CN104707576A - Poly(aminostyrene)@silicon oxide nano material and preparation method thereof - Google Patents
Poly(aminostyrene)@silicon oxide nano material and preparation method thereof Download PDFInfo
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- CN104707576A CN104707576A CN201310689158.XA CN201310689158A CN104707576A CN 104707576 A CN104707576 A CN 104707576A CN 201310689158 A CN201310689158 A CN 201310689158A CN 104707576 A CN104707576 A CN 104707576A
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Abstract
The invention relates to a poly(aminostyrene)@silicon oxide nano material and a preparation method thereof. The preparation method comprises the following specific preparation steps: at a certain temperature and in an acid solvent system, adopting concentrated nitric acid as a nitration reagent, nitrifying a yolk-eggshell type nano material with an inner core of polystyrene balls and an outer shell of silicon oxide, then reducing nitro into amino by a reducing reagent, filtering, washing, drying, and finally obtaining the poly(aminostyrene)@silicon oxide nano material. The process involved in the method is simple, the operation steps are few, and the raw materials are cheap and easy to get. The poly(aminostyrene)@silicon oxide nano material has the weight ratio of the polymer to silicon oxide of 0.1-3, the N content of 0.2-3 mmol/g and the particle size of 30-3000 nm, and has the yolk-eggshell structure. In addition, the material has a certain adsorption capacity on carbon dioxide, and has a certain application prospect in the field of carbon dioxide gas adsorption and separation.
Description
Technical field
The present invention relates to a kind of polymer/silica composite hybridization nano material, specifically a kind of poly-aminostyryl@monox nanometer material and preparation method thereof.
Background technology
The polymeric material of amino functional, due to the avtive spot on its amino, makes the fields such as it is immobilized at homogeneous catalyst, carbon dioxide trapping be with a wide range of applications (ChemicalReviews, the 109th volume, the 815th – 838 pages in 2009; Angewandte ChemieInternational Edition, 2012, the 51st volume, 7480-7484 page; Journal of theAmerican Chemical Society, 2012, the 134th volume, 10757-10760 page).And the polymer of amino functional changes the hydrophilic and hydrophobic of polymer due to the hydrophily of amino, has expanded the application of functional polymer in the field such as catalysis, absorption.At present, although aminoethyl resin has the commercially produced product of polystyrene type and Tentagel form, then the polymer of corresponding aminofunctional is not still (Journal of CombinatorialChemistry, 2007 cheap and easy to get, 7th volume, the 1012nd – 1027 pages).Due to pure amino functional fluidized polymer because heat endurance own is low, specific area is little, be easy to the shortcoming such as swelling in organic solvent and limit its application in the field such as catalysis, absorption.In order to improve heat endurance, the specific area and resistance to swelling etc. of polymer, inorganic nano-particle such as silica is often incorporated in polymer by as additive.In recent years, in order to expand the application of amino functional fluidized polymer, different types of amino functional fluidized polymer-silica composite material prepare extensive concern.The method of conventional synthesis polymer-silica composite material mainly comprises silica and directly adds in the course of the polymerization process and carry out two large class methods (the Chemical Communications such as polymerization in silicon oxide nano pore, 2013,49 volumes, 11776-11778 page).But be difficult under high polymer content, keep high-ratio surface sum large pore volume by polymer-silica composite material prepared by said method.
Summary of the invention
The object of this invention is to provide one simply controlled, by a kind of poly-aminostyryl@monox nanometer material of the method preparation of p-poly-phenyl ethene ball nitration-reduction amination and preparation method thereof.Method of the present invention can effectively overcome in existing technology of preparing be difficult to keep high-ratio surface sum large pore volume under high polymer content, long and may containing shortcomings such as other functional groups are residual to raw material complexity, sluggish, production cycle, the poly-aminostyryl monox nanometer material that simultaneously the present invention relates to has high-specific surface area (550-650m
2/ g), high polymer content (10-75wt%) and yolk-eggshell nanostructured.In addition, this material has certain adsorption capacity to carbon dioxide, has certain application prospect in carbon dioxide absorption with separation field.
For achieving the above object, the present invention is at a certain temperature, under acid flux material system, employing red fuming nitric acid (RFNA) is nitrating agent, be polystyrene spheres by kernel, shell is that the yolk-eggshell type organic-inorganic hybrid material of silica is nitrated, then with reproducibility reagent, nitroreduction is become amino, finally obtain poly-aminostyryl monox nanometer material through filtration, washing, drying.
Specifically can operate as follows:
(1) in the cryostat of 0 DEG C under stirring condition, to be polystyrene spheres containing kernel, shell is add nitrating agent in the acid solution of the yolk-eggshell type organic-inorganic hybrid material of silica, directly transferred in the oil bath at 30-80 DEG C of temperature and stirred 2-12h, suction filtration after room temperature is cooled to rapidly afterwards with ice-water bath, use deionized water, ethanol cyclic washing 3 times respectively, dry 24h at 60-100 DEG C, has namely obtained the polystyrene@monox nanometer material of nitro functionalization;
(2) by the polystyrene@monox nanometer dispersion of materials of obtained nitro functionalization in polar solvent, add reducing agent, return stirring 12-48h at 50-120 DEG C of temperature, be cooled to room temperature subsequently, suction filtration, successively with the washing of ethanol, deionized water, aqueous slkali, deionized water and ethanol, dry, i.e. obtained poly-aminostyryl@monox nanometer material.
In poly-aminostyryl@monox nanometer material involved in the present invention, the weight ratio of polymer and silica is between 0.1-3, and N content is between 0.2-3mmol/g, and granularity is between 30-3000nm, and have yolk-eggshell structure, specific area is at 550-650m
2between/g, pore volume is at 0.2-0.5m
3between/g.The yolk-eggshell type hybrid material that described yolk-eggshell type organic-inorganic hybridization silicon oxide is kernel is polystyrene spheres, shell is silica; Nitrating agent is red fuming nitric acid (RFNA); Acid flux material in nitrifying process is a kind of in trifluoroacetic acid, hydrochloric acid, sulfuric acid or their mixture; In nitrifying process, the ratio of solid material and acid solution, nitrating agent is: 30-80mg has yolk-eggshell type organic-inorganic hybrid material, 5-10ml acid solution and the 10-50 μ L nitrating agent that kernel is polystyrene spheres, shell is silica; Reducing agent is a kind of in lithium aluminium hydride reduction, sodium borohydride, stannous chloride or their mixture; Solid material and polar solvent in reduction process, the ratio of going back original reagent are: the polystyrene monox nanometer material of 30-80mg nitro functionalization, 10-20ml polar solvent and 300-600mg also original reagent; Polar solvent in reduction nitro process is a kind of in water, ethanol, N, N-dimethylformamide, oxolane or their mixture.
Preparation method's tool of the present invention has the following advantages:
1. the method raw material is simple and easy to get, and course of reaction is simple, mild condition;
2. the method preparation process does not relate to the operations such as anhydrous and oxygen-free, is easy to operation, is suitable for large-scale industrial production;
Material tool prepared by the present invention has the following advantages:
1. the material that the present invention relates to is a kind of organic-inorganic hybrid nano material, has both had the structural rigidity of inorganic material, and mechanical stability is strong, has again the active site of amination organic polymer.
2. the polymer of the material amino functional that the present invention relates to has the outer field protection of silica, and stability is high, and solvent resistant erosiveness is strong;
3. the poly-aminostyryl@monox nanometer material that the present invention relates to has high-specific surface area, large pore volume and high polymer content.
Accompanying drawing explanation
Fig. 1 is poly-aminostyryl@monox nanometer material nitrogen adsorption curve and pore-size distribution in embodiment 1.
Fig. 2 is poly-aminostyryl@monox nanometer material transmission electromicroscopic photograph in embodiment 1.
Fig. 3 is the transmission electron microscope photo of poly-aminostyryl@monox nanometer material after N, N-dimethylformamide (a), acetone (b) process in embodiment 1.
Fig. 4 is poly-aminostyryl@monox nanometer material transmission electromicroscopic photograph in embodiment 2.
Fig. 5 is poly-aminostyryl@monox nanometer material transmission electromicroscopic photograph in embodiment 3.
Fig. 6 is poly-aminostyryl@monox nanometer material transmission electromicroscopic photograph in embodiment 4.
Fig. 7 is poly-aminostyryl@monox nanometer material transmission electromicroscopic photograph in embodiment 5.
Fig. 8 be in embodiment 6 material at 25,75,100 DEG C of absorbing carbon dioxide quality change curve in time.
Detailed description of the invention
In order to further illustrate the present invention, enumerate following embodiment, but it does not limit the invention scope that each accessory claim defines.
Embodiment 1
In the cryostat of 0 DEG C under stirring condition, to be polystyrene spheres containing kernel, shell is add concentrated nitric acid solution in the trifluoroacetic acid solution of the yolk-eggshell type organic-inorganic hybrid material of silica, wherein: each component is: 55mg solid material, 8ml trifluoroacetic acid and 25 μ L red fuming nitric acid (RFNA)s, transferred to subsequently in the oil bath at 50 DEG C and stirred 4h, be cooled to rapidly suction filtration after room temperature with ice-water bath afterwards, use deionized water, ethanol cyclic washing respectively.Dry 24h at 100 DEG C, has obtained the yolk@eggshell type organic-inorganic hybridization silicon oxide nanosphere material of nitro functionalization; Then the polystyrene@silica organic-inorganic hybrid nano material of obtained nitro functionalization is dispersed in tetrahydrofuran solution, add the stannous chloride of 490mg as reducing agent, 90 DEG C of return stirring 24h, be cooled to room temperature subsequently, suction filtration, with ethanol, deionized water, 10% sodium hydroxide solution, deionized water, ethanol washing, dry afterwards, i.e. obtained poly-aminostyryl@monox nanometer material.The alkali number of this material is 1.01mmol/g, and specific area is 571m
2/ g, pore volume is 0.47m
3/ g, Fig. 1 are nitrogen adsorption curve and the pore size distribution curve of material.Transmission electron microscope results display material is yolk-eggshell shaped material (Fig. 2).Material is after N, N-dimethylformamide, the process of acetone equal solvent, and material just there occurs swelling (Fig. 3), and organic component is substantially without loss.
Embodiment 2
Adopt the preparation process of embodiment 1, being to reduce in nitro process with its difference is dispersed in ethanolic solution by the polystyrene@silica organic-inorganic hybrid nano material of obtained nitro functionalization, add the stannous chloride of 490mg as reducing agent, 90 DEG C of return stirring 24h, be cooled to room temperature subsequently, suction filtration, with ethanol, deionized water, 10% sodium hydroxide solution, deionized water, ethanol washing, dry afterwards, i.e. obtained poly-aminostyryl@monox nanometer material.The material obtained is yolk-eggshell shaped material, as shown in Figure 4.
Embodiment 3
Adopt the preparation process of embodiment 1, be to reduce in nitro process with its difference and the polystyrene@silica organic-inorganic hybrid nano material of obtained nitro functionalization is dispersed in N, in N-DMF solution, add the stannous chloride of 490mg as reducing agent, 90 DEG C of return stirring 24h, be cooled to room temperature subsequently, suction filtration, with ethanol, deionized water, 10% sodium hydroxide solution, deionized water, ethanol washing, dry afterwards, i.e. obtained poly-aminostyryl@monox nanometer material.The material obtained is yolk-eggshell shaped material, as shown in Figure 5.
Embodiment 4
Adopt the preparation process of embodiment 1, be that with its difference time lengthening nitrated in the oil bath at 50 DEG C is 8h, be cooled to rapidly suction filtration after room temperature with ice-water bath afterwards, use deionized water, ethanol cyclic washing respectively.Dry 24h at 100 DEG C, has obtained the yolk-eggshell type organic-inorganic hybridization silicon oxide nanosphere material of nitro functionalization; Then by the polystyrene@monox nanometer dispersion of materials of obtained nitro functionalization in tetrahydrofuran solution, add the stannous chloride of 490mg as reducing agent, 90 DEG C of return stirring 24h, be cooled to room temperature subsequently, suction filtration, with ethanol, deionized water, 10% sodium hydroxide solution, deionized water, ethanol washing, dry afterwards, i.e. obtained poly-aminostyryl@monox nanometer material, the material obtained has yolk-eggshell type structure, as shown in Figure 6.
Embodiment 5
Adopt the preparation process of embodiment 1, be that with its difference time lengthening nitrated in the oil bath at 50 DEG C is 12h, be cooled to rapidly suction filtration after room temperature with ice-water bath afterwards, use deionized water, ethanol cyclic washing respectively.Dry 24h at 100 DEG C, has obtained the polystyrene@monox nanometer material of nitro functionalization; Then the polystyrene@silica organic-inorganic hybrid nano material of obtained nitro functionalization is dispersed in tetrahydrofuran solution, add the stannous chloride of 490mg as reducing agent, 90 DEG C of return stirring 24h, be cooled to room temperature subsequently, suction filtration, with ethanol, deionized water, 10% sodium hydroxide solution, deionized water, ethanol washing, dry afterwards, i.e. obtained poly-aminostyryl@monox nanometer material, the material obtained is yolk-eggshell shaped material, as shown in Figure 7.
Embodiment 6
Adopt the material prepared of embodiment 1, application and carbon dioxide adsorb.First aminostyryl@monox nanometer material processed 2h under 120 DEG C of nitrogen atmospheres will be gathered, then adsorption temp (being respectively 25,75,100 DEG C) is down to, pass into carbon dioxide with 30ml/min, measure the weight increased with thermogravimetric, carbon dioxide adsorption quality as shown in Figure 8.
The present invention relates to a kind of poly-aminostyryl@monox nanometer material and preparation method thereof.Concrete preparation process is as follows: at a certain temperature, under acid flux material system, employing red fuming nitric acid (RFNA) is nitrating agent, be polystyrene spheres by kernel, shell is that the yolk-eggshell type organic-inorganic hybrid material of silica is nitrated, then with reproducibility reagent, nitroreduction is become amino, finally obtains poly-aminostyryl monox nanometer material through filtration, washing, drying.Technique involved by the method is simple, and operating procedure is few, and cheaper starting materials is easy to get.The polymer of this material and the weight ratio of silica are between 0.1-3, and N content is between 0.2-3mmol/g, and granularity, between 30-3000nm, has yolk-eggshell structure.Specific area is at 550-650m
2between/g, pore volume is at 0.2-0.5m
3between/g, there is higher stability in organic solvent, run off few.In addition, this material has certain adsorption capacity to carbon dioxide, has certain application prospect in carbon dioxide absorption with separation field.
Claims (8)
1. a poly-aminostyryl monox nanometer material, is characterized in that: have yolk-eggshell structure, and granularity is between 30-3000nm, and the weight ratio of polymer and silica is between 0.1-3, and N content is between 0.2-3mmol/g.
2. a preparation method for poly-aminostyryl monox nanometer material, is characterized in that comprising following preparation process:
(1) in the cryostat of 0 DEG C under stirring condition, to be polystyrene spheres containing kernel, shell is add nitrating agent in the acid solution of the yolk-eggshell type organic-inorganic hybrid material of silica, directly transferred in the oil bath at 30-80 DEG C of temperature and stirred 2-12h, suction filtration after room temperature is cooled to rapidly afterwards with ice-water bath, use deionized water, ethanol cyclic washing 3 times respectively, dry 24h at 60-100 DEG C, has namely obtained the polystyrene@monox nanometer material of nitro functionalization;
(2) by the polystyrene@monox nanometer dispersion of materials of obtained nitro functionalization in polar solvent, add reducing agent, return stirring 12-48h at 50-120 DEG C of temperature, be cooled to room temperature subsequently, suction filtration, successively with the washing of ethanol, deionized water, aqueous slkali, deionized water and ethanol, dry, i.e. obtained poly-aminostyryl@monox nanometer material.
3. preparation method according to claim 2, is characterized in that: described nitrating agent is red fuming nitric acid (RFNA).
4. preparation method according to claim 2, is characterized in that: the acid flux material in described nitrifying process is a kind of in trifluoroacetic acid, hydrochloric acid, sulfuric acid or their mixture.
5. preparation method according to claim 2, is characterized in that: the ratio of solid material described in nitrifying process and acid solution, nitrating agent is: 30-80mg has yolk-eggshell type organic-inorganic hybrid material, 5-10ml acid solution and the 10-50 μ L nitrating agent that kernel is polystyrene spheres, shell is silica.
6. preparation method according to claim 2, is characterized in that: described reducing agent is a kind of in lithium aluminium hydride reduction, sodium borohydride, stannous chloride or their mixture.
7. preparation method according to claim 2, is characterized in that: solid material described in reduction process and polar solvent, the ratio of going back original reagent are: the polystyrene monox nanometer material of 30-80mg nitro functionalization, 10-20ml polar solvent and 300-600mg also original reagent.
8. preparation method according to claim 2, is characterized in that: the polar solvent in described reduction nitro process is a kind of in water, ethanol, N, N-dimethylformamide, oxolane or their mixture.
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Cited By (2)
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| CN109475840A (en) * | 2016-05-06 | 2019-03-15 | 黄金企业公司 | Adsorbent composition, Its Preparation Method And Use |
| CN113101906A (en) * | 2021-05-14 | 2021-07-13 | 重庆恩斯特龙通用航空技术研究院有限公司 | Amino-functionalized polystyrene material and application thereof in adsorption of methyl orange |
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