added to a 10mL glass reaction flask with a cock, and then reacted at 100 ℃ for 3 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 36.2%, the selectivity of cyclohexanol was 95.7%, and the yield of cyclohexanol was 34.6%.
Example 13: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added to a 10mL glass reaction flask with a cock, and then reacted at 140 ℃ for 2 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 95.8%, the selectivity of cyclohexanol was 91.3%, and the yield of cyclohexanol was 87.5%.
Example 14: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.05g of APOA are sequentially added into a 10mL glass reaction bottle with a cock, and then the mixture is reacted for 2 hours at 120 ℃ under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 73.2%, the selectivity of cyclohexanol was 95.7%, and the yield of cyclohexanol was 70.1%.
Example 15: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.2g of APOA-were sequentially added into a 10mL glass reaction flask with a cock, and then reacted at 120 ℃ for 2 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 93.8%, the selectivity of cyclohexanol was 95.4%, and the yield of cyclohexanol was 89.5%.
Example 16: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added into a 10mL glass reaction flask with a cock, and then the mixture was reacted at 120 ℃ for 3 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 93.7%, the selectivity of cyclohexanol was 95.4%, and the yield of cyclohexanol was 89.4%.
Example 17: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added into a 10mL glass reaction flask with a cock, and then reacted at 120 ℃ for 8h under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 94.5%, the selectivity of cyclohexanol was 94.4%, and the yield of cyclohexanol was 89.2%.
Example 18: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
2mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added to a 10mL glass reaction flask with a cock, and then reacted at 120 ℃ for 3 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 86.7%, the selectivity of cyclohexanol was 95.3%, and the yield of cyclohexanol was 82.6%.
Example 19: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
1mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added to a 10mL glass reaction flask with a cock, and then reacted at 120 ℃ for 3 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 74.1%, the selectivity of cyclohexanol was 95.4%, and the yield of cyclohexanol was 70.7%.
Example 20: preparation of cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate
5mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added into a 10mL glass reaction flask with a cock, and then reacted at 120 ℃ for 3 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 94.3%, the selectivity of cyclohexanol was 95.5%, and the yield of cyclohexanol was 90.1%.
Example 21: recycling of catalyst
4mL of deionized water, 1.0g of cyclohexyl acetate and 10.1g of APOA-were sequentially added to a 10mL glass reaction flask with a cock, and then reacted at 130 ℃ for 2 hours under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography. The conversion of cyclohexyl acetate was 93.5%, the selectivity of cyclohexanol was 94.8%, and the yield of cyclohexanol was 88.6%.
After the reaction is finished, the centrifuged catalyst is washed by ethanol for 3 times, then is dried in vacuum at 60 ℃ for 12 hours, and is subjected to the catalytic reaction again, which is a first recycling test, and is repeated for 5 times, so that the recycling performance of the catalyst is inspected. The results are as follows:
first recycle test: 0.098g of APOA-1 was recovered from the previous experiment, and the scale of the experiment (referred to as reagent amount) was reduced by the same proportion as the catalyst, the reaction conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 93.4%, the selectivity of cyclohexanol was 95.0%, and the yield of cyclohexanol was 88.7%.
Second recycle test: 0.094g of APOA-1 was recovered from the previous experiment, and the scale of the experiment was scaled down accordingly, with the reaction conditions and parameters unchanged, the conversion of cyclohexyl acetate was 93.4%, the selectivity of cyclohexanol was 94.9%, and the yield of cyclohexanol was 88.6% due to the reduction in catalyst.
Third recycle test: 0.090g of APOA-1 is recovered from the previous test, and the test scale is proportionally reduced due to less catalyst, the reaction conditions and parameters are unchanged, the conversion rate of the cyclohexyl acetate is 93.5%, the selectivity of the cyclohexanol is 95.1%, and the yield of the cyclohexanol is 88.9%.
Fourth recycle test: 0.089g of APOA-1 was recovered from the previous experiment, and the scale of the experiment was reduced proportionally since the amount of catalyst was reduced, the reaction conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 92.6%, the selectivity of cyclohexanol was 95.3%, and the yield of cyclohexanol was 88.2%.
Fifth recycle test: 0.087g of APOA-1 was recovered from the previous test, the scale of the test was reduced proportionally with the catalyst reduced, the reaction conditions and parameters were unchanged, the conversion of cyclohexyl acetate was 90.8%, the selectivity of cyclohexanol was 95.4% and the yield of cyclohexanol was 86.6%.