[go: up one dir, main page]

CN112961353A - Amphiphilic mesoporous organic salt nano particle and preparation method thereof - Google Patents

Amphiphilic mesoporous organic salt nano particle and preparation method thereof Download PDF

Info

Publication number
CN112961353A
CN112961353A CN202110163029.1A CN202110163029A CN112961353A CN 112961353 A CN112961353 A CN 112961353A CN 202110163029 A CN202110163029 A CN 202110163029A CN 112961353 A CN112961353 A CN 112961353A
Authority
CN
China
Prior art keywords
mesoporous
organic salt
pyridine
amphiphilic
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110163029.1A
Other languages
Chinese (zh)
Inventor
王润伟
于洪豪
邹后兵
张宗弢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202110163029.1A priority Critical patent/CN112961353A/en
Publication of CN112961353A publication Critical patent/CN112961353A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/042—Elimination of an organic solid phase
    • C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
    • 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
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Colloid Chemistry (AREA)

Abstract

The invention provides an amphiphilic mesoporous organic salt nanoparticle and a preparation method thereof, wherein an organosilane precursor containing pyridine groups is hydrolyzed and polymerized to prepare mesoporous nanoparticles containing a large number of pyridine groups in a framework, and the mesoporous nanoparticles are reacted with hydrobromic acid to form salts so as to protonate the pyridine groups, thereby obtaining the mesoporous nanoparticles containing a large number of organic groups and ionic groups in the framework, namely mesoporous organic salts. When the mesoporous organic salt nano-particles are placed in water, ionic groups (pyridine hydrobromic acid groups) on the particles can be ionized into free bromine anions and pyridine hydrogen cations. At the moment, the skeleton of the mesoporous organic salt nano particle contains a large number of organic groups with oleophilic ability, and the pyridine hydrogen cation has hydrophilic ability, so the mesoporous organic salt nano particle is an emulsifier capable of emulsifying various oil-water two-phase systems.

Description

Amphiphilic mesoporous organic salt nano particle and preparation method thereof
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to amphiphilic mesoporous organic salt nanoparticles and a preparation method thereof.
Background
The organic reaction is usually carried out in an organic solvent, however, the organic solvent has the disadvantages of environmental pollution and high cost. Water, a green solvent, is rarely used as an organic reaction solvent because, in general, when a water-insoluble organic solvent is mixed with water, the organic phase is separated from the aqueous phase. This immiscible layering can greatly limit the efficiency of many aqueous phase chemical reactions. For this reason, researchers have conducted extensive research to make the two phases miscible. In an initial study, researchers emulsified two immiscible phases by adding an amphiphilic molecule (such as CTAB), to the two phases to dissolve each other. However, the added amphiphilic substance in molecular form is mixed in the final product, which causes difficulty in purification of the product, and the amphiphilic molecule is difficult to recover and reuse. The amphiphilic solid nano particle also has the function of amphiphilic molecules, and can ensure that two mutually insoluble phases are mutually soluble in an emulsifying way. After the chemical reaction is finished, the amphiphilic solid nano particles are easily separated from the final product in a centrifugal or filtering mode, and the separated amphiphilic solid nano particles can be recycled, so that the cost is greatly reduced.
At present, there are two main methods for synthesizing amphiphilic solid nanoparticles: the first is the ability to prepare an oil-water two-phase system with emulsification by precisely adjusting the ratio of hydrophilic part silicon to hydrophilic part carbon; the second is that the quaternary ammonium salt group is modified on the surface of the common solid particle to make the particle have the capacity of emulsifying an oil-water two-phase system. The amphiphilic particles synthesized by the first method have a narrow emulsification range, have the best emulsification effect on a selected oil-water two-phase system, and can greatly reduce the emulsification capacity on other two-phase systems; the second method for preparing the amphiphilic nano particle by modifying the quaternary ammonium salt group can have better emulsifying capacity for various oil-water two-phase systems, but the long chain of the quaternary ammonium salt group can block the pore channel of the solid nano particle, so that the inlet and outlet of reactants and products are influenced, and the long chain group can be broken under severe reaction conditions, so that the amphiphilic property of the particle is greatly reduced.
Disclosure of Invention
The invention aims to provide amphiphilic mesoporous organic salt nanoparticles, which are obtained by reacting mesoporous nanoparticles containing pyridine groups with hydrobromic acid, wherein the skeleton of the mesoporous organic salt nanoparticles contains a large number of organic groups with oleophilic capacity, and pyridine hydrogen cations with hydrophilic capacity, so that the mesoporous organic salt nanoparticles are an emulsifier capable of emulsifying various oil-water two-phase systems.
The invention is realized by the following technical scheme:
an amphiphilic mesoporous organic salt nanoparticle is prepared through hydrolyzing and polymerizing organic silane precursor containing pyridine group to obtain pyridine group mesoporous nanoparticles, and reacting with hydrobromic acid to obtain mesoporous organic salt nanoparticles.
The organosilane precursor containing the pyridine group is 2, 5-bis [ (E) -2- (triethoxysilyl) vinyl ] pyridine.
When the mesoporous organic salt nano particle is placed in water, ionic groups (pyridine hydrobromic acid groups) on the particle can be ionized into free bromine anions and pyridine hydrogen cations. The skeleton of the mesoporous organic salt nano particle contains a large number of organic groups with oleophilic ability, and the pyridine hydrogen cation has hydrophilic ability, wherein the amphiphilicity is derived from the oleophilic property of the organic groups and the hydrophilic property of the cation, and the mesoporous organic salt nano particle has a wider emulsification range. Meanwhile, the organic groups and the ionic groups of the mesoporous organic salt nanoparticles are in the framework, and the groups cannot block the pore channels of the solid nanoparticles, so that the inlet and the outlet of reactants and products are not influenced, and the amphipathy of the particles is more stable under severe reaction conditions.
In another aspect of the present invention, there is provided a method for preparing the amphiphilic mesoporous organic salt nanoparticles, comprising the steps of:
1) preparation of the precursor
Under nitrogen atmosphere, acetonitrile, 2, 5-divinyl pyridine and [ Rh (cod) Cl]2Mixing triphenylphosphine and triethoxysilane under stirring, filtering, concentrating, and distilling the concentrated solution to obtain precursor;
2) preparation of mesoporous organic salt
Mixing and stirring a template CTAB, water and ammonia water until the mixture is clear and transparent, heating and stirring in an oil bath, adding a precursor BTOSVP, centrifugally washing, adding into a hydrogen bromide solution, reacting and drying to obtain MOS solid nanoparticles.
Further, the reaction temperature condition in step 1) was 100 ℃.
Further, Kugelrohr distilling the concentrated solution in the step 1) at 190-200 ℃ under 30Pa to obtain a yellow oily liquid precursor.
Further, the heating temperature of the oil bath in the step 2) is 50 ℃.
The invention has the beneficial effects that:
the amphiphilic mesoporous organic salt prepared by the invention can emulsify various oil-water two-phase systems, and pyridine groups in a mesoporous nanoparticle framework react with hydrobromic acid to protonate the pyridine groups to obtain mesoporous nanoparticles containing a large number of organic groups and ionic groups in the framework, namely the mesoporous organic salt. When the mesoporous organic salt nano particle is placed in water, ionic groups (pyridine hydrobromic acid groups) on the particle can be ionized into free bromine anions and pyridine hydrogen cations, at the moment, a large number of organic groups contained in the skeleton of the mesoporous organic salt nano particle have oleophilic capacity, and the pyridine hydrogen cations have hydrophilic capacity, so that the mesoporous organic salt nano particle is an emulsifier capable of emulsifying various oil-water two-phase systems. The cations and organic groups which respectively play a hydrophilic role and a lipophilic role are in the skeleton of the particles, so that the pore channels of the particles cannot be blocked, and the inlet and outlet of reactants and products cannot be influenced.
Drawings
FIG. 1 is the diameter of the latex foam of particle 2 of example of the present invention and a comparison; a. b is the diameter of the milk foam before and after the comparative experiment of the particle 2; c. d is the diameter of the milk foam before and after the comparative experiment of the MOS particles.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 preparation of amphiphilic mesoporous organic salt nanoparticles
1) Preparation of 2, 5-bis (trimethylsilylethynyl) pyridine
250 ml round bottom flask is added with iPr2NH (120ml) and THF (40ml) were added under ice-bath conditions 2, 5-diiodopyridine (10g,30.2mmol), PdCl2(PPh3)2(0.85g, 1.21mmol), CuI (0.12g, 0.60 mmol). Trimethylacetylene silicon (11.8g, 121mmol) was added under argon atmosphere. Stirring at room temperature for 16 h. Insoluble matter was removed by filtration, and the filtrate was distilled under reduced pressure to obtain a concentrated solution. Silica gel chromatography (n-hexane/AcOEt ═ 10:1) was performed to isolate 2, 5-bis (trimethylsilylethynyl) pyridine (7.4g, 90%).
2) Preparation of 2, 5-divinylpyridine
2, 5-bis (trimethylsilylethynyl) pyridine was added to a THF (160mL) solution, then n-Bu4NF (1.0M THF solution, 60mL, 60mmol) solution was added to the above solution. Then a few drops of H are added2And O. The mixture was stirred at room temperature for 4H, distilled under reduced pressure, and then extracted with diethyl ether/H2And (4) extracting. The ether layer was washed several times with brine, MgSO4The mixture was dried overnight, and the solution was concentrated by distillation under reduced pressure. Silica gel chromatography (n-hexane/AcOEt ═ 3:1) was performed to isolate 2, 5-divinylpyridine (3.0g, 88%).
3) Preparation of 2, 5-bis [ (E) -2- (triethoxysilyl) vinyl ] pyridine
100 ml round bottom flask with CH3CN (27mL), under nitrogen atmosphere 2, 5-Divinylpyridine (0.30g, 2.36mmol), [ Rh (cod) Cl]2(23mg，0.047mmol)，PPh3(50mg, 0.19mmol) and triethoxysilane (1.55g, 9.44 mmol). Stirred at 100 ℃ for 24h, left to stand to room temperature, filtered through a bed of activated carbon and celite, and then distilled under reduced pressure. Kugelrohr distillation is carried out on the concentrated solution at 190-200 ℃ under 30Pa to obtain yellow oily liquidBTOSVP。
4) Preparation of Mesoporous Organic Salt (MOS)
In a typical synthesis, the templating agent CTAB (0.021g), water (9.74ml) and aqueous ammonia (0.26ml, 27 wt%) were added to a 50 ml round bottom flask and stirred at room temperature for 30min to give a clear and transparent solution. The round bottom flask was then placed in a 50 ℃ oil bath, and BTOSVP was added to the above solution with stirring, stirred for 6h, allowed to stand to cool to room temperature, and aged overnight. Centrifuging and washing the obtained product. The product was dispersed in an ethanol solution containing ammonium nitrate and refluxed for 6h (50 degrees centigrade) to remove the surfactant CTAB. Extraction was carried out three times, and 150mg of the product was added to 3 ml of hydrogen bromide solution and stirred. And after the reaction is finished, washing the reaction product for 3 times by using 50 ml of glacial acetic acid, and drying to obtain the MOS solid nanoparticles.
Example 2
Amphiphilic nanoparticles 1 and amphiphilic nanoparticles 2 were prepared by the first and second methods of the background art, respectively, particle 1 being prepared by the method in the literature (h.b.zuo, r.w.wang, j.y.dai, y.wang, x.wang, z.t.zhang and s.l.qiu, chem.commun.,2015,51, 14601-14604.); particle 2 was prepared by a method in the literature (N.Jungmann, M.Schmidt, J.Ebenhoch, J.Weis and M.Maskos, Angew.chem., int.Ed.,2003,42, 1714-.
The emulsification effect of particles 1, 2 and the MOS solid nanoparticles prepared in example 1 were tested in various oil-water biphasic systems. Fracture experiment: respectively placing 0.5 g of the particle 2 and the MOS in a 1M hydrochloric acid aqueous solution at 120 ℃ for refluxing for 3h, and then recovering the particle 2 and the MOS particles by centrifuging and washing. Emulsification experiment: experiment 1, 0.05 g of particle 2 and MOS were sonicated in a cuvette of 5 ml water and 5 ml n-hexane for 5 minutes, respectively. Experiment 2, 0.05 g of particle 2 and MOS were sonicated in a cuvette of 5 ml water and 5 ml toluene for 5 minutes, respectively. The emulsification effect, i.e. the diameter of the milk foam, was observed under a microscope. And the diameter of the milk foam before the rupture test. When the emulsification effect of the particles 1 is optimal for a two-phase system of n-hexane and water in a volume ratio of 1:1, the emulsification effect is not ideal for toluene and water in a volume ratio of 1: 1. The emulsifying effect of a two-phase system of p-methylbenzene and water is also not very desirable. It shows that the particle 1 can only have better emulsification effect on a specific oil-water two-phase system. While the emulsifying effect on other two-phase systems is greatly reduced. When the particles 2 and the MOS nanoparticles are used as the emulsifier, the emulsifier has a good emulsifying effect on various oil-water two-phase systems. It is shown that both the particles 2 having the modified quaternary ammonium salt group on the surface and the MOS particles prepared in the present application, the skeleton of which is composed of a large number of organic groups and ionic groups, have a wide emulsification effect.
Example 3
And (3) placing the particles 2 and the MOS particles in a 1M hydrochloric acid aqueous solution at 120 ℃ for refluxing for 3h, and then recovering the particles 2 and the MOS particles by centrifuging and washing. And then the emulsification effect of the two particles is tested. As shown in fig. 1, it was found that the emulsification effect of the particles 2 was reduced, but the emulsification effect of the MOS particles of the present application was almost unchanged, indicating that the groups modified on the surface of the particles 1 were partially cleaved under severe reaction conditions, and the amphiphilicity was reduced. The amphiphilic structure of the MOS particle with the framework formed by a large number of organic groups and ionic groups is more stable.
Example 4
Au @ Pd nanoparticles were encapsulated in a particle 2 shell and an MOS shell of a hollow structure to obtain egg yolk-shell structured amphiphilic nanoparticles, which were then tested for their catalytic performance in aerobic oxidation reaction of alcohol in an aqueous system.
When Au @ Pd @ particle 2 is used as a catalyst, 5h is needed when the conversion rate reaches 96 percent at most. And when Au @ Pd @ MOS is used as the catalyst, 2 hours are needed when the conversion rate reaches 99 percent. The organic groups and the ionic groups of the mesoporous organic salt nanoparticles are shown in the framework, and the groups can not block the pore channels of the solid nanoparticles, so that the inlet and outlet speeds of reactants and products are greatly improved. Namely, the MOS porous amphiphilic shell is really more beneficial to the inlet and outlet channels of substrates and products, so that the chemical reaction rate is greatly improved.
In summary, example 2 shows that both particle 2 having a modified quaternary ammonium salt group on the surface and MOS particles prepared in the present application, in which the skeleton is composed of a large number of organic groups and ionic groups, have a broad emulsification effect. Example 3 illustrates that the amphiphilic structure of the MOS particles prepared herein, whose backbone is composed of a large number of organic groups and ionic groups, is more stable. Example 4 shows that the organic groups and ionic groups of the mesoporous organic salt nanoparticles are in the framework, and these groups do not block the pore channels of the solid nanoparticles, so that the in-out speed of reactants and products is greatly increased. In summary, the MOS of the present application overcomes the disadvantages of the existing methods, and integrates the advantages of structural stability of the particles 1 and 2 prepared by the existing methods and the advantages of having a wider emulsification range.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. An amphiphilic mesoporous organic salt nanoparticle is characterized in that an organosilane precursor containing a pyridine group is hydrolyzed and polymerized to obtain a pyridine group-containing mesoporous nanoparticle, and the pyridine group-containing mesoporous nanoparticle and hydrobromic acid are used to obtain the mesoporous organic salt nanoparticle.
2. The amphiphilic mesoporous organic salt nanoparticle of claim 1, wherein the organosilane precursor containing a pyridine group is 2, 5-bis [ (E) -2- (triethoxysilyl) vinyl ] pyridine.
3. The method for preparing amphiphilic mesoporous organic salt nanoparticles of claim 1, wherein the amphiphilic mesoporous organic salt nanoparticles are prepared by the following steps,
1) preparation of the precursor
Under nitrogen atmosphere, acetonitrile, 2, 5-divinyl pyridine and [ Rh (cod) Cl]2Mixing triphenylphosphine and triethoxysilane under stirring, filtering, concentrating, and distilling the concentrated solution to obtain precursor;
2) preparation of mesoporous organic salt
Mixing and stirring a template CTAB, water and ammonia water until the mixture is clear and transparent, heating and stirring in an oil bath, adding a precursor BTOSVP, centrifugally washing, adding into a hydrogen bromide solution, reacting and drying to obtain MOS solid nanoparticles.
4. The method according to claim 3, wherein the reaction temperature condition in the step 1) is 100 ℃.
5. The preparation method according to claim 3, wherein the concentrated solution in step 1) is subjected to Kugelrohr distillation at 190-200 ℃ per 30Pa to obtain a yellow oily liquid precursor.
6. The method according to claim 3, wherein the heating temperature of the oil bath in the step 2) is 50 ℃.
CN202110163029.1A 2021-02-05 2021-02-05 Amphiphilic mesoporous organic salt nano particle and preparation method thereof Pending CN112961353A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110163029.1A CN112961353A (en) 2021-02-05 2021-02-05 Amphiphilic mesoporous organic salt nano particle and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110163029.1A CN112961353A (en) 2021-02-05 2021-02-05 Amphiphilic mesoporous organic salt nano particle and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112961353A true CN112961353A (en) 2021-06-15

Family

ID=76274629

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110163029.1A Pending CN112961353A (en) 2021-02-05 2021-02-05 Amphiphilic mesoporous organic salt nano particle and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112961353A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101443048A (en) * 2004-04-20 2009-05-27 德瑞迪克纳米科技公司 Dendritic polymers with enhanced amplification and interior functionality
CN109876860A (en) * 2019-03-14 2019-06-14 吉林大学 A kind of preparation method of amphiphilic catalyst TS-1@AOF

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101443048A (en) * 2004-04-20 2009-05-27 德瑞迪克纳米科技公司 Dendritic polymers with enhanced amplification and interior functionality
CN109876860A (en) * 2019-03-14 2019-06-14 吉林大学 A kind of preparation method of amphiphilic catalyst TS-1@AOF

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
M. WAKI等: "Ionic conductivity of mesoporous electrolytes with a high density of pyridinium groups within their framework", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
MINORU WAKI等: "Crystal-like periodic mesoporous organosilica bearing pyridine units within the framework", 《CHEMICAL COMMUNICATIONS》 *

Similar Documents

Publication Publication Date Title
Calabrese et al. POSS nanostructures in catalysis
CN112121853B (en) Mesoporous hollow silica nanosphere loaded with prolinol catalyst as well as preparation method and application of mesoporous hollow silica nanosphere
CN109607554B (en) Preparation method of microporous mesoporous silica nanoparticles
CN101049575A (en) Solid carried multilaminar ion liquid, preparation method and application
CA2499782A1 (en) Sol gel functionalized silicate catalyst and scavenger
CN112280052B (en) Hierarchical pore ZIF-8 material and preparation method and application thereof
King et al. Heterogeneous and solid supported dendrimer catalysts
Sims et al. Morphosynthesis of macroporous silica frameworks in bicontinuous microemulsions
CN108329486A (en) A kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure
CN105854942A (en) Method for preparing sulfonic acid group-modified mesoporous material-loaded heteropolyacid catalyst and application thereof during esterification reaction
CN111085267A (en) A kind of polymer supported Cu/TEMPO catalyst and its preparation method and application
CN109400903B (en) Cage-type polysilsesquioxane/metal-2-amino terephthalic acid organic framework hybrid material and preparation method thereof
Yuan et al. Ionic liquids enable highly efficient Knoevenagel reaction by dual-responsive emulsion microreactor
US12134087B2 (en) Method for preparing pickering miniemulsion and its catalytic application
Zhang et al. Synthesis and catalytic applications of mesoporous polymer colloids in olefin hydrosilylation
CN111253425B (en) Synthesis method of 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane
CN112934267A (en) Alkylated hydrophobic MOFs material and application thereof in cyclohexene hydration
CN112961353A (en) Amphiphilic mesoporous organic salt nano particle and preparation method thereof
Chen et al. A simple strategy towards the preparation of a highly active bifunctionalized catalyst for the deacetalization reaction
CN110172158B (en) A kind of preparation method of graded porous metal organic framework material MIL-101(Cr)
CN104258813B (en) A kind of preparation method of mesoporous double-deck organic silicon sphere
JP2008222584A (en) Preparation of imine compounds
CN101564687A (en) In situ synthesis of ultramicroporous supported platinum catalysts and solvent-free microwave hydrosilylation
CN109876860B (en) Preparation method of amphiphilic catalyst TS-1@ AOF
CN101972670A (en) Hydrophobic adjustable multi-phase asymmetric catalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210615