CN112973589B - Preparation method of sulfonated RF aerogel microspheres - Google Patents
Preparation method of sulfonated RF aerogel microspheres Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 87
- 239000004005 microsphere Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000243 solution Substances 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 46
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 17
- 239000011324 bead Substances 0.000 claims abstract description 16
- BTLJHKIMMQUWHU-UHFFFAOYSA-N dichloromethane;sulfurochloridic acid Chemical compound ClCCl.OS(Cl)(=O)=O BTLJHKIMMQUWHU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 10
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011949 solid catalyst Substances 0.000 claims description 8
- 238000000352 supercritical drying Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- UUYSCNGPNOYZMC-UHFFFAOYSA-N methyl 2-(4-hydroxyphenoxy)propanoate Chemical compound COC(=O)C(C)OC1=CC=C(O)C=C1 UUYSCNGPNOYZMC-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- B01J35/23—
-
- B01J35/51—
-
- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
Abstract
The invention discloses a preparation method of sulfonated RF aerogel microspheres, which comprises the following steps: stirring and mixing resorcinol, formaldehyde solution, sodium carbonate and deionized water uniformly, heating for reaction, refrigerating, adding a benzoic acid aqueous solution, dropwise adding into the span-80 solution, heating for stirring for reaction, and forming gel beads in the span-80 solution; separating gel beads in the span-80 solution, adding an ethanol exchange solvent, and drying to obtain RF aerogel microspheres; adding the RF aerogel microspheres into dichloromethane, slowly dropping chlorosulfonic acid dichloromethane solution, stirring and reacting at 4 ℃, introducing nitrogen into the dichloromethane solution in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; and drying after the reaction is finished to obtain the sulfonated RF aerogel microspheres. The sulfonated RF aerogel microspheres provided by the invention have excellent formability, high sulfonic acid group grafting rate and uniform distribution, and the prepared sulfonated RF aerogel microspheres have large specific surface area.
Description
Technical Field
The invention relates to the field of preparation of aerogel microspheres, and particularly relates to a preparation method of sulfonated RF aerogel microspheres.
Background
Esters formed by esterification of alcohols and acids have attracted considerable attention because they are always valuable chemicals in industrial processes, such as solvents, fragrances, polymers, biodiesel, and the like. However, the esterification reaction itself has the disadvantages of slow reaction, low conversion efficiency, low selectivity, etc., and a proper catalyst needs to be selected to accelerate the reaction and improve the conversion efficiency and the reaction selectivity. Conventional acid catalysts include strong inorganic acid catalysts (such as sulfuric acid, hydrochloric acid or hydrogen fluoride) and lewis acid catalysts (such as anhydrous aluminum trioxide, trifluoroborane or organotin chloride), and high yield and high selectivity can be obtained using such catalysts, but there are difficulties in separating and recovering the catalyst after the reaction, generation of a large amount of waste, and corrosion of equipment. In order to achieve minimal waste generation, easier product recovery and higher atomic efficiency, the development of "green" catalytic processes is imperative. The solid super acidic catalyst has been produced, wherein the research and development of the sulfonic acid type solid catalyst are very popular, and the sulfonic acid type solid catalyst has the advantages of high selectivity, less side reaction, easy separation from reactants, no corrosion to equipment, reusability, simple treatment of waste catalyst, less environmental pollution and the like because the sulfonic acid type solid catalyst can activate acid catalytic reaction under mild conditions, thereby being a research hotspot in the field of catalysts rapidly and having great application prospect.
Typical sulfonated solid catalysts include sulfonated solid carbon materials and sulfonated polymer materials, each of which has advantages and disadvantages, such as large specific surface area of the sulfonated solid carbon material, but more sulfonation steps, low grafting ratio and low recycling rate. The sulfonated polymer material has high reusability, but has low specific surface area and less acid sites. Therefore, it is important to find a sulfonated solid catalyst material with high specific surface area and high recycling rate, which is easy to prepare. At present, the sulfonated solid catalyst has the defects of low grafting rate, low specific surface area, low acidity and the like.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing sulfonated RF aerogel microspheres, comprising the steps of:
step one, adding resorcinol, a formaldehyde solution, sodium carbonate and deionized water into a reactor, and stirring and mixing uniformly at a speed of 250-350 r/min to obtain a mixed solution; heating the mixed solution to 60-80 ℃ for reacting for 1-2 hours, taking out and refrigerating after the reaction is completed, then adding a benzoic acid aqueous solution while stirring at the speed of 200-300 r/min, then slowly dropwise adding the benzoic acid aqueous solution into the span-80 solution, stirring at the speed of 100-200 r/min for reacting for 1.5-2.5 hours at the temperature of 60-80 ℃, and then pressurizing and ultrasonically treating the reacted material for 5-10 minutes to form gel pellets in the span-80 solution;
separating gel beads in the span-80 solution, adding an ethanol exchange solvent, and drying to obtain RF aerogel microspheres;
adding the RF aerogel microspheres into dichloromethane, slowly dropping chlorosulfonic acid dichloromethane solution into the dichloromethane, stirring the mixture at the temperature of 4 ℃ for reaction for 5 to 7 hours, introducing nitrogen into the dichloromethane solution in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; and drying after the reaction is finished to obtain the sulfonated RF aerogel microspheres.
Preferably, the mass ratio of the resorcinol to the formaldehyde solution to the sodium carbonate to the water is 200-300: 300-450: 1: 60-120; the concentration of the benzoic acid aqueous solution is 1.5-2 g/L; the concentration of the span-80 solution is 0.08-0.15 wt%; the volume ratio of the benzoic acid aqueous solution to the mixed solution is 1: 3-6; the volume ratio of the benzoic acid aqueous solution to the span-80 solution is 1: 20-30.
Preferably, the solvent of the span-80 solution is any one of dibutyl phthalate, dimethyl phthalate and diethyl phthalate; the pressure of the pressurized ultrasonic is 0.3-0.8 MPa, and the frequency is 45-65 KHz.
Preferably, the mass-to-volume ratio of the RF aerogel microspheres to dichloromethane is 1 g: 40-60 mL; the volume ratio of chlorosulfonic acid to dichloromethane in the chlorosulfonic acid and dichloromethane solution is 1-7: 15.
preferably, the particle size of the RF aerogel microspheres is 100-200 um.
Preferably, in the second step, the number of times of adding the ethanol exchange solvent is 4-7, and CO is adopted for drying2Supercritical drying;
the stirring speed in the third step is 300-400 r/min; vacuum drying is adopted for drying, and the temperature is 110-130 ℃; the aeration rate of the nitrogen is 100-300 mL/min.
Preferably, in the third step, the RF aerogel microspheres are added into dichloromethane, and then placed into a ball milling tank, ball milling balls are added, the ball milling tank is sealed by a sealing cover, and ball milling is performed on the ball milling tank at room temperature and at a speed of 300-800 r/min for 60-90 min.
Preferably, the ball grinding ball is a zirconia grinding ball with the particle size of 0.5-2.5 mm; the mass ratio of the ball grinding balls to the RF aerogel microspheres is 1: 3-5; the mass-volume ratio of the RF aerogel microspheres to the dichloromethane is 1 g: 40-60 mL.
Preferably, in the third step, intermittent ultrasound is applied during the stirring reaction; the frequency of the intermittent ultrasound is 35-55 KHz, the process of the intermittent ultrasound is 10-15 min per time, and the ultrasound is stopped for 5 min.
The invention also provides an application of the sulfonated RF aerogel microspheres as a sulfonated solid catalyst in esterification reaction of alcohol and acid, which is characterized in that the alcohol is methanol or ethanol; the acid is 2- (4-hydroxyphenoxy) propionic acid, and the mass ratio of the sulfonated RF aerogel microspheres to the acid is 1: 100.
The invention at least comprises the following beneficial effects: the sulfonated RF aerogel microspheres provided by the invention have excellent formability, high sulfonic acid group grafting rate and uniform distribution, the prepared sulfonated RF aerogel microspheres have large specific surface area, and meanwhile, the preparation method is simple and efficient, and the difficulty of the process is greatly reduced.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM image of RF aerogel microspheres prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of RF aerogel microspheres prepared according to example 1 of the present invention;
FIG. 3 is an SEM image of sulfonated RF aerogel microspheres prepared in example 1 of the present invention;
FIG. 4 is an SEM image of sulfonated RF aerogel microspheres prepared according to example 1 of the present invention;
FIG. 5 is a BET adsorption curve of sulfonated RF aerogel microspheres prepared in example 1 of the present invention;
FIG. 6 is a pore size distribution curve of sulfonated RF aerogel microspheres prepared in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating gel beads in the span-80 solution, adding an ethanol exchange solvent, exchanging for 4 times, and then carrying out CO (carbon monoxide) exchange2Performing supercritical drying to obtain RF aerogel microspheres;
step three, adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ at the speed of 350r/min for reaction for 6 hours, introducing nitrogen into the dichloromethane solution at the speed of 200mL/min in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is formed by mixing 10mL of chlorosulfonic acid and 150mL of dichloromethane;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 448.98m2(iv)/g, S content 10.14%; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 96.1%.
Example 2:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating the gel beads in the span-80 solution,then adding ethanol exchange solvent, exchanging for 4 times, and performing CO exchange2Performing supercritical drying to obtain RF aerogel microspheres;
step three, adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ at the speed of 350r/min for reaction for 6 hours, introducing nitrogen into the dichloromethane solution at the speed of 200mL/min in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is prepared by mixing 30mL of chlorosulfonic acid and 150mL of dichloromethane;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 450.54m2(iv)/g, S content 10.16%; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 96.2%.
Example 3:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating gel beads in the span-80 solution, adding an ethanol exchange solvent, exchanging for 4 times, and then carrying outCO2Performing supercritical drying to obtain RF aerogel microspheres;
step three, adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ at the speed of 350r/min for reaction for 6 hours, introducing nitrogen into the dichloromethane solution at the speed of 200mL/min in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is prepared by mixing 50mL of chlorosulfonic acid and 150mL of dichloromethane;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 449.88m2(iv)/g, S content 10.12%; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 96%.
Example 4:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating gel beads in the span-80 solution, adding an ethanol exchange solvent, exchanging for 4 times, and then carrying out CO (carbon monoxide) exchange2Performing supercritical drying to obtain RF aerogel microspheres;
adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then placing the mixture into a ball milling tank, adding ball milling balls, sealing the ball milling tank by using a sealing cover, carrying out ball milling on the mixture for 60min at the speed of 500r/min at room temperature, then collecting the RF aerogel microspheres and the dichloromethane in the ball milling tank, adding the collected RF aerogel microspheres and the dichloromethane into a reactor, dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ and the speed of 350r/min for reaction for 6 hours, meanwhile introducing nitrogen into the dichloromethane solution at the speed of 200mL/min during the reaction, and collecting gas discharged by the reaction by using sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is formed by mixing 10mL of chlorosulfonic acid and 150mL of dichloromethane; the ball grinding ball is a zirconia grinding ball with the grain diameter of 0.5 mm; the mass ratio of the ball grinding balls to the RF aerogel microspheres is 1: 3;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 465.55m2The content of S is 12.15 percent; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 97.8%.
Example 5:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating gel beads in the span-80 solution, adding an ethanol exchange solvent, exchanging for 4 times, and then carrying out CO (carbon monoxide) exchange2Performing supercritical drying to obtain RF aerogel microspheres;
step three, adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ at the speed of 350r/min for reaction for 6 hours, introducing nitrogen into the dichloromethane solution at the speed of 200mL/min in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is formed by mixing 10mL of chlorosulfonic acid and 150mL of dichloromethane; applying intermittent ultrasound in the stirring reaction process; the frequency of the intermittent ultrasonic is 45KHz, the process of the intermittent ultrasonic is 15min per ultrasonic, and the ultrasonic is stopped for 5 min;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 460.12m2The content of S in the steel is 11.68 percent; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 97.2%.
Example 6:
step one, adding 4.576g of resorcinol, 6.24mL of formaldehyde solution, 0.0161g of sodium carbonate and 63mL of deionized water into a reactor, and uniformly stirring and mixing at the speed of 300r/min to obtain a mixed solution; heating the mixed solution to 70 ℃ for reacting for 1 hour, taking out and refrigerating after the reaction is completed, then adding 20mL of 1.8g/L benzoic acid aqueous solution while stirring at the speed of 200r/min, then dropwise adding the benzoic acid aqueous solution into 500mL of span-80 solution at the speed of 10mL/min, stirring at the speed of 150r/min for reacting for 2 hours at 70 ℃, then pressurizing and ultrasonically treating the reacted material for 8 minutes to form gel beads in the span-80 solution; the concentration of the span-80 solution is 0.1 wt%; the solvent of the span-80 solution is dibutyl phthalate; the pressure of the pressurized ultrasonic wave is 0.5MPa, and the frequency is 55 KHz; the mass fraction of the formaldehyde solution is 38 percent;
step two, separating gel beads in the span-80 solution, adding an ethanol exchange solvent, exchanging for 4 times, and then carrying out CO (carbon monoxide) exchange2Performing supercritical drying to obtain RF aerogel microspheres;
adding 10g of RF aerogel microspheres into 500mL of dichloromethane, then placing the mixture into a ball milling tank, adding ball milling balls, sealing the ball milling tank by using a sealing cover, carrying out ball milling on the mixture for 60min at the speed of 500r/min at room temperature, then collecting the RF aerogel microspheres and the dichloromethane in the ball milling tank, adding the collected RF aerogel microspheres and the dichloromethane into a reactor, dripping chlorosulfonic acid dichloromethane solution into the mixture at the speed of 8mL/min, stirring the mixture at the temperature of 4 ℃ and the speed of 350r/min for reaction for 6 hours, meanwhile introducing nitrogen into the dichloromethane solution at the speed of 200mL/min during the reaction, and collecting gas discharged by the reaction by using sodium hydroxide solution; after the reaction is finished, vacuum drying is carried out at 120 ℃ to obtain sulfonated RF aerogel microspheres; the chlorosulfonic acid dichloromethane solution is formed by mixing 10mL of chlorosulfonic acid and 150mL of dichloromethane; the ball grinding ball is a zirconia grinding ball with the grain diameter of 0.5 mm; the mass ratio of the ball grinding balls to the RF aerogel microspheres is 1: 3; applying intermittent ultrasound in the stirring reaction process; the frequency of the intermittent ultrasonic is 45KHz, the process of the intermittent ultrasonic is 15min per ultrasonic, and the ultrasonic is stopped for 5 min;
the sulfonated RF aerogel microspheres prepared in this example had a specific surface area of 478.36m2The content of S is 12.95 percent; the sulfonated RF aerogel microspheres were used for esterification of methanol and 2- (4-hydroxyphenoxy) propionic acid (22.7 g of 2- (4-hydroxyphenoxy) propionic acid was added to 50mL of methanol, followed by 0.227g of sulfonated RF aerogel microspheres, and the reaction was stirred at 70 ℃ and 300 rpm), which was carried out for 10 hours, and the yield of methyl 2- (4-hydroxyphenoxy) propionate was 98.6%.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (7)
1. A preparation method of sulfonated RF aerogel microspheres is characterized by comprising the following steps:
step one, adding resorcinol, a formaldehyde solution, sodium carbonate and deionized water into a reactor, and stirring and mixing uniformly at a speed of 250-350 r/min to obtain a mixed solution; heating the mixed solution to 60-80 ℃ for reacting for 1-2 hours, taking out and refrigerating after the reaction is completed, then adding a benzoic acid aqueous solution while stirring at the speed of 200-300 r/min, then slowly dropwise adding the benzoic acid aqueous solution into the span-80 solution, stirring at the speed of 100-200 r/min for reacting for 1.5-2.5 hours at the temperature of 60-80 ℃, and then pressurizing and ultrasonically treating the reacted material for 5-10 minutes to form gel pellets in the span-80 solution; the pressure of the pressurized ultrasonic is 0.3-0.8 MPa, and the frequency is 45-65 KHz;
separating gel beads in the span-80 solution, adding an ethanol exchange solvent, and drying to obtain RF aerogel microspheres;
adding the RF aerogel microspheres into dichloromethane, slowly dropping chlorosulfonic acid dichloromethane solution into the dichloromethane, stirring the mixture at the temperature of 4 ℃ for reaction for 5 to 7 hours, introducing nitrogen into the dichloromethane solution in the reaction process, and collecting gas discharged by the reaction by adopting sodium hydroxide solution; drying after the reaction is finished to obtain sulfonated RF aerogel microspheres;
in the third step, adding the RF aerogel microspheres into dichloromethane, then putting into a ball milling tank, adding ball milling balls, sealing the ball milling tank with a sealing cover, and ball milling for 60-90 min on a ball mill at the room temperature at the speed of 300-800 r/min;
the ball grinding ball is a zirconia grinding ball with the particle size of 0.5-2.5 mm; the mass ratio of the ball grinding balls to the RF aerogel microspheres is 1: 3-5; the mass-volume ratio of the RF aerogel microspheres to the dichloromethane is 1 g: 40-60 mL;
in the third step, intermittent ultrasound is applied in the stirring reaction process; the frequency of the intermittent ultrasound is 35-55 KHz, the process of the intermittent ultrasound is 10-15 min per time, and the ultrasound is stopped for 5 min.
2. The method for preparing sulfonated RF aerogel microspheres according to claim 1, wherein the mass ratio of the resorcinol, the formaldehyde solution, the sodium carbonate and the water is 200-300: 300-450: 1: 60-120; the concentration of the benzoic acid aqueous solution is 1.5-2 g/L; the concentration of the span-80 solution is 0.08-0.15 wt%; the volume ratio of the benzoic acid aqueous solution to the mixed solution is 1: 3-6; the volume ratio of the benzoic acid aqueous solution to the span-80 solution is 1: 20-30.
3. The method for preparing sulfonated RF aerogel microspheres according to claim 1, wherein the solvent of the span-80 solution is any one of dibutyl phthalate, dimethyl phthalate, and diethyl phthalate.
4. The method of preparing sulfonated RF aerogel microspheres of claim 1, wherein the mass to volume ratio of RF aerogel microspheres to methylene chloride is 1 g: 40-60 mL; the volume ratio of chlorosulfonic acid to dichloromethane in the chlorosulfonic acid and dichloromethane solution is 1-7: 15.
5. the method of preparing sulfonated RF aerogel microspheres of claim 1, wherein the RF aerogel microspheres have a particle size of 100 to 200 um.
6. The method for preparing sulfonated RF aerogel microspheres according to claim 1, wherein in the second step, the number of times of adding the ethanol exchange solvent is 4-7, and CO is used for drying2Supercritical drying;
the stirring speed in the third step is 300-400 r/min; vacuum drying is adopted for drying, and the temperature is 110-130 ℃; the aeration rate of the nitrogen is 100-300 mL/min.
7. Use of sulfonated RF aerogel microspheres as defined in any one of claims 1 to 6 as sulfonated solid catalyst in esterification reaction of alcohol and acid, wherein the alcohol is methanol or ethanol; the acid is 2- (4-hydroxyphenoxy) propionic acid, and the mass ratio of the sulfonated RF aerogel microspheres to the acid is 1: 100.
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