CN112246282A - Acidic porous polymer catalyst, and preparation method and application thereof - Google Patents
Acidic porous polymer catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112246282A CN112246282A CN202011223989.4A CN202011223989A CN112246282A CN 112246282 A CN112246282 A CN 112246282A CN 202011223989 A CN202011223989 A CN 202011223989A CN 112246282 A CN112246282 A CN 112246282A
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- Prior art keywords
- porous polymer
- polymer catalyst
- acidic porous
- acidic
- structural unit
- Prior art date
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses an acidic porous polymer catalyst, and a preparation method and application thereof. The acidic porous polymer catalyst is formed by polymerizing a styrene derivative structural unit, a vinyl ionic liquid structural unit and a divinylbenzene and/or 1, 5-hexadiene structural unit in a covalent bond form through a vinyl group, and has a structure comprising a reticular skeleton, rigid aryl side chains and flexible acidic ionic liquid arms. The preparation method of the oligomeric polyether compound provided by the invention does not need heating and pressurizing equipment, can synthesize a target product by reaction raw materials under the action of the acidic porous polymer catalyst prepared by the invention at normal temperature or under the condition of no pressurization at nearly normal temperature, can recycle the acidic porous polymer catalyst, and has the advantages of extremely low energy consumption, greatly reduced fixed investment and greatly improved safety in the preparation process of the oligomeric polyether compound.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, relates to an acidic porous polymer catalyst, a preparation method and an application thereof, and particularly relates to an acidic porous polymer catalyst for acetalization, a preparation method thereof, and a reaction for synthesizing an oligomeric polyether compound by using the acidic porous polymer catalyst.
Background
Oligomeric polyethers, e.g. polymethoxy dimethyl ether CH3O(CH2O)nCH3(n is more than or equal to 3 and less than or equal to 8, also called DMMn，PODEn) The diesel additive is a novel clean and environment-friendly diesel additive, and the physical and chemical properties of the diesel additive are very close to those of the traditional diesel, so that the diesel additive is mixed with the diesel for combustion, the combustion efficiency can be effectively improved, and the emission of soot is reduced. The polyoxymethylene dimethyl ethers and diesel oil have good concoction property, can be mutually soluble, and have self-lubricating property, can prolong the mechanical life of the diesel oil.
The polymethoxy dimethyl ether can also be used as a novel diesel oil substitute fuel. Patent documents such as US7235113B2 and EP1422285B1 propose that polyoxymethylene dimethyl ethers are used to completely replace diesel oil in percentage, and the polyoxymethylene dimethyl ethers are used as a novel alternative fuel to obtain the alternative fuel which can be directly used for an internal combustion engine by compounding acetals with different polymerization degrees in a certain proportion. When using DMM2-6When the fuel is used, the NOx emission is 1.2g/kwh when the engine speed is 500 rpm; the Particulate Matter (PM) emission amount is: 0.001 g/kwh; hydrocarbon compound (b): 0.3g/kwh, at a level below the Euro V standard (Euro V limit). The oligomeric polyether compound can be mixed with other components to obtain high-performance fuel. For example, in patent CN110117507A, polyoxymethylene dimethyl ether is blended with levulinic acid ester, and is blended with levulinic acid ester; for example, in patent CN108753384A, the oligomeric polyether compound is blended with diesel oil, and clean diesel oil with high cetane number can also be obtained.
For clean energy, the clean energy is often used by end users more cleanly, but additional energy, such as hydrogen energy, is consumed for producing and storing the clean energy; or to transfer the contaminants to a production stage, such as a battery. From the viewpoint of environmental friendliness and energy conservation, if the energy consumption or pollution in the process of producing clean energy is additionally increased (which is often the case in reality) in order to reduce the emission of fuel in the combustion process, the whole energy efficiency and cleanness are not necessarily required from the viewpoint of the whole life cycle of the energy. Similar problems exist for the production of oligomeric polyethers, and although there are many effective catalysts for polyoxymethylene dimethyl ethers and few catalysts for polyethoxy dimethyl ether have been reported, one problem in the current synthetic production of oligomeric polyethers is the need for heating and pressurizing equipment, e.g., reaction conditions (temperature 130 ℃, pressure 3.0 MPa). Heating means extra steam, electrical energy consumption, and pressurization means higher capital investment of equipment is required. How to synthesize the target product under the condition of normal temperature or nearly normal temperature without pressurization only by mixing and stirring raw materials for reaction is a breakthrough development no matter from the viewpoint of economy or green degree of energy utilization.
Disclosure of Invention
The invention mainly aims to provide an acidic porous polymer catalyst, and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an acidic porous polymer catalyst, which is formed by polymerizing a styrene derivative structural unit, a vinyl ionic liquid structural unit and a divinylbenzene and/or 1, 5-hexadiene structural unit in a covalent bond form through a vinyl group, and has a structure comprising a reticular framework, a rigid aryl side chain and a flexible acidic ionic liquid arm;
wherein, R is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any one of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBu;
the vinyl ionic liquid has a structure represented by any one of the following formulas:
wherein n is 1-16, X-Selected from CF3SO3 -、HSO4 -、Cl-And p-toluenesulfonic acid anion.
The embodiment of the invention also provides a preparation method of the acidic porous polymer catalyst, which comprises the following steps:
reacting a first mixed reaction system containing sultone, N-vinyl imidazole and/or vinyl pyridine and a first solvent at 25-100 ℃ for 3-72 hours to prepare a first intermediate product;
under a protective atmosphere, carrying out polymerization reaction on a second mixed reaction system containing the obtained first intermediate product, a styrene derivative, divinylbenzene and/or 1, 5-hexadiene, sodium dodecyl sulfate, tween 80, sodium bicarbonate, an initiator and a second solvent at 50-100 ℃ for 3-48 h to obtain a second intermediate product;
and mixing the obtained second intermediate product with an acid solution, and carrying out acidification treatment at 25-80 ℃ for 1-72 h to obtain the acidic porous polymer catalyst.
The embodiment of the invention also provides the acidic porous polymer catalyst prepared by the method.
The embodiment of the invention also provides application of the acidic porous polymer catalyst in preparation of oligomeric polyether compounds.
The embodiment of the invention also provides a preparation method of the oligomeric polyether compound, which comprises the following steps:
providing the aforementioned acidic porous polymer catalyst;
and mixing trioxymethylene and formal compounds with the acidic porous polymer catalyst, and reacting at room temperature to obtain the oligomeric polyether compounds.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method of the oligomeric polyether compound, heating and pressurizing equipment is not needed, the target product can be synthesized by reaction raw materials under the action of the acidic porous polymer catalyst prepared by the invention at normal temperature or under the condition of no pressurization at near normal temperature, and meanwhile, the preparation method of the oligomeric polyether compound has the advantages of extremely low energy consumption, greatly reduced fixed investment and greatly improved safety; the acidic porous polymer catalyst is linked by covalent bonds, has stable chemical properties and can be recycled; the catalyst is rich in porous structure and is favorable for reaction. The catalyst has simple preparation method, high atom economy and less pollution.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the structure of an acidic porous polymer catalyst in an exemplary embodiment of the present invention;
FIG. 2 is an infrared characterization of the acidic porous polymer catalyst prepared in example 3 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An aspect of an embodiment of the present invention provides an acidic porous polymer catalyst formed by polymerizing a styrene derivative structural unit, a vinyl ionic liquid structural unit, and a divinylbenzene and/or 1, 5-hexadiene structural unit through a vinyl group in a covalent bond form, the acidic porous polymer catalyst having a structure comprising a network skeleton, rigid aryl side chains, and flexible acidic ionic liquid arms;
the styrene derivative has a structure represented by any one of the following formulae:
wherein, R is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any one of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBu;
the vinyl ionic liquid has a structure represented by any one of the following formulas:
wherein n is 1-16, X-Selected from CF3SO3 -、HSO4 -、Cl-And p-toluenesulfonic acid anion.
Further, the acidic porous polymer catalyst consists of C, H, O, N, S elements.
Further, the aperture of the acidic porous polymer catalyst is 1-220nm, and the specific surface area is 11-116 m2/g。
Furthermore, the molar ratio of the structural unit of the styrene derivative in the acidic porous polymer catalyst to the structural unit of the ionic liquid is 0.1: 1-80: 1.
Further, the molar ratio of the structural unit of the styrene derivative to the structural unit of the divinylbenzene and/or the 1, 5-hexadiene in the acidic porous polymer catalyst is 5:1 to 200: 1.
The acidic porous polymer catalyst consists of C, H, O, N, S elements, and the structure of the acidic porous polymer catalyst consists of a net-shaped framework, rigid aryl side chains and flexible acidic ionic liquid arms. Specifically, the structure of the acidic porous polymer catalyst is schematically shown in FIG. 1, and A, B, C structural units are polymerized in a covalent bond form through vinyl. The structure of A can have one or more substituent groups, and the R group is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any one of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBu; in the structure B, n is 1-16, X-Selected from CF3SO3 -、HSO4 -、Cl-Or p-toluenesulfonate anion; c is divinylbenzene or 1, 5-hexadiene. In the acidic porous polymer catalyst, the structural ratio (molar ratio) of A to B is 0.1: 1-80: 1, and the structural ratio of A to C is 5: 1-200: 1.
Another aspect of an embodiment of the present invention also provides a method for preparing an acidic porous polymer catalyst, including:
reacting a first mixed reaction system containing sultone, N-vinyl imidazole and/or vinyl pyridine and a first solvent at 25-100 ℃ for 3-72 hours to prepare a first intermediate product;
under a protective atmosphere, carrying out a polymerization reaction for 3-48 h at 50-100 ℃ on a second mixed reaction system containing the obtained first intermediate product, a styrene derivative, divinylbenzene and/or 1, 5-hexadiene, sodium dodecyl sulfate and/or Tween 80, sodium bicarbonate, an initiator and a second solvent to obtain a second intermediate product;
and mixing the obtained second intermediate product with an acid solution, and carrying out acidification treatment at 25-80 ℃ for 1-72 h to obtain the acidic porous polymer catalyst.
In some more specific embodiments, the sultone is selected from sultones having 2 to 16 carbon atoms, preferably 1, 4-butanesultone.
Further, sodium lauryl sulfate, tween 80 may be replaced by emulsifiers with similar functions, such as block polymers F123, P123, e.g. cetyl trimethylammonium bromide CTAB.
Furthermore, the mol ratio of the sultone to the N-vinyl imidazole and/or vinyl pyridine is 1: 0.8-1: 1.2, preferably 1:1.
Further, the preparation method further comprises the following steps: and after the reaction of the first mixed reaction system is finished, washing, distilling and drying the obtained solid.
Further, the first solvent includes toluene or xylene, and is not limited thereto.
In some more specific embodiments, the preparation method comprises: respectively pretreating styrene derivatives, divinylbenzene and/or 1, 5-hexadiene, mixing and emulsifying the pretreated styrene derivatives, divinylbenzene and/or 1, 5-hexadiene with the first intermediate product, sodium dodecyl sulfate and/or Tween 80, sodium bicarbonate and a second solvent, heating the obtained mixture to 50-100 ℃, adding an initiator into the mixture to form a second mixed reaction system, and carrying out polymerization reaction.
Further, the molar ratio of the pretreated styrene derivative to the divinylbenzene is 5: 1-200: 1.
Further, the molar ratio of the pretreated styrene derivative to the first intermediate product is 10: 1-1: 80.
Further, the dosage of the sodium dodecyl sulfate and/or the tween 80 is 0.1-10 wt% of the second mixed reaction system.
Further, the amount of the sodium bicarbonate is 0.1-15 wt% of the second mixed reaction system.
Further, the preprocessing comprises: respectively mixing and stirring the aqueous alkali with a p-styrene derivative and divinyl benzene for 0.1-3 h, then separating an organic phase, then mixing and stirring the aqueous alkali with the aqueous alkali for 0.1-3 h, separating the organic phase, and drying to obtain the pretreated p-styrene derivative, divinyl benzene and/or 1, 5-hexadiene.
Further, the alkali solution includes a sodium hydroxide solution, and is not limited thereto.
Further, the concentration of the sodium hydroxide solution is 0.5-15 wt%.
Further, the styrene derivative has a structure represented by any one of the following formulae:
wherein, R is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBuAnd are intended to be, without being limited thereto.
Further, the protective atmosphere comprises an inert gas atmosphere and/or a nitrogen atmosphere, preferably a nitrogen atmosphere.
Further, the initiator includes any one or a combination of two or more of potassium persulfate, ammonium persulfate, sodium persulfate, and azoisobutyronitrile, and is not limited thereto.
Further, the second solvent includes any one or a combination of two or more of water, ethanol, methanol, and butanol, and is not limited thereto.
Further, the preparation method further comprises the following steps: and after the reaction of the second mixed reaction system is finished, filtering, washing and drying the obtained mixture.
In some more specific embodiments, the preparation method further comprises: and after the acidification treatment is finished, separating, washing and drying the obtained solid.
Further, the drying treatment manner includes vacuum drying and/or freeze drying, and is not limited thereto.
Further, the acid solution includes any one or a combination of two or more of a sulfuric acid solution, a trifluoromethanesulfonic acid solution, a hydrochloric acid solution, and a p-toluenesulfonic acid solution, and is not limited thereto.
Further, the concentration of the acid solution is 0.5-20 wt%.
In some more specific embodiments, the method for preparing the acidic porous polymer catalyst comprises:
step (1): adding sultone and N-vinyl imidazole or vinyl pyridine into a solvent, stirring and reacting for 3-72 h at 25-100 ℃, washing the generated solid with the solvent, carrying out reduced pressure distillation, recovering the solvent, and drying the obtained solid, wherein the mark is W.
Preferably, in the step (1), the sultone is a sultone having 2 to 16 carbon atoms, and preferably 1, 4-butanesultone.
Preferably, the ratio of the sultone to the N-vinylimidazole or vinylpyridine in step (1) is 1: 0.8-1: 1.2, preferably 1:1.
Preferably, the solvent in step (1) is preferably toluene or xylene.
Preferably, the drying method in the step (1) is vacuum drying, and the drying temperature is 60-150 DEG C
Step (2): mixing the component A in the catalyst structure (shown in figure 1) with sodium hydroxide solution, stirring at normal temperature for a certain time, taking the organic liquid phase layer, mixing with the sodium hydroxide solution again, stirring for a certain time, separating the organic liquid phase layer, and drying. The C component of the catalyst structure (see fig. 1) was also treated as such. Adding the processed component A and component C, the W in the step 1, Sodium Dodecyl Sulfate (SDS), tween 80, sodium bicarbonate and a reaction solvent into a reaction vessel, replacing the reaction vessel with inert gas, heating to 50-100 ℃, adding an initiator, carrying out polymerization reaction for 3-48 hours under the stirring condition, removing the solvent, washing to remove impurities, and drying to obtain the solid P.
Preferably, the concentration of the sodium hydroxide solution in the step (2) is preferably 0.5-15%, and the stirring time is 0.1-3 h.
Preferably, the reaction solvent in the step (2) is water, ethanol, methanol, butanol, or a mixed solution, and the inert gas is preferably nitrogen gas.
Preferably, in the step (2), the initiator is preferably potassium persulfate, ammonium persulfate, sodium persulfate or azoisobutyronitrile.
And (3): and (4) acidifying the solid P. And adding the solid P into an acid solution, stirring for a certain time at 25-80 ℃, separating, washing and drying the solid to obtain the light acidic porous polymer catalyst LICP-V.
Preferably, in the step (3), the acid solution is preferably sulfuric acid, the concentration of the sulfuric acid is preferably 0.5-20%, and the stirring time is 1-72 h. The drying method is preferably vacuum drying or freeze drying.
Another aspect of an embodiment of the present invention also provides an acidic porous polymer catalyst prepared by the foregoing method.
Go toThe aperture of the acidic porous polymer catalyst is 1-220nm, and the specific surface area is 11-116 m2/g。
In another aspect of the embodiments of the present invention, there is also provided a use of the acidic porous polymer catalyst in preparation of oligomeric polyether compounds.
The embodiment of the invention also provides a preparation method of the oligomeric polyether compound, which comprises the following steps:
providing the aforementioned acidic porous polymer catalyst;
trioxymethylene and formal compounds are mixed with the acidic porous polymer catalyst and react at normal temperature and normal pressure or near normal temperature and normal pressure to prepare oligomeric polyether compounds.
Further, the formal compound includes any one or a combination of two or more of dimethoxymethane, diethoxymethane, dipropoxymethane, and dibutoxymethane, and is not limited thereto.
Further, the molar ratio of the trioxymethylene to the formal compound is 0.7: 1-4: 1.
Further, the reaction time of the reaction is 0.1-100 h.
Further, the oligomeric polyether compound DXMnIncluding any one or a combination of two or more of polyoxymethylene dimethyl ether, polyoxymethylene diethyl ether, polyoxymethylene dipropyl ether and polyoxymethylene dibutyl ether, but not limited thereto.
In the preparation process of the oligomeric polyether compound, a liquid product is taken for chromatographic analysis, and the conversion rate and selectivity calculation mode is as follows:
conversion rate: cTOXPercent reacted trioxymethylene/added trioxymethylene 100%;
and (3) selectivity: sDXM2-8% DXM in product2-8Amount of substance (v)/amount of total substance of the product + 100%;
the technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
Example 1
(1) Adding 1, 4-butanesultone or 1, 3-propanesultone and N-vinyl imidazole or vinyl pyridine into a xylene solvent according to a molar ratio of 1:0.8, or 1:1, or 1:1.2 or within a range (which means a range formed by the endpoints, and the same is not repeated below), reacting for 72 hours, or 48 hours, or 24 hours, or 12 hours, or 3 hours or a certain time duration within the range under stirring at 25 ℃, or 40 ℃, or 60 ℃, or 80 ℃, or 100 ℃, or a certain temperature within the range, cooling, washing the generated solid for three times by using the xylene solvent, distilling under reduced pressure, recovering the solvent, and carrying out vacuum drying on the obtained solid at 60-150 ℃ to obtain solid powder W2;
(2) the component A in the catalyst structure (as shown in figure 1) is mixed with sodium hydroxide aqueous solution with the concentration of 0.5%, or 1%, or 5%, or 10%, or 15%, or a certain concentration in the interval, stirred for 3 hours, or 2 hours, or 1 hour, or 0.5 hour, or 0.1 hour, or a certain time period in the interval at normal temperature, taken out of an organic liquid phase layer, and treated with the sodium hydroxide solution again. The C component of the catalyst structure (as in figure 1) was also treated as such.
The above-treated a component, C component, solid powder W2 in step 1, Sodium Dodecyl Sulfate (SDS), tween 80, sodium bicarbonate and reaction solvent were added to a glass flask. The component A can have one, two or three substituent groups, and the R group is-H or- (CH)2)nCH3or-OH or-SO3H. or-COOH or-Cl or-Br or diphenylphosphine-PPh2Or di-tert-butylphosphine-PtBu2Or phenylpyridylphosphine-PPhPy or phenyl tert-butylphosphine-PPhtBu; the C component can be p-or m-divinylbenzene, or 1, 5-hexadiene. The feeding molar ratio of A to C is 51, or 10:1 or 100:1, or 200:1, or a certain ratio within the interval; the molar ratio of the A to the W2 is 10:1, or 5:1, or 1:5, or 1:10, or 1:80, or a value within the interval; the feeding amount of the Sodium Dodecyl Sulfate (SDS) and the Tween 80 is 0.1 percent, or 1 percent, or 10 percent of the mass of the solution, or a certain value in the intervals; the feeding amount of the sodium bicarbonate is 0.1 percent, or 1 percent, or 15 percent of the mass of the solution, or a certain value in the intervals; the solvent is water, ethanol, methanol, butanol, or their mixture. Replacing the reaction vessel with nitrogen, heating to 50 ℃, or 60 ℃, or 70 ℃, or 80 ℃, or 100 ℃, or a certain temperature in the interval, adding an initiator potassium persulfate, or ammonium persulfate, or sodium persulfate, or azoisobutyronitrile, carrying out a polymerization reaction for 48 hours, or 36 hours, or 24 hours, or 12 hours, or 3 hours, or a certain time in the interval under the stirring condition, cooling to obtain a product, removing the solvent, washing to remove impurities, and drying to obtain the solid P2.
(3) Acidifying the solid P2, adding the solid P2 into 0.5%, or 5%, or 10%, or 15%, or 20% trifluoromethanesulfonic acid, or sulfuric acid, or hydrochloric acid, or P-toluenesulfonic acid solution, stirring at 25 ℃, or 40 ℃, or 60 ℃, or 80 ℃, or a certain temperature in the interval for 72h, or 48h, or 24h, or 1h, or a certain time in the interval, separating, washing and drying the solid to obtain the light acidic porous polymer catalyst.
Example 2
(1) 1, 4-Butanesulfonate lactone and N-vinyl imidazole are added into a toluene solvent in a molar ratio of 1:1, then the mixture is reacted for 12 hours at 80 ℃ under the condition of mechanical stirring at 500rpm, the temperature is reduced by cooling, the generated solid is washed three times by the toluene solvent and is evaporated in a rotary manner under reduced pressure, and the obtained solid is dried in vacuum (0.1atm) at 80 ℃ to obtain a solid powder of 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer (first intermediate product). The nuclear magnetism of the monomer is characterized and found that the hydrogen spectrum is1H NMR(400MHz,D2O)δ7.72(d,J＝1.9Hz,1H),7.54(d,J＝1.9Hz,1H),7.07(dd,J＝15.6,8.7Hz,1H),5.73(dd,J＝15.6,2.7Hz,1H),5.36(dd,J＝8.7,2.7Hz,1H),4.23(t,J ═ 7.1Hz,1H),2.99(m,1H),1.99(m,1H),1.70(m,1H) carbon spectrum13C NMR(101MHz,D2O)δ134.45(s),128.20(s),122.76(s),119.54(s),109.27(s),49.98(s),49.25(s),27.91(s),20.87(s)；
(2) Adding divinylbenzene and styrene which are treated and dried by 5 wt% of sodium hydroxide aqueous solution at normal temperature for 0.5h, 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer, sodium dodecyl sulfate, Tween 80 and sodium bicarbonate into the aqueous solution for mixing, wherein the feeding molar ratio of the styrene to the imidazolium salt monomer is 4:1, the feeding molar ratio of the styrene to the divinylbenzene is 8:1, the feeding amounts of Sodium Dodecyl Sulfate (SDS) and tween 80 are respectively 2 percent of the mass of the solution, the feeding amount of sodium bicarbonate is 1 percent of the mass of the solution, after the reaction bottle is replaced by nitrogen, stirring rapidly for 12h with mechanical stirring, emulsifying completely, heating to 70 deg.C, adding 0.5 wt% potassium persulfate to initiate polymerization, after reacting for 12h under stirring, cooling, washing and drying the product to obtain a solid product.
(3) And (3) adding the solid product obtained in the step (2) into a cyclohexane sulfate solution with the concentration of 5 wt%, stirring and acidifying at 60 ℃ for 24h, cooling to obtain a white solid, washing with ethanol and ethyl acetate ethanol, and vacuum-drying at 60 ℃ for 12h to obtain the light acidic porous polymer catalyst. Through N2Adsorption and desorption tests show that the pore range is 1-50nm, the average pore diameter is 28nm, and the BET specific surface area is 12m2/g。
Example 3
(1) Adding 1, 4-butanesultone and N-vinyl imidazole into a toluene solvent according to a molar ratio of 0.9:1, reacting at 70 ℃ at a speed of mechanically stirring 300rpm for 24 hours, cooling, washing, rotary steaming and drying the generated solid to obtain an imidazolium salt monomer solid (a first intermediate product).
(2) Divinylbenzene and styrene which are treated by 5 weight percent of sodium hydroxide aqueous solution at normal temperature for 1 hour, 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer, sodium dodecyl sulfate, Tween 80 and sodium bicarbonate are added into the aqueous solution to be mixed, wherein the feeding molar ratio of the styrene to the imidazolium salt monomer is 4:1, the feeding molar ratio of the styrene to the divinylbenzene is 16:1, the feeding amount of Sodium Dodecyl Sulfate (SDS) is 5 percent of the mass of the solution, the feeding amount of sodium bicarbonate is 2 percent of the mass of the solution, after replacing the reaction bottle with nitrogen, stirring rapidly for 12h with mechanical stirring, emulsifying completely, heating to 80 deg.C, adding 0.5 wt% potassium persulfate to initiate polymerization, after reacting for 24h under stirring, cooling, washing and drying the product to obtain a solid product.
(3) Adding the solid product obtained in the step (2) into 10 wt% cyclohexane sulfate solution, stirring and acidifying at 80 ℃ for 12h, cooling to obtain white solid, washing with ethanol and ethyl acetate ethanol, vacuum drying at 50 ℃ for 24h to obtain light acidic porous polymer catalyst, and performing N-phase separation on the light acidic porous polymer catalyst2Adsorption and desorption tests show that the pore range is 1-60nm, the average pore diameter is 29nm, and the BET specific surface area is 11m2(ii) in terms of/g. The infrared spectrum of the acidic polymer catalyst is shown in FIG. 2.
Example 4
(1) 1, 4-butyl sultone and N-vinyl imidazole are added into a xylene solvent in a molar ratio of 1:0.8, the mixture is reacted for 3 hours at 100 ℃ under the speed of mechanical stirring and 500rpm, the temperature is reduced by cooling, the generated solid is washed three times by the xylene solvent and is reduced by pressure rotary evaporation, and the obtained solid is dried in vacuum (0.1atm) at 80 ℃ to obtain a solid powder of 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer (first intermediate product).
(2) Divinylbenzene, styrene, p-chlorostyrene, 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer, 1, 5-hexadiene, sodium dodecyl sulfate and sodium bicarbonate which are treated by 1 wt% of sodium hydroxide aqueous solution at normal temperature for 1 hour are added into the aqueous solution and mixed, wherein the feeding molar ratio of the styrene to the imidazolium salt monomer is 10:1, the feeding molar ratio of the styrene to the divinylbenzene is 200:1, the feeding molar ratio of the styrene to the p-chlorostyrene is 20:1, the feeding molar ratio of the divinylbenzene to the 1, 5-hexadiene is 5:1, the feeding amount of the Sodium Dodecyl Sulfate (SDS) is 10% of the mass of the solution, and the feeding amount of the sodium bicarbonate is 15% of the mass of the solution. Replacing a reaction bottle with nitrogen, quickly stirring for 12h by mechanical stirring, fully emulsifying, heating to 100 ℃, adding 0.25 wt% of ammonium persulfate to initiate polymerization, reacting for 3h under a stirring state, cooling, and washing and drying a product to obtain a solid product.
(3) And (3) adding the solid product obtained in the step (2) into 0.5 wt% cyclohexane trifluoromethanesulfonate, stirring and acidifying at 60 ℃ for 24 hours, paying attention to safety during acidification, possibly splashing strong acid liquid, operating in a fume hood, recycling or properly treating waste liquid, cooling to obtain white solid, sequentially washing with ethanol and ethyl acetate, and vacuum-drying at 60 ℃ for 72 hours to obtain the light acidic porous polymer catalyst. Through N2Adsorption and desorption experiment tests show that the pore range is 1-220nm, the average pore diameter is 35nm, and the BET specific surface area is 28m2/g。
Example 5
(1) 1, 3-propane sultone and N-vinylpyridine are added into xylene solvent in a molar ratio of 1:1.2, and reacted for 72 hours at 25 ℃ under the speed of mechanical stirring at 800rpm, and then cooled, and the resulting solid is washed three times with xylene solvent and rotary evaporated under reduced pressure, and the obtained solid is vacuum-dried (0.1atm) at 150 ℃ to obtain solid powder of pyridinium salt monomer (first intermediate).
(2) Divinyl benzene and styrene, ethyl styrene, 6-vinyl-2-naphthol after being treated by 0.1 wt% of sodium hydroxide aqueous solution at normal temperature for 3 hours are added into the aqueous solution and mixed with sodium vinylbenzene sulfonate, pyridinium salt monomer, hexadecyl trimethyl ammonium bromide and sodium bicarbonate, wherein the feeding ratio of the styrene to the pyridinium salt monomer is 1:80, the feeding molar ratio of the styrene to the divinyl benzene is 5:1, the feeding molar ratio of the styrene to the sodium vinylbenzene sulfonate is 10:1, the feeding molar ratio of the styrene to the 6-vinyl-2-naphthol is 5:1, the feeding molar ratio of the styrene to the ethyl styrene is 5:1, the feeding amount of the hexadecyl trimethyl ammonium bromide) is 0.1% of the mass of the solution, and the amount of the sodium bicarbonate is 0.1% of the mass of the solution. Replacing the reaction bottle with nitrogen, rapidly stirring for 6h by mechanical stirring, heating to 50 ℃, adding 1 wt% of sodium persulfate to initiate polymerization, reacting for 48h under a stirring state, cooling, and washing and drying the product to obtain a solid product.
(3) And (3) adding the solid product obtained in the step (2) into a hydrochloric acid solution with the concentration of 20 wt%, stirring and acidifying at 25 ℃ for 72h, cooling the obtained solid, washing, and freeze-drying to obtain the acid polymer catalyst. Through N2Adsorption and desorption experiment tests show that the pore range is 1-45nm, the average pore diameter is 22nm, and the BET specific surface area is 97m2/g。
Example 6
(1) Adding 1, 4-butyl sultone and N-vinyl imidazole into a xylene solvent according to a molar ratio of 1:0.8, reacting for 3h at 100 ℃ under the speed of mechanically stirring 500rpm, cooling, washing the generated solid with the xylene solvent for three times, carrying out reduced pressure rotary evaporation, and carrying out vacuum drying on the obtained solid at 80 ℃ to obtain a solid powder of 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer (first intermediate product).
(2) After a 15 wt% sodium hydroxide aqueous solution is treated at normal temperature for 0.1h, fully removing water and deoxidized divinylbenzene and styrene, adding 1-vinyl-3- (4-butyl sulfonate) imidazolium salt monomer, 2-hydroxy-4-vinylbenzaldehyde, 1, 5-hexadiene, tween 80 and sodium bicarbonate into a tetrahydrofuran solution, and mixing, wherein the feeding molar ratio of the styrene to the imidazolium salt monomer is 10:3, the feeding molar ratio of the styrene to the divinylbenzene is 50:1, the feeding molar ratio of the styrene to the p-2-hydroxy-4-vinylbenzaldehyde is 5:1, the feeding molar ratio of the divinylbenzene to the 1, 5-hexadiene is 10:1, the feeding amount of the tween 80 is 5% of the mass of the solution, and the feeding amount of the sodium bicarbonate is 0.1% of the mass of the solution. Fully degassing a reaction system, replacing with helium, quickly stirring for 12 hours by mechanical stirring, fully emulsifying, heating to 60 ℃, adding 0.5 wt% of azoisobutyronitrile and 1 wt% of isobutyronitrile dithiobenzoate, reacting for 24 hours, adding 0.25% of ammonium persulfate, heating to 80 ℃, continuing to react for 24 hours, and cooling. The product was washed with methanol and dried to give a solid product.
(3) And (3) adding the solid product obtained in the step (2) into a cyclohexane p-toluenesulfonate solution with the concentration of 0.5 wt%, stirring and acidifying at 60 ℃ for 24 hours, and then cooling, washing and drying to obtain the porous acidic polymer with the function of expanding the ligand. Through N2Adsorption and desorption tests show that the pore range is 1-60nm, the average pore diameter is 29nm, and the BET specific surface area is 116m2/g。
Example 7
(1) P-bromostyrene and lithium diphenylphosphine react in an ice bath to remove redundant lithium salt, so that the vinyl triphenylphosphine is obtained.
(2) After 5 wt% of sodium hydroxide aqueous solution is processed for 1 hour at normal temperature, divinylbenzene, styrene, vinyl triphenylphosphine, 1, 5-hexadiene and a block polymer F123 which are fully dewatered and deoxidized are added into tetrahydrofuran solution to be mixed, wherein the feeding ratio (molar ratio) of styrene to an imidazolium salt monomer is 5:1, the feeding molar ratio of styrene to divinylbenzene is 50:1, the feeding molar ratio of styrene to vinyl triphenylphosphine is 5:1, the feeding molar ratio of divinylbenzene to 1, 5-hexadiene is 10:1, the feeding amount of F123 is 5 percent of the mass of the solution, a reaction system is fully degassed and replaced by helium, the mixture is heated to 60 ℃, 0.5 wt% of azoisobutyronitrile and 1 wt% of isobutyl dithiocarbamate are added, after stirring reaction is carried out for 24 hours, 0.5 wt% of ammonium persulfate is added, the temperature is raised to 80 ℃, the mixture is continuously reacted for 24 hours and then cooled, the product was washed with methanol and dried to give a solid product.
(3) And (3) adding the solid product obtained in the step (2) into a cyclohexane p-toluenesulfonate solution with the concentration of 5 wt%, stirring and acidifying at 60 ℃ for 24 hours, and then cooling, washing and drying to obtain the porous acidic polymer with the ligand expanding function.
Example 8
The light acidic porous polymer catalyst prepared in example 2 was used for the reaction of trioxymethylene with diethoxymethane DEM. 10kg of diethoxymethane and 5kg of trioxymethylene were charged into a glass reactor, and simultaneously, 750g of an acidic porous polymer catalyst was added thereto, and after stirring at room temperature of 25 ℃ for one day (24 hours), the product was taken out and analyzed by chromatography.
About 0.5g of a sample was taken, and an ethyl acetate solvent and tetrahydrofuran were added as internal standards, followed by detection with a FID detector. The conversion and selectivity of the reaction were calculated as follows:
conversion rate CTOXReacted trioxymethylene/added trioxymethylene%Aldehyde X100%
Selectivity SDXM2-8% DXM in product2-8Amount of substance (s)/amount of total substance(s) of the product X100%
The detection shows that the conversion rate is CTOX％＝88％，DEM2-8Selectivity is SDEM2-8％＝99％。
Example 9
The diethoxymethane DMM was used in place of diethoxymethane and stirred at 30 ℃ for one day (24 hours) according to the method in example 8, and the product was chromatographically analyzed to find conversion rate CTOX％＝89％，DMM2-8Selectivity is SDMM2-8％＝99％。
Example 10
After stirring at room temperature for one day (24 hours) using the acidic porous polymer catalyst prepared in example 3, Dipropoxymethane (DPM) was used in place of diethoxymethane according to the method in example 8, the product was taken out and analyzed by chromatography. The detection shows that the conversion rate is CTOX％＝91％，DPM2-8Selectivity is SDPM2-8％＝98％。
Example 11
Following the procedure described in example 8, dibutoxymethane DBM was used instead of diethoxymethane, and after stirring at 25 ℃ for 100h, the product was chromatographed. The detection shows that the conversion rate is CTOX％＝92％，DBM2-8Selectivity is SDBM2-8％＝98％。
Example 12
After stirring at 60 ℃ for 0.1h according to the method in example 8 using the acidic porous polymer catalyst prepared in example 3, the product was chromatographed. Through detection, the conversion rate is C when the ratio of diethoxymethane to trioxymethylene is 0.7:1TOX％＝29％，DEM2-8Selectivity is SDEM2-8％＝97％。
Example 13
The acidic porous polymer catalyst prepared in example 4 was used according to the method of example 8, and stirred at 25 deg.CAfter 100h, the product was chromatographed. The detection shows that the conversion rate is CTOX％＝91％，DEM2-8Selectivity is SDEM2-8％＝99％。
Example 14
The acidic porous polymer catalyst prepared in example 5 was used in the same manner as in example 8, and after stirring at 50 ℃ for 1 hour, the product was chromatographed. The detection shows that the conversion rate is CTOX％＝90％，DEM2-8Selectivity is SDPM2-8Percent is 99%. The ratio of the raw material diethoxymethane to trioxymethylene is changed to 4:1, the conversion rate is still very high, CTOX92% selectivity SDEM2-8％＝99％
Example 15
The product was chromatographed as in example 8, with temperature change, after stirring at 40 ℃ for 2 h. The detection shows that the conversion rate is CTOX％＝90％，DEM2-8Selectivity is SDEM2-8％＝99％。
After the reaction, the catalyst still keeps good performance after being recycled for 10 times, and the conversion rate is CTOX％＝90％，DEM2-8Selectivity is SDEM2-8Percent is 99%. The catalyst has good stability, is convenient to recycle, and can effectively reduce pollution and reduce cost.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. An acidic porous polymer catalyst characterized by: the acidic porous polymer catalyst is formed by polymerizing a styrene derivative structural unit, a vinyl ionic liquid structural unit and a divinylbenzene and/or 1, 5-hexadiene structural unit in a covalent bond form through a vinyl group, and has a structure comprising a reticular skeleton, rigid aryl side chains and flexible acidic ionic liquid arms;
the styrene derivative has a structure represented by any one of the following formulae:
wherein, R is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any one of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBu;
the vinyl ionic liquid has a structure represented by any one of the following formulas:
wherein n is 1-16, X-Selected from CF3SO3 -、HSO4 -、Cl-And p-toluenesulfonic acid anion.
2. The acidic porous polymer catalyst according to claim 1, characterized in that: the acidic porous polymer catalyst consists of C, H, O, N, S elements;
and/or the aperture of the acidic porous polymer catalyst is 1-220nm, and the specific surface area is 11-116 m2/g；
And/or the molar ratio of the structural unit of the styrene derivative to the structural unit of the ionic liquid in the acidic porous polymer catalyst is 0.1: 1-80: 1;
and/or the molar ratio of the structural unit of the styrene derivative to the structural unit of the divinylbenzene and/or the 1, 5-hexadiene in the acidic porous polymer catalyst is 5:1 to 200: 1.
3. A method for preparing an acidic porous polymer catalyst, comprising:
reacting a first mixed reaction system containing sultone, N-vinyl imidazole and/or vinyl pyridine and a first solvent at 25-100 ℃ for 3-72 hours to prepare a first intermediate product;
under a protective atmosphere, carrying out a polymerization reaction for 3-48 h at 50-100 ℃ on a second mixed reaction system containing the obtained first intermediate product, a styrene derivative, divinylbenzene and/or 1, 5-hexadiene, sodium dodecyl sulfate and/or Tween 80, sodium bicarbonate, an initiator and a second solvent to obtain a second intermediate product;
and mixing the obtained second intermediate product with an acid solution, and carrying out acidification treatment at 25-80 ℃ for 1-72 h to obtain the acidic porous polymer catalyst.
4. The production method according to claim 3, characterized in that: the sultone is selected from sultones with 2-16 carbon atoms, and is preferably 1, 4-butanesultone;
and/or the molar ratio of the sultone to the N-vinylimidazole and/or vinylpyridine is 1: 0.8-1: 1.2;
and/or, the preparation method further comprises the following steps: after the reaction of the first mixed reaction system is finished, washing, distilling and drying the obtained solid; and/or, the first solvent comprises toluene and/or xylene.
5. The production method according to claim 3, characterized by comprising: respectively pretreating styrene derivatives, divinylbenzene and/or 1, 5-hexadiene, mixing and emulsifying the pretreated styrene derivatives, divinylbenzene and/or 1, 5-hexadiene with the first intermediate product, sodium dodecyl sulfate and/or Tween 80, sodium bicarbonate and a second solvent, heating the obtained mixture to 50-100 ℃, adding an initiator into the mixture to form a second mixed reaction system, and carrying out polymerization reaction; preferably, the molar ratio of the pretreated styrene derivative to the divinylbenzene is 5: 1-200: 1; preferably, the molar ratio of the pretreated styrene derivative to the first intermediate product is 10: 1-1: 80; preferably, the amount of the sodium dodecyl sulfate and/or the tween 80 is 0.1-10 wt% of the second mixed reaction system; preferably, the amount of the sodium bicarbonate is 0.1-15 wt% of the second mixed reaction system; preferably, the pretreatment comprises: respectively mixing and stirring the aqueous alkali with a p-styrene derivative and divinyl benzene for 0.1-3 h, then separating an organic phase, then mixing and stirring the aqueous alkali with the aqueous alkali for 0.1-3 h, separating the organic phase, and drying to obtain a pretreated p-styrene derivative, divinyl benzene and/or 1, 5-hexadiene; preferably, the alkali solution comprises a sodium hydroxide solution; preferably, the concentration of the sodium hydroxide solution is 0.5-15 wt%;
and/or the styrene derivative has a structure represented by any one of the following formulae:
wherein, R is selected from-H, - (CH)2)nCH3、-OH、-SO3H. -COOH, -Cl, -Br, diphenylphosphine-PPh2di-tert-butylphosphine-PtBu2Any one of phenylpyridylphosphine-PPhPy and phenyl tert-butylphosphine-PPhtBu;
and/or, the protective atmosphere comprises an inert gas atmosphere and/or a nitrogen atmosphere, preferably a nitrogen atmosphere;
and/or the initiator comprises any one or the combination of more than two of potassium persulfate, ammonium persulfate, sodium persulfate and azoisobutyronitrile;
and/or the second solvent comprises any one or the combination of more than two of water, ethanol, methanol and butanol;
and/or, the preparation method further comprises the following steps: and after the reaction of the second mixed reaction system is finished, filtering, washing and drying the obtained mixture.
6. The method of claim 3, further comprising: after the acidification treatment is finished, separating, washing and drying the obtained solid; preferably, the drying treatment mode comprises vacuum drying and/or freeze drying;
and/or the acid solution comprises any one or the combination of more than two of sulfuric acid solution, trifluoromethanesulfonic acid solution, hydrochloric acid solution and p-toluenesulfonic acid solution, and is preferably sulfuric acid solution; preferably, the concentration of the acid solution is 0.5 to 20 wt%.
7. An acidic porous polymer catalyst prepared by the process of any one of claims 3-6.
8. Use of the acidic porous polymer catalyst according to any one of claims 1, 2 or 7 for the preparation of oligomeric polyether compounds.
9. A preparation method of an oligomeric polyether compound is characterized by comprising the following steps:
providing an acidic porous polymer catalyst according to any one of claims 1, 2 or 7;
and mixing trioxymethylene and formal compounds with the acidic porous polymer catalyst, and reacting at room temperature to obtain the oligomeric polyether compounds.
10. The method of claim 9, wherein: the formal compound comprises any one or the combination of more than two of dimethoxymethane, diethoxymethane, dipropoxymethane and dibutoxymethane;
and/or the oligomeric polyether compound comprises any one or the combination of more than two of polyoxymethylene dimethyl ether, polyoxymethylene diethane, polyoxymethylene dipropyl oxide and polyoxymethylene dibutyl oxide;
and/or the molar ratio of the trioxymethylene to the formal compound is 0.7: 1-4: 1;
and/or the reaction time is 0.1-100 h.
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