CN108299610A - The preparation method of the porous polymer material of doped meso-porous carbon microspheres - Google Patents
The preparation method of the porous polymer material of doped meso-porous carbon microspheres Download PDFInfo
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- CN108299610A CN108299610A CN201711281248.XA CN201711281248A CN108299610A CN 108299610 A CN108299610 A CN 108299610A CN 201711281248 A CN201711281248 A CN 201711281248A CN 108299610 A CN108299610 A CN 108299610A
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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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
The invention discloses the preparation methods of the porous polymer material of doped meso-porous carbon microspheres, specifically include following steps：（1）Using stalk as raw material, surfactant is soft template, and stirring is until be completely dissolved；（2）Mesoporous carbon microspheres are collected by filtration after taking the stalk powder after grinding and above-mentioned mixed liquor hybrid reaction；（3）Two kinds of 1,5 diaminonaphthalenes of monomer and equal benzene trioxin are added in reaction vessel, mesoporous carbon microspheres are added in stirring；（4）Appropriate acetic acid, reaction is added in the mixed solvent；（5）By the product vacuum drying after abundant washing.Natural biomass resource is made full use of, abundant raw material is cheap and easy to get, and reaction condition is mild, shortens the reaction time, forms orderly meso-hole structure；By changing solvent burden ratio, it can obtain adulterating novel hollow/solid controllable covalent organic porous polymer material of spherical shape of orderly meso-hole structure, structure-controllable and thermal stability is good；With multifunctionality, adsorption efficiency is high, can repeatedly use.
Description
Technical field
The invention belongs to field of material technology, and in particular to the preparation side of the porous polymer material of doped meso-porous carbon microspheres
Method.
Background technology
Carbon Materials with ordered mesopore structure are usually with high specific surface area, pore volume, narrow pore-size distribution and company
Continue adjustable pore structure, is effectively applied to metal ion in water solution system, organic pollution and small molecule dyes extensively
Removal, capacitor electrode material, fuel-cell catalyst etc..Orderly pore structure directly affects the items for preparing Carbon Materials
Physics and chemical property.
Porous material widely exists in nature, such as zeolite, molecular sieve, sponge are all typical porous materials.
Porous material is since its large specific surface area, the adjustable unique advantage in aperture have been favored by people, and people are in natural porous material
On the basis of synthesized some functional porous materials.Covalent organic porous polymer material is a kind of novel porous material,
It is formed by connecting by covalent bond by lightweight element carbon, hydrogen, oxygen, nitrogen, boron etc..Covalent organic porous polymer material with common are
Machine porous material, which is compared, incomparable advantage：Therefore being made of lightweight element has lower skeletal density；Its structure
By being covalently keyed between unit, there is excellent thermal stability and chemical stability；Its aperture and function can be set in advance
Meter, has the function of structural controllability and adjustability；Its synthetic method is numerous, and synthesis condition is simple, and synthon is various.Based on
Upper characteristic, covalent organic porous polymer material the energy, substance absorption with detach, be catalyzed, chemical sensitisation and biological medicine etc.
Aspect presents huge potential.How by with ordered mesopore structure Carbon Materials and porous material be combined, make its tool
The material advantage for having the two, is the technical problem to be solved in the present invention.
Invention content
For problems of the prior art, the purpose of the present invention is to provide the porous polymerics of doped meso-porous carbon microspheres
The preparation method of object material.
The technical solution that the present invention takes is：
The preparation method of the porous polymer material of doped meso-porous carbon microspheres, specifically includes following steps：
（1）Using stalk as raw material, surfactant is soft template, according to quality g：It is soluble in water that volume ml ratios weigh template,
It is stirred continuously in 60 DEG C of water-baths until being completely dissolved；
（2）According to quality g：Volume ml ratios are transferred to volume after taking the stalk powder after grinding to be mixed with above-mentioned mixed liquor be polytetrafluoro
In ethylene liner reaction kettle, be warming up to 260 DEG C -280 DEG C, constant temperature 14h-16h of temperature, cool down to after room temperature be collected by filtration it is mesoporous
Carbon microspheres；
（3）It is 10 in molar ratio by two kinds of monomer 1,5- diaminonaphthalenes and equal benzene trioxin:（3-4）It is added in reaction vessel, stirs
Mix the mesoporous carbon microspheres for being added that mixed liquor mass percent is 5-7%；
（4）Mixed solvent is added in above-mentioned reaction vessel, appropriate acetic acid is then added, reaction vessel is sealed, constant temperature adds
Heat stands and reacts several days；
（5）After reaction, it is cooled to room temperature, product vacuum is filtered, fully washed with organic solvent, after abundant washing
Product vacuum is dried.
Further, the step（1）In surfactant be dodecyl sodium sulfate.
Further, the step（2）It is heated up with 5 DEG C/min heating rates when middle heating.
Further, the step（4）In mixed solvent be dichloromethane and acetone according to volume ratio 3:5 compositions mix
Bonding solvent.
Further, the step（5）In vacuum drying method be vacuum drying chamber drying, 120 DEG C of drying temperature-
150 DEG C, drying time 6-8 hour.
Beneficial effects of the present invention are：
Natural biomass resource is made full use of, abundant raw material is cheap and easy to get, and high temperature and pressure hydrothermal conditions can make it rapid
Dehydrating condensation is hydrolyzed, using water as solvent, raw material is not required to pre-process, and reaction condition is mild, shortens the reaction time, forms orderly Jie
Pore structure, by adjusting reaction density ratio and reaction condition, the ordered mesopore structure that can regulate and control different mesoporous patterns generates；It is logical
Change solvent burden ratio is crossed, novel hollow/solid controllable spherical shape that can obtain adulterating orderly meso-hole structure is covalently organic
Porous polymer material, structure-controllable and thermal stability are good；With multifunctionality, can be used for Dye Adsorption and storage especially with
Toward the absorption and storage of reluctant azo dyes or harmful substance, adsorption efficiency is high, and sorption cycle performance is good, can repeatedly weigh
It is multiple to use, it is good sorbing material.
Description of the drawings
Fig. 1 has the 3-D cubes of SEM picture to order mesoporous carbon microspheres for what the embodiment of the present invention 1 was prepared；
Fig. 2 is Fourier transform-infrared spectrogram of this hair embodiment 1 and example 2.
Specific implementation mode
It further illustrates the present invention below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the porous polymer material of doped meso-porous carbon microspheres, specifically includes following steps：
（1）Using stalk as raw material, surfactant sodium dodecyl base sodium sulfonate is soft template, according to quality g：Volume ml ratios weigh mould
Plate agent is soluble in water, is stirred continuously in 60 DEG C of water-baths until being completely dissolved；
（2）According to quality g：Volume ml ratios are transferred to volume after taking the stalk powder after grinding to be mixed with above-mentioned mixed liquor be polytetrafluoro
In ethylene liner reaction kettle, 260 DEG C of temperature is warming up to 5 DEG C/min heating rates, constant temperature 16h is filtered after cooling down to room temperature
Collect mesoporous carbon microspheres；As shown in Figure 1, what is be prepared has the 3-D cubes of SEM picture to order mesoporous carbon microspheres；
（3）It is 10 in molar ratio by two kinds of monomer 1,5- diaminonaphthalenes and equal benzene trioxin:3 are added in reaction vessel, and stirring adds
Enter the mesoporous carbon microspheres that mixed liquor mass percent is 5%；
（4）Dichloromethane and acetone are according to volume ratio 3:5 composition mixed solvents, above-mentioned reaction vessel is added to by mixed solvent
In, appropriate acetic acid is then added, reaction vessel is sealed, heated at constant temperature stands and reacts several days；
（5）After reaction, it is cooled to room temperature, product vacuum is filtered, fully washed with organic solvent, after abundant washing
Product vacuum is dried, and vacuum drying method is dried for vacuum drying chamber, 120 DEG C of drying temperature, 8 hours drying times.
Embodiment 2
The preparation method of the porous polymer material of doped meso-porous carbon microspheres, specifically includes following steps：
（1）Using stalk as raw material, surfactant sodium dodecyl base sodium sulfonate is soft template, according to quality g：Volume ml ratios weigh mould
Plate agent is soluble in water, is stirred continuously in 60 DEG C of water-baths until being completely dissolved；
（2）According to quality g：Volume ml ratios are transferred to volume after taking the stalk powder after grinding to be mixed with above-mentioned mixed liquor be polytetrafluoro
In ethylene liner reaction kettle, 270 DEG C of temperature is warming up to 5 DEG C/min heating rates, constant temperature 15h is filtered after cooling down to room temperature
Collect mesoporous carbon microspheres；
（3）It is 10 in molar ratio by two kinds of monomer 1,5- diaminonaphthalenes and equal benzene trioxin:4 are added in reaction vessel, and stirring adds
Enter the mesoporous carbon microspheres that mixed liquor mass percent is 6%；
（4）Dichloromethane and acetone are according to volume ratio 3:5 composition mixed solvents, above-mentioned reaction vessel is added to by mixed solvent
In, appropriate acetic acid is then added, reaction vessel is sealed, heated at constant temperature stands and reacts several days；
（5）After reaction, it is cooled to room temperature, product vacuum is filtered, fully washed with organic solvent, after abundant washing
Product vacuum is dried, and vacuum drying method is dried for vacuum drying chamber, 140 DEG C of drying temperature, 7 hours drying times.
As shown in Fig. 2, Fourier transform-infrared spectrogram of this hair embodiment 1 and example 2；Wherein 1 represents the equal benzene of monomer three
Formaldehyde, 2 represent monomer 1,5-diaminonaphthalene, and by spectrogram, it can be seen that, 1627cm-1 is-N-H- bending vibrations, 3400- in 2
3200cm-1 is-N-H- stretching vibrations, and after reaction generates COPs-1a, 3400-3200-N-H- stretching vibration peaks obviously disappear,
Thus the disappearance of proof-N-H- illustrates that 1627cm-1 is-C=N stretching vibration peaks in COPs-1a, it was demonstrated that the formation of imine linkage.
Embodiment 3
The preparation method of the porous polymer material of doped meso-porous carbon microspheres, specifically includes following steps：
（1）Using stalk as raw material, surfactant sodium dodecyl base sodium sulfonate is soft template, according to quality g：Volume ml ratios weigh mould
Plate agent is soluble in water, is stirred continuously in 60 DEG C of water-baths until being completely dissolved；
（2）According to quality g：Volume ml ratios are transferred to volume after taking the stalk powder after grinding to be mixed with above-mentioned mixed liquor be polytetrafluoro
In ethylene liner reaction kettle, 280 DEG C of temperature is warming up to 5 DEG C/min heating rates, constant temperature 14h is filtered after cooling down to room temperature
Collect mesoporous carbon microspheres；
（3）It is 10 in molar ratio by two kinds of monomer 1,5- diaminonaphthalenes and equal benzene trioxin:4 are added in reaction vessel, and stirring adds
Enter the mesoporous carbon microspheres that mixed liquor mass percent is 7%；
（4）Dichloromethane and acetone are according to volume ratio 3:5 composition mixed solvents, above-mentioned reaction vessel is added to by mixed solvent
In, appropriate acetic acid is then added, reaction vessel is sealed, heated at constant temperature stands and reacts several days；
（5）After reaction, it is cooled to room temperature, product vacuum is filtered, fully washed with organic solvent, after abundant washing
Product vacuum is dried, and vacuum drying method is dried for vacuum drying chamber, 150 DEG C of drying temperature, 6 hours drying times.
The above is not limitation of the present invention, it should be pointed out that：Those skilled in the art are come
It says, under the premise of not departing from essential scope of the present invention, several variations, modifications, additions or substitutions can also be made, these improvement
Protection scope of the present invention is also should be regarded as with retouching.
Claims (5)
1. the preparation method of the porous polymer material of doped meso-porous carbon microspheres, which is characterized in that specifically include following steps：
（1）Using stalk as raw material, surfactant is soft template, according to quality g：It is soluble in water that volume ml ratios weigh template,
It is stirred continuously in 60 DEG C of water-baths until being completely dissolved；
（2）According to quality g：Volume ml ratios are transferred to volume after taking the stalk powder after grinding to be mixed with above-mentioned mixed liquor be polytetrafluoro
In ethylene liner reaction kettle, be warming up to 260 DEG C -280 DEG C, constant temperature 14h-16h of temperature, cool down to after room temperature be collected by filtration it is mesoporous
Carbon microspheres；
（3）It is 10 in molar ratio by two kinds of monomer 1,5- diaminonaphthalenes and equal benzene trioxin:（3-4）It is added in reaction vessel, stirs
Mix the mesoporous carbon microspheres for being added that mixed liquor mass percent is 5-7%；
（4）Mixed solvent is added in above-mentioned reaction vessel, appropriate acetic acid is then added, reaction vessel is sealed, constant temperature adds
Heat stands and reacts several days；
（5）After reaction, it is cooled to room temperature, product vacuum is filtered, fully washed with organic solvent, after abundant washing
Product vacuum is dried.
2. the preparation method of the porous polymer material of doped meso-porous carbon microspheres according to claim 1, which is characterized in that institute
State step（1）In surfactant be dodecyl sodium sulfate.
3. the preparation method of the porous polymer material of doped meso-porous carbon microspheres according to claim 1, which is characterized in that institute
State step（2）It is heated up with 5 DEG C/min heating rates when middle heating.
4. the preparation method of the porous polymer material of doped meso-porous carbon microspheres according to claim 1, which is characterized in that institute
State step（4）In mixed solvent be dichloromethane and acetone according to volume ratio 3:The mixed solvent of 5 compositions.
5. the preparation method of the porous polymer material of doped meso-porous carbon microspheres according to claim 1, which is characterized in that institute
State step（5）In vacuum drying method be vacuum drying chamber drying, 120 DEG C -150 DEG C of drying temperature, drying time, 6-8 was small
When.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082160A (en) * | 2016-06-02 | 2016-11-09 | 浙江大学 | Preparation method of Carbon Hollow material and products thereof |
| CN106632933A (en) * | 2016-12-30 | 2017-05-10 | 东华大学 | Mechanical preparation method of aromatic polyimide porous material |
| CN107381535A (en) * | 2017-09-15 | 2017-11-24 | 青岛科技大学 | A kind of method for preparing order mesoporous carbon microspheres |
| CN107556472A (en) * | 2017-09-14 | 2018-01-09 | 青岛科技大学 | The covalent organic porous polymer material of hollow/solid controllable spherical of one kind, Preparation method and use |
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2017
- 2017-12-07 CN CN201711281248.XA patent/CN108299610A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106082160A (en) * | 2016-06-02 | 2016-11-09 | 浙江大学 | Preparation method of Carbon Hollow material and products thereof |
| CN106632933A (en) * | 2016-12-30 | 2017-05-10 | 东华大学 | Mechanical preparation method of aromatic polyimide porous material |
| CN107556472A (en) * | 2017-09-14 | 2018-01-09 | 青岛科技大学 | The covalent organic porous polymer material of hollow/solid controllable spherical of one kind, Preparation method and use |
| CN107381535A (en) * | 2017-09-15 | 2017-11-24 | 青岛科技大学 | A kind of method for preparing order mesoporous carbon microspheres |
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