阅读说明：本技术 一种两亲性有机多孔聚合物固体酸催化剂及其制备方法和应用 (Amphiphilic organic porous polymer solid acid catalyst and preparation method and application thereof ) 是由 雷以柱 陈再飞 万亚荔 王仁舒 李帅 于 2019-11-18 设计创作，主要内容包括：本发明涉及催化剂的制备技术领域,具体公开了一种两亲性有机多孔聚合物固体酸催化剂及其制备方法和应用。本发明采用4-乙烯基苯磺酸钠和(4-乙烯基苄基)三(4-乙烯基苯基)氯化膦为共聚单体,通过溶剂热自由基聚合法合成了苯磺酸钠功能化有机多孔聚合物载体；进一步与酸进行离子交换得到有机多孔聚合物固体酸催化剂。该有机多孔聚合物固体酸催化剂具有比表面积大、两亲性能优异、孔径分布宽、酸含量可调等优点。该催化剂在催化醋酸环己酯水解制备环己醇反应中,表现出了优异的催化性能和良好的循环使用性能,具有极大的应用潜力。(The invention relates to the technical field of catalyst preparation, and particularly discloses an amphiphilic organic porous polymer solid acid catalyst, and a preparation method and application thereof. The invention adopts 4-vinyl sodium benzenesulfonate and (4-vinylbenzyl) tri (4-vinylphenyl) phosphine chloride as comonomers, and synthesizes the sodium benzenesulfonate functionalized organic porous polymer carrier by a solvothermal free radical polymerization method; further carrying out ion exchange with acid to obtain the organic porous polymer solid acid catalyst. The organic porous polymer solid acid catalyst has the advantages of large specific surface area, excellent amphiphilic performance, wide pore size distribution, adjustable acid content and the like. The catalyst shows excellent catalytic performance and good recycling performance in the reaction of catalyzing the hydrolysis of the cyclohexyl acetate to prepare cyclohexanol, and has great application potential.)

1. An amphiphilic organic porous polymer solid acid catalyst is prepared by the following method:

(1) preparation of sodium benzenesulfonate functionalized organic porous polymer carrier

Dissolving 4-vinylbenzene sulfonic acid sodium salt and (4-vinylbenzyl) tri (4-vinylphenyl) phosphine chloride in an organic solvent according to a certain proportion, stirring for 2 hours, transferring the solution to a reaction kettle, adding a free radical initiator into the kettle, raising the temperature of the reaction kettle to 80-150 ℃ under the protection of nitrogen, reacting for 10-48 hours, and filtering, washing and vacuum drying the obtained product to obtain the sodium benzenesulfonate functionalized organic porous polymer carrier;

(2) ion exchange

Adding the sodium benzenesulfonate functionalized organic porous polymer carrier prepared in the step (1) into an acid aqueous solution, stirring for 12-24 hours, filtering, repeatedly exchanging for 2 times, washing the precipitate with water for 3-5 times, and vacuum drying to obtain an amphiphilic organic porous polymer solid acid catalyst;

the molar ratio of the sodium 4-vinylbenzene sulfonate to the (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride in the step (1) is 100: (100-20).

2. The catalyst according to claim 1, wherein the radical initiator in step (1) is azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and/or azobisisobutyramidine hydrochloride.

3. The catalyst according to claim 2, wherein the amount of the free radical initiator used in the step (1) is 1-5% of the total mass of the monomers of sodium 4-vinylbenzenesulfonate and (4-vinylbenzyl) tris (4-vinylphenyl) phosphonium chloride.

4. The catalyst according to claim 1, wherein the organic solvent for the polymerization reaction in step (1) isN,N-dimethylformamide,N,N-dimethylacetamide, dimethylsulfoxide and/or N-methyl-2-pyrrolidone.

5. The catalyst according to claim 1, wherein the solvent used for washing the precipitate in step (1) is methanol, ethanol and/or ethyl acetate.

6. The catalyst according to claim 1, wherein the acid in step (2) is sulfuric acid, nitric acid and/or hydrochloric acid; the concentration of the acid solution is 0.5-6 mol/L.

7. The application of the amphiphilic organic porous polymer solid acid catalyst of any one of claims 1 to 6 in hydrolysis reaction of cyclohexyl acetate.

8. The application of claim 7, wherein the specific steps of the application are as follows:

adding deionized water, cyclohexyl acetate and an organic porous polymer solid acid catalyst into a reaction bottle, sealing the reaction bottle, and then reacting for 2-8 hours at 100-140 ℃ under magnetic stirring. After the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography.

9. The application of the organic porous polymer solid acid catalyst as claimed in claim 8, wherein the amount of the organic porous polymer solid acid catalyst is 5-20% of the mass of the cyclohexyl acetate.

10. The use according to claim 9, wherein the mass ratio of cyclohexyl acetate to water is 1: (5-1).

Technical Field

The invention relates to the technical field of catalyst preparation, in particular to an amphiphilic organic porous polymer solid acid catalyst and a preparation method and application thereof.

Background

Liquid acids, such as sulfuric acid, hydrochloric acid, and the like, are widely used as acid catalysts in aqueous organic reactions such as hydrolysis, hydration, and the like. However, liquid acid has the problems of strong corrosivity, difficult recycling of the catalyst, difficult waste acid treatment and the like. Therefore, the development of a novel solid acid catalyst instead of the conventional liquid acid catalyst has received extensive attention from both academic and industrial fields.

Cyclohexanol is an important chemical intermediate and has wide application value in the aspects of producing nylon, caprolactam and the like. In the traditional process, for example, a production line for producing cyclohexanol by partially hydrogenating benzene to generate cyclohexene and then directly hydrating the cyclohexene is influenced by low solubility and low equilibrium conversion rate of the cyclohexene in water, and has the defects of high difficulty in directly hydrating the cyclohexene and low cyclohexanol yield. The process for preparing cyclohexanol by hydrolyzing cyclohexyl acetate adopts an indirect hydration route of firstly esterifying cyclohexene and then hydrolyzing the cyclohexene, and the route has high conversion rate and cyclohexanol yield. However, the hydrolysis reaction of cyclohexyl acetate is a water-organic two-phase reaction, and the catalytic reaction activity is influenced by the mass transfer of the two phases. When the traditional liquid acid catalysts such as sulfuric acid, benzenesulfonic acid and the like are used for hydrolysis reaction of cyclohexyl acetate, the catalysts are usually in a water phase or an oil phase due to poor oleophylic or hydrophilic properties, so that the activity is not high; while the traditional sulfonic acid resin solid acid catalyst is used for catalyzing the hydrolysis reaction of cyclohexyl acetate, the activity is low due to poor amphipathy. Therefore, the amphiphilic solid acid catalyst with excellent hydrophilicity and lipophilicity is developed, the contact area of the two-phase reaction is enlarged, the cyclohexyl acetate hydrolysis reaction is efficiently carried out, and the method has important significance for promoting the industrialization of an indirect hydration route.

The organic porous polymer is a novel porous material developed in recent years, has the characteristics of large specific surface area, adjustable pore diameter, high stability, various synthetic methods, easy functionalization and the like, and shows good application prospect in heterogeneous catalysis. However, most organic porous polymers are composed of an aromatic ring skeleton and thus have hydrophobicity. When the hydrophobic porous polymer catalyst is used in a water-organic two-phase reaction, the catalyst is not well dispersed in water, so that the catalytic activity is often very low. Currently, some organic porous polymer solid acid catalysts have been reported to be substantially hydrophobic, which greatly limits their use as solid acids in various aqueous phase acid-catalyzed reactions. Therefore, the preparation of organic porous polymer solid acid catalysts with good amphipathy, high activity and good recycling performance is still a challenge.

Disclosure of Invention

Aiming at the defects in the prior art, the inventor of the application adopts quaternary phosphonium salt and 4-vinyl sodium benzenesulfonate to carry out free radical copolymerization and further ion exchange to prepare the organic porous polymer solid acid catalyst with excellent hydrophilic and oleophilic properties, large specific surface area and wide pore size distribution range. The characteristics enable the prepared solid acid catalyst to have excellent catalytic activity in the hydrolysis reaction of cyclohexyl acetate, and the activity is higher than that of homogeneous and heterogeneous acid catalysts such as sulfuric acid, benzenesulfonic acid, Amberlyst 15 and the like. The work provides a high-efficiency catalyst for the hydrolysis reaction of the cyclohexyl acetate and provides important reference for developing a novel and high-efficiency aqueous phase organic reaction solid acid catalyst.

The invention aims to provide an amphiphilic organic porous polymer solid acid catalyst aiming at the problem of low activity of a catalyst for hydrolysis reaction of cyclohexyl acetate.

In order to achieve the purpose, the invention adopts the following technical scheme:

the specific surface area of the amphiphilic organic porous polymer solid acid catalyst is 89-460 m²The acid-resistant material has a hierarchical pore structure containing micropores, mesopores and macropores, the acid content is 2.6-3.8 mmol/g, and the preparation route is as follows:

the preparation method comprises the following steps:

1. preparation of sodium benzenesulfonate functionalized organic porous polymer carrier

Dissolving 4-vinylbenzene sulfonic acid sodium salt and (4-vinylbenzyl) tris (4-vinylphenyl) phosphine chloride in an organic solvent, stirring at room temperature for 2 hours, transferring the solution to a reaction kettle, adding a free radical initiator into the kettle, heating the reaction kettle to 80-150 ℃ under the protection of nitrogen, reacting for 10-48 hours, and filtering, washing and vacuum drying the obtained product to obtain the sodium benzenesulfonate functionalized organic porous polymer carrier.

Further, the sodium 4-vinylbenzene sulfonate: the molar ratio of (4-vinylbenzyl) tri (4-vinylphenyl) phosphine chloride is 100: (100 to 20), preferably 100: (50-20).

Further, the free radical initiator is azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide and/or azobisisobutyramidine hydrochloride, preferably azobisisobutyronitrile and/or azobisisoheptonitrile.

Furthermore, the amount of the free radical initiator is 1-5%, preferably 1-3% of the total mass of the monomers of the 4-vinylbenzene sulfonic acid sodium salt and the (4-vinylbenzyl) tris (4-vinylphenyl) phosphonium chloride.

Further, the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and/or N-methyl-2-pyrrolidone, preferably N, N-dimethylformamide, N-dimethylacetamide and/or N-methyl-2-pyrrolidone.

Further, the solvent used for washing is methanol, ethanol and/or ethyl acetate.

2. Ion exchange

And (2) adding the sodium benzenesulfonate functionalized organic porous polymer carrier prepared in the step (1) into an acid aqueous solution (the carrier is completely immersed), stirring at room temperature for 12-24 hours, filtering, repeatedly adding the sodium benzenesulfonate functionalized organic porous polymer carrier into the acid aqueous solution for exchange for 2 times, washing the precipitate with water for 3-5 times, and drying in vacuum to obtain the amphiphilic organic porous polymer solid acid catalyst.

Further, the acid is sulfuric acid, nitric acid and/or hydrochloric acid, preferably sulfuric acid and/or nitric acid.

Furthermore, the concentration of the acid water solution is 0.5-6 mol/L, and preferably 0.5-2 mol/L.

The invention also provides the application of the catalyst prepared by the method in the reaction of preparing cyclohexanol by hydrolyzing aqueous-phase cyclohexyl acetate, and the applied reaction formula is as follows:

the specific operation is as follows:

adding deionized water, cyclohexyl acetate and an organic porous polymer solid acid catalyst into a pressure-resistant glass reaction bottle, sealing the reaction bottle, and then reacting for 2-8 hours at 100-140 ℃ under stirring; after the reaction, the reaction product was extracted with ether and qualitatively and quantitatively analyzed by gas chromatography.

Further, the dosage of the organic porous polymer solid acid catalyst is 5-20% of the mass of the cyclohexyl acetate.

Further, the mass ratio of the cyclohexyl acetate to the water is 1: (5-1).

Compared with the prior art, the invention has the following advantages and beneficial effects:

the invention adopts 4-vinyl sodium benzenesulfonate and (4-vinylbenzyl) tri (4-vinylphenyl) phosphine chloride as comonomers, and synthesizes the sodium benzenesulfonate functionalized organic porous polymer by a solvothermal free radical polymerization method; further carrying out ion exchange with acid to obtain the organic porous polymer solid acid catalyst. The catalyst prepared by the invention has the characteristics of good amphiphilic property, large specific surface area, wide pore size distribution, high activity, easy recovery and good recycling performance. The characteristics enable the prepared organic porous polymer solid acid catalyst to show excellent catalytic activity in the hydrolysis reaction of cyclohexyl acetate, and the activity is higher than that of homogeneous and heterogeneous acid catalysts such as sulfuric acid, benzenesulfonic acid, Amberlyst 15 and the like.

Drawings

FIG. 1 is a graph showing the contact angle of APOA-1 prepared in example 1 with water.

FIG. 2 shows the contact angle of APOA-1 prepared in example 1 with cyclohexyl acetate.

FIG. 3 shows the solid nuclear magnetism of APOA-1 prepared in example 1¹³And (C) diagram.

FIG. 4 shows the solid nuclear magnetism of APOA-1 prepared in example 1³¹And (7) a P diagram.

FIG. 5 is a full X-ray photoelectron spectrum of the catalyst (APOA-1) prepared in example 1.

FIG. 6 is an X-ray photoelectron spectrum of S2p of the catalyst (APOA-1) prepared in example 1.

FIG. 7 is a field emission scanning electron microscope photograph of the catalyst prepared in example 1 (APOA-1).

FIG. 8 is a field emission transmission electron microscope photograph of the catalyst prepared in example 1 (APOA-1).

FIG. 9 is a graph showing a nitrogen desorption and pore size distribution of the catalyst (APOA-1) prepared in example 1.

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 procedures (j. mater. chem.a,2015,3, 23871). Contact angle measurements were made on a Dataphysics OCA20 contact angle measuring instrument. N is a radical of₂The gas wash desorption isotherm was performed on a Micrometrics ASAP 2020 instrument at 77K. Scanning electronMicroscopy 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 2000.¹³C and³¹p 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 magnetism¹³The 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 magnetism³¹The 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-SO₃H and HSO₄ ^-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 228m²Per g, pore volume of 0.55cm³·g^-1The 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 magnetism¹³The spectrum C of APOA-2 was characterized and analyzed, and 127.5 to 144.4ppm of APOA-2 was attributed to the aromatic ring carbon and 41ppm was attributed to the polymerized ethyleneCarbon atoms on the alkenyl group.

Using solid nuclear magnetism³¹The P spectrum is characterized and analyzed by APOA-2, 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-SO₃H and HSO₄Two 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 found to be 412m²Per g, pore volume of 0.73cm³·g^-1The pore diameter 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 nuclear magnetism¹³The spectrum C of APOA-3 was characterized and analyzed, and 127.5 to 144.5ppm of the aromatic ring carbon and 41ppm of the polymerized aromatic ring carbonCarbon atom of vinyl group.

Using solid nuclear magnetism³¹The P spectrum is characterized and analyzed by APOA-3, 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-SO₃H and HSO₄Two 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 139m²Per g, pore volume of 0.48cm³·g^-1The 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, to give the catalyst 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 magnetism¹³The spectrum C of APOA-4 is characterized and analyzed, 127.2-144.5ppm belong to the aromatic ring carbon, 41.5ppm belong to the polymerizationThe carbon atom of the vinyl group.

Using solid nuclear magnetism³¹The 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-SO₃H and HSO₄Two 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 89m²Per g, pore volume of 0.32cm³·g^-1The 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 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 determined by acid-base titration by using 1mol/LNaOH solution, and the acid content of APOA-5 is 3.47 mmol/g.

Using solid nuclear magnetism¹³The 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.

By means of a fastenerNuclear magnetic resonance of body³¹The 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-SO₃H and HSO₄Two forms are provided.

The morphology and the size of the 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 185m²Per g, pore volume of 0.51cm³·g^-1The 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 magnetism¹³The 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 nuclear magnetism³¹The P spectrum is characterized and analyzed on APOA-6, and the chemical shift of P is 21ppmIndicating that P has a chemical environment and is a quaternary phosphonium salt.

The result of the analysis of APOA-6 by an X-ray photoelectron spectrometer shows that C, P, S, O element exists and S has-SO₃H and HSO₄Two forms are provided.

The appearance 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 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-6 by using a specific surface area and pore size analyzer. The specific surface area of APOA-6 was found to be 216m²Per g, pore volume of 0.54cm³·g^-1The 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 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 magnetism¹³The 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 magnetism³¹The P spectrum is characterized and analyzed by APOA-7, 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-SO₃H and HSO₄Two 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 207m²Per g, pore volume of 0.53cm³·g^-1The 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 nuclear magnetism¹³The 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 magnetism³¹The P spectrum is characterized and analyzed by APOA-8, 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-8 by an X-ray photoelectron spectrometer shows C, P, SThe presence of an element O and S having-SO₃H and HSO₄Two 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 (3) carrying out specific surface area and pore size analysis on the APOA-8 by using a specific surface area and pore size analyzer. The specific surface area of APOA-8 was found to be 149m²Per g, pore volume of 0.47cm³·g^-1The 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 nuclear magnetism¹³The 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 magnetism³¹The P spectrum is characterized and analyzed by APOA-9, 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-9 by an X-ray photoelectron spectrometer shows that C, P, S, O, N element exists and S only has-SO₃The H form.

The appearance and the size of the 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 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-9 by using a specific surface area and pore size analyzer. The specific surface area of APOA-9 was found to be 236m²Per g, pore volume of 0.58cm³·g^-1The pore diameter 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 the same manner as in example 9 except that the nitric acid solution used was changed to a concentration of 0.5mol/L and the ion exchange time was changed to 12 hours, and the operation was otherwise exactly the same as in example 9, whereby the catalyst was obtained and was designated as APOA-10.

The APOA-10 thus prepared is characterized, 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 magnetism¹³The 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 nuclear magnetism³¹The P spectrum is characterized and analyzed on APOA-10, 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-SO₃The 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 (3) carrying out specific surface area and pore size analysis on the APOA-10 by using a specific surface area and pore size analyzer. The specific surface area of APOA-10 was found to be 242m²Per g, pore volume of 0.58cm³·g^-1The 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 percent, the selectivity of the cyclohexanol is 95.6 percent, and the yield of the cyclohexanol is 82.8 percent.

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 percent, the selectivity of the cyclohexanol is 95.7 percent, and the yield of the cyclohexanol is 81.7 percent.

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%.

5.6mg of benzenesulfonic acid (acid content, 0.357mmol) was substituted for 0.1g of APOA-1 (acid content, 0.357mmol), and the other 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%.

0.71mL of a 0.25mol/L sulfuric acid aqueous solution (acid content in terms of hydrogen ion, 0.357mmol) was substituted for 0.1g of an APOA-1 (acid content, 0.357mmol), and the remaining 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 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 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 the mixture was reacted for 8 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 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 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 90.8%, the selectivity of cyclohexanol was 95.4%, and the yield of cyclohexanol was 86.6%.