CN110180474A - The preparation method and product of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary - Google Patents
The preparation method and product of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary Download PDFInfo
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- CN110180474A CN110180474A CN201910473954.7A CN201910473954A CN110180474A CN 110180474 A CN110180474 A CN 110180474A CN 201910473954 A CN201910473954 A CN 201910473954A CN 110180474 A CN110180474 A CN 110180474A
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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
- B01J13/02—Making microcapsules or microballoons
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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
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/415—Sonogashira / Hagihara reactions
Abstract
The present invention relates to a kind of preparation methods and products thereof of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, it is put forward for the first time in the synthesis for applying to microporous polymer nano material using titanium dioxide nanometer microballoons as nanotopography controlling agent, disclose a kind of using the titanium dioxide nanometer microballoons that partial size is 100-500 nm or so as auxiliary, the method that the microporous polymer nano-hollow microballoon that partial size is 100-500 nm or so is synthetically prepared by transition metal-catalyzed metal coupling reaction in the solution.The method is simple to operation, stability is good, yield is high, and the polymer nanocomposite tiny balloon pattern synthesized is uniform.
Description
Technical field
The present invention relates to a kind of preparation methods of micropore organic polymer nano-hollow microballoon.More particularly to a kind of titanium dioxide
The preparation method and product of the micropore organic polymer nano-hollow microballoon of titanium nanosphere auxiliary.
Background technique
Micropore organic polymer material belongs to one kind of porous organic polymer material, mainly utilize two kinds containing multiple
The rigid organic monomer molecule of reaction site is synthetically prepared in the solution, does not dissolve in any organic solvent, and when synthesis is used
Polymerization reaction is mainly Sonogashira coupling reaction, Oxidative coupling reaction and Yamamoto coupling reaction etc..Due to
It is to be cross-linked with each other to be polymerized by two kinds of rigid organic monomer molecules, and at three dimensional network structure between strand, therefore
Its material itself contains microcellular structure.In addition to this, since the polymerization process of two kinds of rigid molecules is mixed and disorderly unordered more reactions
Site dissipates polymerization simultaneously, therefore, finally synthesize the microscopic appearance of obtained material be it is mixed and disorderly unordered, mainly by nanosphere,
Nanometer sheet, nano wire and irregular nano particle composition.
Since the microcosmic nanotopography of micropore organic polymer material is disorderly and unsystematic, it is hindered in catalysis, the energy, environment
And the application in the fields such as photoelectric sensor, people do a lot of work in terms of the control synthesis of its nanotopography in recent years, than
Synthetic microporous polymer nanocomposite film, the synthetic microporous polymer nano rice noodles of regulation monomer molecule structure are such as controlled by template and are received
Rice ball etc..But since above method operates extremely complex, it is difficult widely to be promoted, for example close by regulatory molecule structure
It is related to complicated Molecular Design and organic synthesis process at the method for microporous polymer nano wire or nanosphere, it is not only time-consuming
Length, yield is very low and nanotopography controllability is bad, therefore greatly limits its popularization and application.Currently, a kind of letter not yet
It is single effectively, the good method of stability realize the synthesis of micropore organic polymer nano-hollow microballoon.
Present invention firstly provides a kind of using the titanium dioxide nanometer microballoons that partial size is 100-500 nm or so as auxiliary
It helps, the method for being synthetically prepared microporous polymer nano-hollow microballoon.Titanium dioxide nanometer microballoons are that a kind of partial size is 100-500
The spheric granules of nm, titanium dioxide nanometer microballoons play a kind of work of spherical nuclei during microporous polymer molecular growth
With microporous polymer strand can be adsorbed on titanium dioxide using titanium dioxide nanometer microballoons as core during aggregation growth
Gradually aggregation growth becomes microporous polymer nanosphere to microsphere surface, is then carved titanium dioxide nanometer microballoons using hydrofluoric acid
Etching off removes, and micropore organic polymer nano-hollow ball can be obtained.The method is simple to operation, stability is good, yield is high, and
The polymer nanocomposite tiny balloon pattern of synthesis is uniform.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of micropores of titanium dioxide nanometer microballoons auxiliary to have
The preparation method of machine polymer nanocomposite tiny balloon.
Another object of the present invention is: providing a kind of micropore of the titanium dioxide nanometer microballoons auxiliary of above method preparation
Organic polymer nano-hollow microspheres product.
The object of the invention passes through following proposal and realizes: a kind of micropore organic polymer of titanium dioxide nanometer microballoons auxiliary is received
The preparation method of rice tiny balloon, it is characterised in that the specific steps of this method are as follows:
A, the organic solvent for ultrasonic dispersion 5-10 min that a certain amount of titanium dioxide microballoon sphere is added to certain volume is weighed；
B, according to the requirement of transition metal-catalyzed metal coupling reaction, select two kinds of rigid organic molecule monomers former as polymerization
Material, weighs the above monomer according to reaction ratio and is added in the organic solvent dissolved with silica solution, after stirring 5-10 min, Xiang Qi
It is middle that the required catalyst of reaction is added；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, it is to slowly warm up to set temperature, and quickly stir；
E, solid powder is filtered and collected after reacting 6h, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, uses vacuum oven
Dry 12h；
F, obtained powder made above is added in hydrofluoric acid solution and is stirred to react 6h, it is therefore an objective to which nano titania is micro-
Ball etching removal, can obtain microporous polymer nano-hollow microballoon.
The particle size range of the titanium dioxide is 100-500 nm, the solvents of titanium dioxide nanometer microballoons be benzene, toluene,
The benzene class organic solvent such as dimethylbenzene.
The described transition metal-catalyzed metal coupling reaction type include: Sonogashira coupling reaction,
Oxidative coupling reaction, Yamamoto coupling reaction, Suzuki coupling reaction etc..Reaction needed for organic monomer molecule and
Catalyst type is selected according to the type of the above metal coupling reaction.
The present invention provides a kind of micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, according to upper
Any the method is stated to be prepared.
The titanium dioxide nanometer microballoons that partial size is 100-500 nm or so are utilized for the first time and are used as auxiliary by the present invention, pass through
The metal coupling reaction for crossing metal catalytic has been synthetically prepared the microporous polymer that partial size is 100-500 nm or so in the solution and has received
Rice tiny balloon.Titanium dioxide nanometer microballoons are a kind of spheric granules that partial size is 100-500 nm, in microporous polymer molecule
Play the role of a kind of spherical nuclei during growth, microporous polymer strand can be with titanium dioxide during aggregation growth
Titanium nanosphere is core, and being adsorbed on its surface, gradually aggregation growth becomes microporous polymer nanosphere, then utilizes hydrofluoric acid
Titanium dioxide nanometer microballoons are dissolved and are removed, microporous polymer nano-hollow microballoon has been finally obtained.The method is simple to operation,
Stability is good, yield is high, and the polymer nanocomposite tiny balloon pattern synthesized is uniform.
Detailed description of the invention
Fig. 1 is the TEM figure for the microporous polymer nano-hollow microballoon that the embodiment of the present invention 1 synthesizes；
Fig. 2 is the TEM figure for the microporous polymer nano-hollow microballoon that the embodiment of the present invention 2 synthesizes；
Fig. 3 is the TEM figure for the microporous polymer nano-hollow microballoon that the embodiment of the present invention 3 synthesizes.
Specific embodiment
The present invention is described in detail below by specific example, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment 1
A kind of micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, is prepared according to the following steps:
A, weighing 2.0g partial size is about that 300 nm or so are dispersed in the xylene solvent that silica solution in toluene solvant is added to 20 ml
Middle 10 min of ultrasonic disperse, obtains the dispersion liquid of silica solution；
B, according to the requirement of Sonogashira coupling reaction, the 1 of 52 mg is weighed, the 4 of 3,5- tri- acetylene benzene monomers and 135mg,
4 '-two kinds of diiodide monomers rigidity organic molecule monomer is added in the dispersion liquid of above-mentioned silica solution, stirs as polymer raw
After mixing 5 min, the triphenylphosphine palladium and cuprous iodide catalyst and 10 ml triethylamines of catalytic amount are added thereto；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 60 DEG C and is quickly stirred；
E, solid is filtered and collects after reacting 6h, it is dry with vacuum oven after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol
12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution the microporous polymer for being stirred to react 6h, synthesizing
The TEM figure of object nano-hollow microballoon, product is shown in Fig. 1.
Embodiment 2
A kind of micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, is prepared according to the following steps:
A, weigh 2.0g partial size be about 200 nm or so be dispersed in silica solution in toluene solvant be added to 20 ml dimethylbenzene it is molten
10 min of ultrasonic disperse in agent；
B, according to the requirement of Sonogashira coupling reaction, weigh 109 mg Isosorbide-5-Nitrae-diiodo- benzene monomer and 52 mg 1,3,5-
Three two kinds of acetylene benzene monomers rigidity organic molecule monomer is added in the dispersion liquid of above-mentioned silica solution, stirring 5 as polymer raw
After min, the triphenylphosphine palladium and cuprous iodide catalyst and 10 ml triethylamines of catalytic amount are added thereto；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 60 DEG C and is quickly stirred；
E, reaction solution is filtered after reacting 6h, and collects solid, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, with vacuum drying
Case dries 12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution the microporous polymer for being stirred to react 6h, synthesizing
The TEM figure of object nano-hollow microballoon, product is shown in Fig. 2.
Embodiment 3
A kind of micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, is prepared according to the following steps:
A, weighing 2.0g partial size is about that 150 nm or so are dispersed in silica solution in toluene solvant and are added in the toluene solvant of 40 ml
10 min of ultrasonic disperse；
B, according to the requirement of Suzuki coupling reaction, weigh the 1 of 91 mg, 3,5- triiodo benzene monomers and 50 mg to benzene hypoboric acid
Two kinds of monomer rigid organic molecule monomers are added in the dispersion liquid of above-mentioned silica solution, ultrasonic disperse 10 as polymer raw
After min, triphenylphosphine palladium catalyst and the 1 ml concentration that catalytic amount is added thereto are the potassium carbonate of 10 mg/ml
Aqueous solution, and 5 min of ultrasonic dissolution；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 90 DEG C and is quickly stirred；
E, reaction solution is filtered after reacting 6h and collects solid, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, with vacuum drying
Case dries 12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution and is stirred to react 6h.Synthesize obtained microporous polymer
The TEM figure of object nano-hollow microballoon, product is shown in Fig. 3.
Claims (7)
1. a kind of preparation method of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, feature exist
In the specific steps of this method are as follows:
A, the organic solvent for ultrasonic dispersion 5-10 min that a certain amount of titanium dioxide microballoon sphere is added to certain volume is weighed；
B, according to the requirement of transition metal-catalyzed metal coupling reaction, select two kinds of rigid organic molecule monomers former as polymerization
Material, weighs the above monomer according to reaction ratio and is added in the organic solvent dissolved with silica solution, after stirring 5-10 min, Xiang Qi
It is middle that the required catalyst of reaction is added；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, it is to slowly warm up to set temperature, and quickly stir；
E, solid powder is filtered and collected after reacting 6h, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, uses vacuum oven
Dry 12h；
F, obtained powder made above is added in hydrofluoric acid solution and is stirred to react 6h, it is therefore an objective to which nano titania is micro-
Ball etching removal, can obtain microporous polymer nano-hollow microballoon.
2. the preparation of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary according to claim 1
Method, which is characterized in that the particle size range of the titanium dioxide is 100-500 nm, and the solvent of titanium dioxide nanometer microballoons is
The benzene class organic solvent such as benzene,toluene,xylene.
3. the preparation of the micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary according to claim 1
Method, it is characterised in that the described transition metal-catalyzed metal coupling reaction type include: Sonogashira coupling reaction,
Oxidative coupling reaction, Yamamoto coupling reaction, Suzuki coupling reaction etc..Reaction needed for organic monomer molecule and
Catalyst type is selected according to the type of the above metal coupling reaction.
4. the micropore organic polymer nano-hollow of titanium dioxide nanometer microballoons auxiliary according to any one of the claim 1 to 3
The preparation method of microballoon, which is characterized in that be prepared according to the following steps:
A, weighing 2.0g partial size is about that 300 nm or so are dispersed in the xylene solvent that silica solution in toluene solvant is added to 20 ml
Middle 10 min of ultrasonic disperse, obtains the dispersion liquid of silica solution；
B, according to the requirement of Sonogashira coupling reaction, the 1 of 52 mg is weighed, the 4 of 3,5- tri- acetylene benzene monomers and 135mg,
4 '-two kinds of diiodide monomers rigidity organic molecule monomer is added in the dispersion liquid of above-mentioned silica solution, stirs as polymer raw
After mixing 5 min, the triphenylphosphine palladium and cuprous iodide catalyst and 10 ml triethylamines of catalytic amount are added thereto；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 60 DEG C and is quickly stirred；
E, solid is filtered and collects after reacting 6h, it is dry with vacuum oven after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol
12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution the microporous polymer for being stirred to react 6h, synthesizing
Object nano-hollow microballoon.
5. the micropore organic polymer nano-hollow of titanium dioxide nanometer microballoons auxiliary according to any one of the claim 1 to 3
The preparation method of microballoon, which is characterized in that be prepared according to the following steps:
A, weigh 2.0g partial size be about 200 nm or so be dispersed in silica solution in toluene solvant be added to 20 ml dimethylbenzene it is molten
10 min of ultrasonic disperse in agent；
B, according to the requirement of Sonogashira coupling reaction, weigh 109 mg Isosorbide-5-Nitrae-diiodo- benzene monomer and 52 mg 1,3,5-
Three two kinds of acetylene benzene monomers rigidity organic molecule monomer is added in the dispersion liquid of above-mentioned silica solution, stirring 5 as polymer raw
After min, the triphenylphosphine palladium and cuprous iodide catalyst and 10 ml triethylamines of catalytic amount are added thereto；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 60 DEG C and is quickly stirred；
E, reaction solution is filtered after reacting 6h, and collects solid, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, with vacuum drying
Case dries 12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution the microporous polymer for being stirred to react 6h, synthesizing
Object nano-hollow microballoon.
6. the micropore organic polymer nano-hollow of titanium dioxide nanometer microballoons auxiliary according to any one of the claim 1 to 3
The preparation method of microballoon, which is characterized in that be prepared according to the following steps:
A, weighing 2.0g partial size is about that 150 nm or so are dispersed in silica solution in toluene solvant and are added in the toluene solvant of 40 ml
10 min of ultrasonic disperse；
B, according to the requirement of Suzuki coupling reaction, weigh the 1 of 91 mg, 3,5- triiodo benzene monomers and 50 mg to benzene hypoboric acid
Two kinds of monomer rigid organic molecule monomers are added in the dispersion liquid of above-mentioned silica solution, ultrasonic disperse 10 as polymer raw
After min, triphenylphosphine palladium catalyst and the 1 ml concentration that catalytic amount is added thereto are the potassium carbonate of 10 mg/ml
Aqueous solution, and 5 min of ultrasonic dissolution；
C, after catalyst is added, by vacuumize-operation of inflated with nitrogen comes out the air displacement in reaction solution；
D, then under nitrogen protection, above-mentioned reaction solution is warming up to 90 DEG C and is quickly stirred；
E, reaction solution is filtered after reacting 6h and collects solid, after successively being rinsed with acetone, tetrahydrofuran, ethyl alcohol, with vacuum drying
Case dries 12h；
F, obtained powder made above is added in 3% hydrofluoric acid solution and is stirred to react 6h.Synthesize obtained microporous polymer
Object nano-hollow microballoon.
7. a kind of micropore organic polymer nano-hollow microballoon of titanium dioxide nanometer microballoons auxiliary, it is characterised in that according to right
It is required that any the method for 1-6 is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110646526A (en) * | 2019-09-11 | 2020-01-03 | 山东省分析测试中心 | Enrichment analysis method of perfluorinated compounds in food based on magnetic microporous organic network composite material |
| CN110668423A (en) * | 2019-10-08 | 2020-01-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano hollow carbon spheres with uniform particle size |
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Application publication date: 20190830 |
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