CN113398986A - PH sensitive catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof - Google Patents
PH sensitive catalyst for catalyzing asymmetric Aldol reaction and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000005575 aldol reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 30
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 30
- 239000002086 nanomaterial Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003277 amino group Chemical group 0.000 claims abstract description 13
- -1 biaryl proline derivatives Chemical class 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000011258 core-shell material Substances 0.000 claims abstract description 11
- 239000002539 nanocarrier Substances 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
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- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
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- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 14
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- 238000009833 condensation Methods 0.000 claims description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
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- 238000001291 vacuum drying Methods 0.000 claims description 5
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- 239000007788 liquid Substances 0.000 claims description 4
- 229930182821 L-proline Natural products 0.000 claims description 3
- KEGQWGXRELVPRH-NSHDSACASA-N benzyl n-[(2s)-pyrrolidine-2-carbonyl]carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC(=O)[C@@H]1CCCN1 KEGQWGXRELVPRH-NSHDSACASA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
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- 229910001868 water Inorganic materials 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 239000003814 drug Substances 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
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- YLOCGHYTXIINAI-XKUOMLDTSA-N (2s)-2-amino-3-(4-hydroxyphenyl)propanoic acid;(2s)-2-aminopentanedioic acid;(2s)-2-aminopropanoic acid;(2s)-2,6-diaminohexanoic acid Chemical compound C[C@H](N)C(O)=O.NCCCC[C@H](N)C(O)=O.OC(=O)[C@@H](N)CCC(O)=O.OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 YLOCGHYTXIINAI-XKUOMLDTSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 108010072051 Glatiramer Acetate Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000575 polymersome Polymers 0.000 description 1
- 150000003147 proline derivatives Chemical class 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000013268 sustained release 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
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
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- B01J35/40—
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- B01J35/51—
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- B01J35/647—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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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
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a pH sensitive catalyst for catalyzing asymmetric Aldol reaction and a preparation method thereof, wherein the preparation method comprises the following steps: taking polyacrylic acid derivatives as shells and mesoporous silica nano-carriers as cores; activating carboxyl groups in polyacrylic acid derivatives, and then carrying out amidation coupling reaction and other coating processes on the activated carboxyl groups and amino groups on mesoporous silica nano material carriers to prepare core-shell type organic-inorganic nano materials, and loading chiral bipyridine/biaryl proline derivatives on the core-shell type organic-inorganic nano materials to prepare the pH sensitive catalyst for catalyzing asymmetric Aldol reaction. The pH sensitive catalyst provided by the invention can solve the problems that the mesoporous silicon oxide nano-carrier is easy to aggregate in a solution, so that the dispersibility of Z on the mesoporous surface is poor, and the like, and can achieve a high-efficiency catalytic effect by intelligently releasing the loaded active species Z in different pH environments in a catalytic process.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a pH sensitive catalyst for catalyzing asymmetric Aldol reaction and a preparation method thereof.
Background
In recent years, asymmetric Aldol reactions (Aldol condensation reactions) have been widely recognized as the most important type of carbon-carbon bond-forming reaction in organic synthesis.
As early as 2000, List et al (Journal of the American Chemical Society,2000,122, (10): 2395-. Therefore, Zhao et al (Synlett,2012,23, (13): 1990) -1994) have excellent catalytic performance (up to 99% yield) using a variety of bipyridine/biarylproline and its derivatives (Z) as homogeneous catalysts. However, such homogeneous catalysts cannot be recovered; for this reason, researchers have attempted to transfer these homogeneous catalytic reactions to heterogeneous systems in order to achieve catalyst recycling.
At present, the porous material is one of the commonly used supports for heterogeneous catalysts, such as: fern index-Mayoralas et al (Advanced Synthesis & Catalysis,2005,347, (10): 1395) -1403) immobilized proline on MCM-41 mesoporous surface, showing better catalytic performance in direct asymmetric Aldol reaction of hydroxyacetone and aldehyde; gao et al (Journal of Molecular Catalysis A: Chemical,2009,313, (1-2):79-87) modified proline and grafted on SBA-15 mesoporous surface, showed better catalytic performance in catalyzing asymmetric Aldol reaction of p-nitrobenzaldehyde and cyclohexanone at low temperature (yield: 87%, enantioselectivity: 90%); patent CN101879459A (2010) discloses a preparation method of a functionalized PMO mesoporous material supported cu (i), which is applied to glatiramer coupling reaction (glasercouping) in an aqueous medium and has a good catalyst recycling effect.
In recent years, Bimodal Mesoporous Silicas (BMMs) have a relatively high specific surface area>700m2G), larger pore volume (. about.3.5 cm)3(g)) and a controllable bimodal mesoporous structure (small holes with the diameter of about 2-3nm and stacking holes with the diameter of 10-30 nm), and has important application value in the fields of adsorption separation, drug delivery and the like (Langmuir,2003,19, (20): 8395-. Tang (Microporous)&Meso pore Materials,2018,260, 245-. However, heterogeneous catalysts based on BMMs, on one hand, have poor Z dispersibility on the mesoporous surface due to easy aggregation of mesoporous silica particles in solution during the preparation process; on the other hand, the supported active species Z can not be driven to realize high-efficiency catalysis through controllable release in a special environment in the catalysis process. Among them, one of the key influencing factors is that the prepared catalyst has no intelligent responsiveness.
The polyacrylic acid derivatives are pH-sensitive polymers which are widely applied to the fields of macromolecular separation, enzyme immobilization, drug controlled release and the like. Suzuki et al (Polymers for Advanced Technologies,2000,11, (2):92-97) earlier reported the feasibility of grafting polyacrylic acid onto mesoporous silica surfaces; hong et al (Journal of Materials Chemistry,2009,19, (29): 5155-. The prior patent US2013034609 discloses a pH-responsive polymersome prepared by grafting polymethacrylic acid to the surface of hollow mesoporous silica by a covalent bond coupling method. Although the intelligent response type nano materials have potential application prospects in the field of drug sustained and controlled release, relevant documents that polyacrylic acid is adopted to modify BMMs, and then chiral molecules with catalytic activity are loaded to realize controllable release of active species under different pH values and to catalyze asymmetric Aldol reactions are rarely reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a pH sensitive catalyst for catalyzing asymmetric Aldol reaction and a preparation method thereof.
The invention discloses a pH sensitive catalyst for catalyzing asymmetric Aldol reaction, which comprises the following components:
the core-shell organic-inorganic nano material is prepared by taking a polyacrylic derivative as a shell and a mesoporous silicon oxide nano carrier as a core, and activating carboxyl groups in the polyacrylic derivative and amino groups on the mesoporous silicon oxide nano material carrier through a coating process;
a chiral bipyridine/biaryl proline derivative (Z) supported on the core-shell organic-inorganic nanomaterial.
As a further improvement of the invention, the molecular structural formula of the polyacrylic acid derivative is as follows:
in the formula, R represents H, CH3、CH2CH3、CH2CH2CH2CH3One kind of (1).
As a further improvement of the invention, the mesoporous silica nano-carrier is a bimodal mesoporous silica nano-material (BMMs) with 2-3nm small holes and 10-30nm spherical particle stacking holes.
As a further improvement of the invention, the activation of carboxyl groups in the polyacrylic acid derivatives is an activation system consisting of a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and N-hydroxysuccinimide (NHS), and the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) to the N-hydroxysuccinimide (NHS) is (1-5): 1.
As a further improvement of the present invention, the molecular structural formula of the chiral bipyridine/biaryl proline derivative (Z) is as follows:
in the formula, X represents one of N, C, R represents H, L-proline and 1-C10H7SO2、3-CH3C6H4SO2And N-Cbz-prolinamide.
The invention also discloses a preparation method of the pH sensitive catalyst for catalyzing the asymmetric Aldol reaction, which comprises the following steps:
step 5, preparing BMMs of the demoulding plate agent coated by the polyacrylic acid derivatives based on the P-t-BMMs, and marking as the P-BMMs;
and 6, preparing a pH sensitive catalyst for catalyzing the asymmetric Aldol reaction based on Z and P-BMMs, and marking as P-Z @ BMMs.
As a further improvement of the present invention, the step 3 includes:
step 3.1, drying the t-BMMs at 150 ℃ for 3 hours;
step 3.2 dried t-BMMs and 3-aminopropyltriethoxysilane in 1 g/40 mL of N2Mixing and stirring under the protection of (1) and heating and refluxing for 12 hours; the solvent was removed by centrifugation and washed with ethanol several times and the resulting solid was dried under vacuum at 150 ℃ for 3 hours to give t-BMMs-APS.
As a further improvement of the present invention, the step 4 includes:
step 4.1, dissolving the polyacrylic acid derivative in N, N-dimethylformamide solution, heating and stirring;
step 4.2, dissolving EDCI in N, N-dimethylformamide solution, and adding into the solution in the step 4.1 to continuously heat and stir;
step 4.3, dissolving NHS in the N, N-dimethylformamide solution, adding the solution into the solution in the step 4.2, and continuously heating and stirring;
step 4.4, adding the t-BMMs-APS into the solution obtained in the step 4.3, and carrying out heating reflux reaction for 6-10 hours;
and 4.5, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-t-BMMs.
As a further improvement of the present invention, the step 5 includes:
step 5.1, dispersing the P-t-BMMs in a mixed solution of ammonium nitrate/ethanol, heating and refluxing for 4-8 hours at 80 ℃ to remove a template CTAB, and repeatedly heating and refluxing for 3 times; wherein the concentration of the ammonium nitrate/ethanol solution in the mixed solution is 10-20 mg/mL, and the solid-to-liquid ratio is 1g (100-200) mL;
and 5.2, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-BMMs.
As a further improvement of the present invention, the step 6 includes:
step 6.1, dispersing the P-BMMs in a dichloromethane solution containing Z, and carrying out condensation reflux reaction; wherein, the temperature of the condensation reflux reaction is as follows: the reaction time is 8-12 hours at 42 ℃;
step 6.2, centrifugally washing and drying to obtain P-Z @ BMMs; wherein, the drying conditions are as follows: vacuum drying at 80-100 deg.c for 8-12 hr.
Compared with the prior art, the invention has the beneficial effects that:
the pH sensitive catalyst provided by the invention can solve the problems that the mesoporous silicon oxide nano-carrier is easy to aggregate in a solution, so that the dispersibility of Z on the mesoporous surface is poor, and the like, and can achieve a high-efficiency catalytic effect by intelligently releasing the loaded active species Z in different pH environments in a catalytic process.
Drawings
FIG. 1 is a flow chart of a method for preparing a pH sensitive catalyst for catalyzing an asymmetric Aldol reaction according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of a pH sensitive catalyst during each step of the preparation process according to an embodiment of the present invention;
fig. 3 is a graph showing a low-temperature nitrogen adsorption and desorption curve and a corresponding pore size distribution diagram of a pH-sensitive catalyst according to an embodiment of the present invention during each preparation process.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention is described in further detail below with reference to the attached drawing figures:
the invention provides a pH sensitive catalyst for catalyzing asymmetric Aldol reaction, which comprises the following components: core-shell organic-inorganic nanomaterials and chiral bipyridine/biaryl proline derivatives (Z); wherein the content of the first and second substances,
the core-shell organic-inorganic nano material is prepared by taking a polyacrylic acid derivative as a shell and a mesoporous silicon oxide nano carrier as a core, and performing coating processes such as amidation coupling reaction and the like on carboxyl groups in the polyacrylic acid derivative and amino groups on the mesoporous silicon oxide nano material carrier after activation;
the chiral bipyridine/biaryl proline derivative (Z) is loaded on a core-shell organic-inorganic nano material.
Among the above pH sensitive catalysts, specific ones are:
the molecular structural formula of the polyacrylic acid derivative is as follows:
in the formula, R represents H, CH3、CH2CH3、CH2CH2CH2CH3One kind of (1).
The mesoporous silica nano-carrier is a bimodal mesoporous silica nano material (BMMs) with small holes of 2-3nm and spherical particle stacking holes of 10-30 nm.
The activation of carboxyl groups in the polyacrylic acid derivatives is an activation system consisting of a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and N-hydroxysuccinimide (NHS), and the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) to the N-hydroxysuccinimide (NHS) is (1-5): 1.
The molecular structural formula of the chiral bipyridine/biaryl proline derivative (Z) is as follows:
in the formula, X represents one of N, C, R represents H, L-proline and 1-C10H7SO2、3-CH3C6H4SO2And N-Cbz-prolinamide.
The pH sensitive catalyst provided by the invention can solve the problems that the mesoporous silicon oxide nano-carrier is easy to aggregate in a solution, so that the dispersibility of Z on the mesoporous surface is poor, and the like, and can achieve a high-efficiency catalytic effect by intelligently releasing the loaded active species Z in different pH environments in a catalytic process.
The invention provides a preparation method of a pH sensitive catalyst for catalyzing asymmetric Aldol reaction, which comprises the following steps:
taking polyacrylic acid derivatives as shells and mesoporous silica nano-carriers as cores; activating carboxyl groups in polyacrylic acid derivatives, and then carrying out amidation coupling reaction and other coating processes on the activated carboxyl groups and amino groups on mesoporous silica nano material carriers to prepare core-shell type organic-inorganic nano materials, and loading chiral bipyridine/biaryl proline derivatives on the core-shell type organic-inorganic nano materials to prepare the pH sensitive catalyst for catalyzing asymmetric Aldol reaction.
As shown in fig. 1, the preparation method specifically includes:
z was prepared according to the literature (Synlett,2012,23, (13): 1990) -1994; chemistry select,2020,5, (35): 10996-11003).
BMMs of CTAB, an undecalant, were prepared according to the literature (Langmuir,2003,19, (20): 8395-8402).
step 3.1, drying the t-BMMs at 150 ℃ for 3 hours;
step 3.2 dried t-BMMs and 3-aminopropyltriethoxysilane in dry toluene (2.73% concentration) in 1g:40mL N2Mixing and stirring under the protection of (1) and heating and refluxing for 12 hours; the solvent was removed by centrifugation and washed with ethanol several times and the resulting solid was dried under vacuum at 150 ℃ for 3 hours to give t-BMMs-APS.
step 4.1, dissolving the polyacrylic acid derivative in N, N-dimethylformamide solution (concentration: 0.21%), heating and stirring;
step 4.2, dissolving EDCI in N, N-dimethylformamide solution (concentration: 0.45%), adding into the solution of step 4.1, and continuously heating and stirring;
step 4.3, dissolving NHS in the N, N-dimethylformamide solution (the concentration is 0.05-0.27 percent), and adding the solution into the solution in the step 4.2 for continuous heating and stirring; wherein the molar ratio of EDCI to NHS is (1-5) to 1;
step 4.4, adding the t-BMMs-APS into the solution obtained in the step 4.3, and carrying out heating reflux reaction for 6-10 hours;
and 4.5, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-t-BMMs.
Step 5, preparing BMMs of the demoulding plate agent coated by the polyacrylic acid derivatives based on the P-t-BMMs, and marking as the P-BMMs; the method specifically comprises the following steps:
step 5.1, dispersing the P-t-BMMs in ammonium Nitrate (NH)4NO3) Heating and refluxing the mixed solution of alcohol (EtOH) for 4-8 hours at 80 ℃ to remove the template CTAB, and repeatedly heating and refluxing for 3 times; wherein the concentration of the ammonium nitrate/ethanol solution in the mixed solution is 10-20 mg/mL, and the solid-to-liquid ratio is 1g (100-200) mL;
and 5.2, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-BMMs.
step 6.1, dispersing the P-BMMs in a dichloromethane solution (solid-to-liquid ratio: 1g:60mL) containing Z, and condensing and refluxing for reaction; wherein, the temperature of the condensation reflux reaction is as follows: the reaction time is 8-12 hours at 42 ℃;
step 6.2, centrifugally washing and drying to obtain P-Z @ BMMs; wherein, the drying conditions are as follows: vacuum drying at 80-100 deg.c for 8-12 hr.
As shown in FIGS. 2(t-BMMs) and (P-Z @ BMMs), the (100) plane diffraction peak of the sample P-Z @ BMMs after removal of the templating agent CTAB shifts to the high angle direction, indicating that CTAB has eluted. However, after coating the surface of the BMMs with the polyacrylic derivatives (shown in FIG. 2 (P-t-BMMs)) and loading the active species Z (shown in FIG. 2(P-Z @ BMMs)), the peak shapes of the diffraction peaks of all samples are not substantially changed, indicating that the samples maintain the bimodal mesoporous structure of the BMMs during the coating and loading processes.
As shown in FIG. 3 (low temperature nitrogen desorption curve and corresponding pore size distribution plot), the pore size distribution plot of sample t-BMMs before CTAB (shown in FIG. 3 (t-BMMs)) without the template agent showed no pinholes. However, after the amino group modification on the surface of the t-BMMs, the t-BMMs-APS of the sample showed a mode of pore size of about 2.35nm (shown in FIG. 3 (t-BMMS-APS)), and further after the surface-coating with the polyacrylic acid derivative and subsequent removal of the template, the P-BMMs of the sample showed a mode of pore size of about 2.60nm (shown in FIG. 3 (P-BMMs)). Finally, after loading with the active species Z, the P-Z @ BMMs have a maximum pore size of about 2.59nm (FIG. 3(P-Z @ BMMs)).
The preparation process has the advantages of easily obtained raw materials and simple operation; the catalyst shows higher response performance to pH and has good catalytic activity (stereoselectivity (ee: 3%; dr: 53:47) for asymmetric Aldol reaction, and the yield is about 80%).
Example 1:
the invention provides a preparation method of a pH sensitive catalyst for catalyzing asymmetric Aldol reaction, which comprises the following steps:
2.62g CTAB was dissolved in 105mL of distilled water, magnetically stirred to complete dissolution, 8mL of tetraethyl orthosilicate (TEOS) was removed and slowly added to the above solution followed by the rapid addition of 3.5mL of 25% by mass aqueous ammonia (NH)3·H2O), stirring is continued until the solution becomes a white gel. The white gel was suction filtered, washed thoroughly with distilled water, and dried to give BMMs without the template, noted as t-BMMs.
step 3.1, weighing 0.5012g of the t-BMMs obtained in the step 2 into a round-bottom flask, and drying for 3 hours in vacuum at 150 ℃;
step 3.2, the dried t-BMMs are dispersed in an anhydrous toluene solution (concentration: 2.73%) containing 3-aminopropyltriethoxysilane in a volume of 1g:40mL in N2Mixing and stirring under the protection of (1), and placing in an oil bath at 110 ℃ for heating and refluxing for 12 hours; after the reaction is finished, centrifuging to remove the solvent, and repeatedly washing for 3 times by using ethanol; the resulting solid was dried in a vacuum oven at 150 ℃ for 3 hours to give the amino group modified BMMs without the release agent, which was designated t-BMMs-APS.
step 4.1, weighing 20mg of polyacrylic acid, dissolving the polyacrylic acid in 10mL of N, N-dimethylformamide solution (concentration: 0.23 percent), and continuously heating and stirring the solution for 30min under the condition of 80 ℃ oil bath;
step 4.2, weighing 20mg of EDCI, dissolving in 5mL of N, N-dimethylformamide solution (concentration: 0.45%), then dropwise adding into the solution in the step 4.1, and continuously heating and stirring for 15 min;
step 4.3, weighing 12.0mg of NHS, dissolving in 5mL of N, N-dimethylformamide solution (concentration: 0.27%), then dropwise adding into the solution of step 4.2, and continuously heating and stirring for 1 hour; wherein the molar ratio of EDCI to NHS is 1: 1.
Step 4.4, weighing 150mg of the t-BMMs-APS sample dried in the step 3.2, adding the t-BMMs-APS sample into the solution in the step 4.3, and heating and refluxing for 6 hours;
and 4.5, centrifuging to remove the solvent after the reaction is finished, alternately washing for 3 times by using deionized water and ethanol, and performing vacuum drying for 3 hours at 150 ℃ to obtain the BMMs (poly acrylic acid) -coated without the stripper, which are marked as PAA-t-BMMs.
Step 5, preparing polyacrylic acid coated BMMs:
step 5.1, weighing 100mg of the PAA-t-BMMs in the step 4.5, and dispersing in 10mL of ammonium nitrate/ethanol (NH) with the concentration of 10mg/mL4NO3EtOH), heating and refluxing for 4 hours at 80 ℃ to remove the CTAB template, and repeatedly heating and refluxing for 3 times;
and 5.2, centrifuging to remove the solvent after the reaction is finished, alternately washing for 3 times by using deionized water and ethanol, and drying for 3 hours in vacuum at 150 ℃ to obtain the polyacrylic acid coated BMMs, which are marked as PAA-BMMs.
step 6.1, weighing 100mg of PAA-BMMs in the step 5.2, and dispersing in the solution containing active substance (Z)1Quality: 50mg) of a dichloromethane solution (concentration: 0.63%) and reacted at 42 ℃ for 8 hours under reflux by condensation;
step 6.2, centrifuging the mixture after reaction, alternately washing the solid precipitate for 3 times by using dichloromethane and ethanol, and drying the solid precipitate for 8 hours in vacuum at the temperature of 80 ℃ to obtain Z1The pH sensitive catalyst is marked as PAA-Z1@BMMs。
Using Z1The pH sensitive catalyst is used for catalyzing asymmetric Aldol reaction:
p-nitrobenzaldehyde (0.1mmol,15.1mg), cyclohexanone (1.0mmol, 104. mu.L), catalyst (5 mol%) and solvent water (0.5mL) were added sequentially to reaction flask A, while trifluoroacetic acid (20 mol%, 1.48. mu.L) was additionally added to reaction flask B, wherein the pH values, as measured by pH meter, were 7.21 and 1.53, respectively. The flask A, B was sealed and stirred, and the reaction was followed by TLC, which was stopped after 5 days, showing that almost no product was formed in A and substantially no reactant was present in B. The crude product from B was subjected to column chromatography (mobile phase: petroleum ether/ethyl acetate) and purified to give the product in 81% yield (ratio of actual to theoretical mass), with an ee value of 3% determined by HPLC and a dr value of 53: 47.
The reaction equation is:
the invention adopts a load Z1pH sensitive catalyst (PAA-Z) of (1)1@ BMMs) was subjected to a catalytic asymmetric Aldol reaction. The results show that the catalyst releases virtually no active substance Z in solution under acidic conditions (pH 1.53)1On the contrary, in a neutral (pH 7.21) solution,the catalytic yield of the catalyst to Aldol reaction is high (81%). The catalyst of the invention has high sensitivity to pH, so that PAA-Z is ensured1@ active Z in BMMs1Can meet the requirement of realizing controllable release catalysis under different pH environments.
Example 2:
the invention provides a preparation method of a pH sensitive catalyst for catalyzing asymmetric Aldol reaction, which comprises the following steps:
2.81g CTAB in 105mL distilled water, magnetic stirring to complete dissolution, removing 8mL TEOS slowly into the solution, followed by rapid addition of 4.5mL NH 25% mass fraction3·H2And O, continuing stirring until the solution is totally changed into white gel. The white gel was suction filtered, washed thoroughly with distilled water, and dried to give BMMs without the template, noted as t-BMMs.
step 3.1, weighing 0.5012g of the t-BMMs obtained in the step 2 into a round-bottom flask, and drying for 3 hours in vacuum at 150 ℃;
step 3.2, the dried t-BMMs are dispersed in an anhydrous toluene solution (concentration: 2.73%) containing 3-aminopropyltriethoxysilane in a volume of 1g:40mL in N2Mixing and stirring under the protection of (1), and placing in an oil bath at 110 ℃ for heating and refluxing for 12 hours; after the reaction is finished, centrifuging to remove the solvent, and repeatedly washing for 3 times by using ethanol; the resulting solid was dried in a vacuum oven at 150 ℃ for 3 hours to give the amino group modified BMMs without the release agent, which was designated t-BMMs-APS.
step 4.1, weighing 20mg of polymethacrylic acid, dissolving the polymethacrylic acid in 10mL of N, N-dimethylformamide solution (concentration: 0.23 percent), and continuously heating and stirring the solution for 30min under the condition of 80 ℃ oil bath;
step 4.2, weighing 20mg of EDCI, dissolving in 5mL of N, N-dimethylformamide solution (concentration: 0.45%), then dropwise adding into the solution in the step 4.1, and continuously heating and stirring for 15 min;
step 4.3, weighing 2.4mg of NHS, dissolving in 5mL of N, N-dimethylformamide solution (concentration: 0.05%), then dropwise adding into the solution of step 4.2, and continuously heating and stirring for 1 hour; the molar ratio of EDCI to NHS described above was 5: 1.
Step 4.4, weighing 150mg of the t-BMMs-APS sample dried in the step 3.2, adding the t-BMMs-APS sample into the solution in the step 4.3, and heating and refluxing for reaction for 10 hours;
and 4.5, after the reaction is finished, centrifuging to remove the solvent, alternately washing for 3 times by using deionized water and ethanol, and performing vacuum drying for 3 hours at 150 ℃ to obtain the BMMs (polymethylacrylic acid) without the stripper, which are marked as PMAA-t-BMMs.
Step 5, preparing polymethacrylic acid coated BMMs:
step 5.1, weighing 100mg of the PMAA-t-BMMs in the step 4.5, and dispersing in 20mL of NH with the concentration of 20mg/mL4NO3Heating and refluxing the mixed solution of/EtOH at 80 ℃ for 8 hours to remove the template CTAB, and repeatedly heating and refluxing for 3 times;
and 5.2, centrifuging to remove the solvent after the reaction is finished, alternately washing for 3 times by using deionized water and ethanol, and drying for 3 hours in vacuum at 150 ℃ to obtain the polymethacrylic acid coated BMMs, which are marked as PMAA-BMMs.
step 6.1, weigh 100mg of the PMAA-BMMs from step 5.2 above, and disperse them in the solution containing the active substance (Z)2Quality: 50mg) of a dichloromethane solution (concentration: 0.63%) and reacted at 42 ℃ under reflux for 12 hours;
step 6.2, centrifuging the mixture after reaction, alternately washing the solid precipitate for 3 times by using dichloromethane and ethanol, and drying the solid precipitate for 12 hours in vacuum at the temperature of 100 ℃ to obtain Z2The pH sensitive catalyst is marked as PMAA-Z2@BMMs。
Using Z2The pH sensitive catalyst is used for catalyzing asymmetric Aldol reaction:
p-nitrobenzaldehyde (0.1mmol,15.1mg), cyclohexanone (1.0mmol, 104. mu.L), catalyst (5 mol%) and solvent water (0.5mL) were added sequentially to reaction flask A, while trifluoroacetic acid (20 mol%, 1.48. mu.L) was additionally added to reaction flask B, wherein the pH values, as measured by pH meter, were 7.25 and 1.56, respectively. The flask A, B was sealed and stirred, and the reaction was followed by TLC, which was stopped after 5 days, showing that almost no product was formed in A and substantially no reactant was present in B. The crude product from B was subjected to column chromatography (mobile phase: petroleum ether/ethyl acetate) and purified to give the product in 78% yield (ratio of actual product mass to theoretical product mass), with an ee value of 2% determined by HPLC and a dr value of 51: 49.
The reaction equation is:
the invention aims to solve the problem of excessively complex synthesis of the conventional polymer in the process of modifying the silicon oxide nano material and further widen the application range of the conventional polymer, and provides a preparation method of polyacrylic acid derivative modified bimodal mesoporous silicon dioxide (BMMs), and then the asymmetric Aldol reaction is further catalyzed by a bipyridyl/biaryl proline-loaded chiral molecule, so that the aims of simple and feasible preparation process, low cost and synthesis of a high-sensitivity pH response catalyst are fulfilled.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A pH sensitive catalyst for catalyzing an asymmetric Aldol reaction comprising:
the core-shell organic-inorganic nano material is prepared by taking a polyacrylic derivative as a shell and a mesoporous silicon oxide nano carrier as a core, and activating carboxyl groups in the polyacrylic derivative and amino groups on the mesoporous silicon oxide nano material carrier through a coating process;
a chiral bipyridine/biaryl proline derivative (Z) supported on the core-shell organic-inorganic nanomaterial.
2. The pH-sensitive catalyst of claim 1, wherein the polyacrylic derivative has the following molecular formula:
in the formula, R represents H, CH3、CH2CH3、CH2CH2CH2CH3One kind of (1).
3. The pH sensitive catalyst of claim 1, wherein the mesoporous silica nanocarriers are bimodal mesoporous silica nanomaterials (BMMs) having pores of 2 to 3nm and spherical particle packing pores of 10 to 30 nm.
4. The pH-sensitive catalyst according to claim 1, wherein the activation of carboxyl groups in the polyacrylic derivative is an activation system consisting of a mixture of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) and N-hydroxysuccinimide (NHS), and the molar ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDCI) to N-hydroxysuccinimide (NHS) is (1-5): 1.
5. The pH-sensitive catalyst according to claim 1, wherein the molecular structural formula of the chiral bipyridine/biaryl proline derivative (Z) is as follows:
in the formula, X represents one of N, C, R represents H, L-proline and 1-C10H7SO2、3-CH3C6H4SO2And N-Cbz-prolinamide.
6. A method for preparing the pH-sensitive catalyst according to any one of claims 1 to 5, comprising:
step 1, preparing a chiral bipyridine/biaryl proline derivative Z;
step 2, preparing BMMs without the stripper plate agent, and marking as t-BMMs; wherein the template agent is cetyl trimethyl ammonium bromide CTAB;
step 3, preparing BMMs without the template agent modified by amino groups based on the t-BMMs, and marking as t-BMMs-APS;
step 4, preparing the BMMs without the template release agent coated by the polyacrylic acid derivatives based on the t-BMMs-APS, and marking as P-t-BMMs;
step 5, preparing BMMs of the demoulding plate agent coated by the polyacrylic acid derivatives based on the P-t-BMMs, and marking as the P-BMMs;
and 6, preparing a pH sensitive catalyst for catalyzing the asymmetric Aldol reaction based on Z and P-BMMs, and marking as P-Z @ BMMs.
7. The method of claim 6, wherein step 3 comprises:
step 3.1, drying the t-BMMs at 150 ℃ for 3 hours;
step 3.2 dried t-BMMs and 3-aminopropyltriethoxysilane in 1 g/40 mL of N2Mixing and stirring under the protection of (1) and heating and refluxing for 12 hours; centrifuging to remove the solvent, washing with ethanol several times to obtain a solidDrying at 150 deg.C for 3 hr under vacuum to obtain t-BMMs-APS.
8. The method of claim 6, wherein step 4 comprises:
step 4.1, dissolving the polyacrylic acid derivative in N, N-dimethylformamide solution, heating and stirring;
step 4.2, dissolving EDCI in N, N-dimethylformamide solution, and adding into the solution in the step 4.1 to continuously heat and stir;
step 4.3, dissolving NHS in the N, N-dimethylformamide solution, adding the solution into the solution in the step 4.2, and continuously heating and stirring;
step 4.4, adding the t-BMMs-APS into the solution obtained in the step 4.3, and carrying out heating reflux reaction for 6-10 hours;
and 4.5, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-t-BMMs.
9. The method of claim 6, wherein step 5 comprises:
step 5.1, dispersing the P-t-BMMs in a mixed solution of ammonium nitrate/ethanol, heating and refluxing for 4-8 hours at 80 ℃ to remove a template CTAB, and repeatedly heating and refluxing for 3 times; wherein the concentration of the ammonium nitrate/ethanol solution in the mixed solution is 10-20 mg/mL, and the solid-to-liquid ratio is 1g (100-200) mL;
and 5.2, centrifuging to remove the solvent, washing with deionized water and ethanol for multiple times, and drying in vacuum at 150 ℃ for 3 hours to obtain the P-BMMs.
10. The method of claim 6, wherein step 6 comprises:
step 6.1, dispersing the P-BMMs in a dichloromethane solution containing Z, and carrying out condensation reflux reaction; wherein, the temperature of the condensation reflux reaction is as follows: the reaction time is 8-12 hours at 42 ℃;
step 6.2, centrifugally washing and drying to obtain P-Z @ BMMs; wherein, the drying conditions are as follows: vacuum drying at 80-100 deg.c for 8-12 hr.
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