CN109748279A - One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application - Google Patents
One kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of based on poromeric micro-pore carbon material of novel benzoxazine and its preparation method and application.The microporous carbon is to prepare without one step of template that specific surface area is very big, micro-pore carbon material of micropore structure prosperity by chemical activation method using the novel benzoxazine porous polymer T synthesized for the first time as presoma.Presoma benzoxazine porous polymer of invention itself has certain pore structure, excellent heat resistance, and preparation method is simple, and cost of material is low, no coupling product, without adding catalyst；Microporous carbon microcellular structure obtained by activating is flourishing, aperture is uniform controllable, yield is higher, it has good performance in terms of gas absorption separation, 0 DEG C, the carbon dioxide adsorption under 1bar be 4.02~7.06mmol/g, and seven circulation absorptions have adsorbance high without being decreased obviously, the advantages such as regenerating easily have important prospects for commercial application.
Description
Technical field
The invention belongs to micro-pore carbon material technical field, it is related to preparing a kind of novel benzoxazine porous polymer, in order to
Cellular structure is promoted to expand it in fields purposes such as gas separation, ionic adsorption and catalysis and pass through chemistry as presoma
Micro-pore carbon material of the activation method without one step of template preparation high yield high-specific surface area, is applied to carbon dioxide adsorption research,
Can efficient absorption carbon dioxide, for environmental protection, reduce atmospheric carbon dioxide levels a kind of new method is provided；More particularly to one
Kind is based on poromeric micro-pore carbon material of benzoxazine and its preparation method and application.
Background technique
Micro-pore carbon material refers to that aperture is less than a kind of carbon material of 2nm, has chemical stability height, good conductivity, price
The features such as cheap.Meanwhile the introducing of microcellular structure makes it have the features such as large specific surface area, cellular structure are controllable, aperture is adjustable.
Micro-pore carbon material has obtained extensively in gas separation, the purification of water, chromatography, catalysis and the fields such as photocatalysis and energy stores
Application.This material [M.Oschatz, Energy&Environmental Sci., 2018,11,57-70.] generally by
It is pyrolyzed what suitable presoma obtained, such as biological material and organic polymer.[S.J.Kou, the L.Sun and such as Kou
J.M.C.A, J.Mater.Chem.A, 2016,4,17299-17307.] with ethylenediamine and 2,4,6- tri- (chloromethyl) mesitylene
For Material synthesis polymer NUT-1, then as presoma, KOH is that activator prepares a series of very big micropore of specific surface areas
Carbon shows good potentiality (7.5mmol g in terms of the adsorbing separation of carbon dioxide-1)。
However, aperture is difficult to control, and yield is lower using the microporous carbon that biomass is obtained as precursor preparation, limitation
Its application in certain fields.It can be by the design and work of presoma using the microporous carbon that polymer is obtained as precursor preparation
The means such as the type and activation temperature of agent control the size of microporous carbon, to improve its application value.In polymer
In preparation process, it can inevitably be related to the addition and production of monomer and catalyst, the reaction condition of complexity, template costly
The difficulty of object purification；After being carbonized simultaneously, microporous carbon yield is lower, and aperture is undesirable.Therefore searching preparation cost is low, reaction condition
Mildly, the simple presoma of preparation method, by chemical activation method without one step of template prepare specific area is big, microcellular structure is flourishing,
The micro-pore carbon material of aperture controllable is very necessary [H.Zhao, Z.Jin, H.Su, J.Zhang, X.Yao, H.Zhao and
G.Zhu, Chem.Commun., 2013,49,2780-2782.].
Benzoxazine is the heterocyclic polymer polymer that a kind of thermal stability is fine, carbon yield is high, because preparation condition is mild,
The advantages that without adding catalyst, reacting no coupling product, be a kind of ideal presoma.[L.Wan, J.Wang, C.Feng,
Y.Sun and K.Li, Nanoscale, 2015,7,6534-44.] using oxazines ring as link unit, select that price is lower, has
The regular benzoxazine porous polymer of the monomer of rigid structure, first preparation structure, then by chemical activation method without one step of template
It prepares that specific area is big, microcellular structure is flourishing, the micro-pore carbon material of aperture controllable, is applied to carbon dioxide adsorption research,
It can efficient absorption carbon dioxide.
Summary of the invention
Goal of the invention: being directed to the deficiencies in the prior art, and the object of the present invention is to provide one kind to be based on benzoxazine
The preparation method of poromeric micro-pore carbon material prepares high yield high-specific surface area without one step of template by chemical activation method
Micro-pore carbon material.It is a further object of the present invention to provide a kind of above method materials obtained.Further object of the present invention
Be by above-mentioned material be applied to carbon dioxide adsorption, can efficient absorption carbon dioxide, be environmental protection, reduce atmosphere in titanium dioxide
Concentration of carbon provides a kind of new method and application.
Technical solution: in order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A kind of preparation method based on the poromeric micro-pore carbon material of benzoxazine, includes the following steps:
1) amine, phenol and paraformaldehyde back flow reaction synthesize benzoxazine porous polymer, are denoted as T；
2) above-mentioned benzoxazine porous polymer T and activator are subjected to liquid impregnation；
3) above-mentioned liquid phase mixture is lyophilized, obtained solid carries out chemical activation processing, pickling, and washing obtains described
Micro-pore carbon material, be denoted as BMC；Specific reaction equation is as follows:
In step 1), used amine is 1,3,5- tri- (4- aminophenyl) benzene, 2,4,6- tri- (4- aminophenyls) -1,3,5-
One or more inside triazine, three (4- aminophenyl) amine and melamine, phenol is '-biphenyl diphenol, 1,5- dihydroxy naphthlene, right
One or more inside benzenediol and resorcinol；The molar ratio of amine, phenol and paraformaldehyde is 1: (0.5-5): (5-20)；Instead
It is 4-72h between seasonable；Selected organic solvent be mesitylene, toluene, tetrahydrofuran, dioxane and chloroform inside one kind or
It is several；The concentration of selected amine in organic solvent is 0.01~0.5mol L-1, reaction temperature is 60-130 DEG C, using alkalinity
One or more inside substance sodium hydroxide, triethylamine, ammonium hydroxide, sodium carbonate and potassium hydroxide are come to adjust reaction system pH be 8-
13。
In step 2), the mass ratio of the activator and benzoxazine porous polymer T are 1~4: 1, and selected activator is
One or more inside potassium hydroxide, sodium hydroxide, zinc chloride, potassium carbonate and sodium carbonate.
In step 3), described be activated is carried out in high pure nitrogen atmosphere, and gas flow rate is 20~200mL/
min。
In step 3), the activation temperature is 500~900 DEG C, and heating rate is 1~10 DEG C/min, activation time 1h.
It is described clear based on the poromeric micro-pore carbon material dilute hydrochloric acid of benzoxazine and deionized water in step 3)
It washes, to remove remaining inorganic matter.
The poromeric specific surface area of presoma benzoxazine is 50~500m2/ g, total pore volume be 0.15~
0.66cm3/g
The specific surface area of microporous carbon obtained by the activation is 601~2167m2/ g, micropore size are 0.6~2nm；Total hole
Holding is 0.31~1.34cm3/g。
The described resulting micro-pore carbon material of preparation method based on the poromeric micro-pore carbon material of benzoxazine or
Benzoxazine porous polymer.
The application in absorption carbon dioxide of the micro-pore carbon material.
Preparation method provided by the invention based on the poromeric micro-pore carbon material of benzoxazine, first by raw material
Amine, phenol and paraformaldehyde are added in organic solvent, and agitating and heating back flow reaction synthesizes benzoxazine porous polymer T, to production
Object is washed；Benzoxazine porous polymer T and activator are mixed with dipping again, activated after freeze-drying in tube furnace, pickling, water
It washes, finally dries.Wherein, amine used by the benzoxazine porous polymer T is 1,3,5- tri- (4- aminophenyl) benzene, 2,
One or more inside 4,6- tri- (4- aminophenyl) -1,3,5-triazines, three (4- aminophenyl) amine and melamine, phenol are
One or more inside '-biphenyl diphenol, 1,5- dihydroxy naphthlene, hydroquinone and resorcinol.Amine, phenol and paraformaldehyde rub
You are than being 1: (0.5-5): (5-20).The organic solvent is in mesitylene, toluene, tetrahydrofuran, dioxane and chloroform
The one or more in face.Reaction terminates to obtain pale yellow solid product.
In order to improve the cellular structure of benzoxazine porous polymer T as far as possible, while there is very high yield, it is described
The concentration of amine in organic solvent is 0.01~0.5mol L-1, preferably 0.03~0.4mol L-1；Add alkaline matter hydrogen-oxygen
Changing the one or more inside sodium, triethylamine, ammonium hydroxide, sodium carbonate and potassium hydroxide to carry out regulation system PH is 8-13, preferably
8.5-12.5；Reaction temperature is 60-130 DEG C, preferably 70-120 DEG C；Reaction time is 4-72h, preferably 5-60h.
The benzoxazine porous polymer T and activator are mixed with dipping, activator be potassium hydroxide, sodium hydroxide,
One or more inside zinc chloride, potassium carbonate and sodium carbonate, mass ratio 1: 1-4, dip time are for 24 hours.
The activation, atmosphere are high pure nitrogen, and gas flow rate is 20~200mL/min, preferably 30~180mL/
min；Activation temperature is 500-900 DEG C, and heating rate is 1~10 DEG C/min, preferably 1.5~8 DEG C/min；Activation time is
1h。
The pickling solution selects the aqueous hydrochloric acid solution of 1mol/L.
The utility model has the advantages that compared with prior art, of the invention first synthesizes a kind of novel benzo with certain pore structure
Oxazines porous polymer, and as presoma, prepares without one step of template that specific surface area is very big, hole by chemical activation method
(specific surface area is 50~500m to the micro-pore carbon material of structure prosperity2/g).The micro-pore carbon material has the benzene of pore structure at itself
And on the basis of oxazines, further reaming, the duct of formation is uniform controllable.Micro-pore carbon material of the invention is answered in carbon dioxide adsorption
With in research, showing high carbon dioxide adsorption ability and good circulation absorption performance.The microporous carbon preparation method is simple,
Low raw-material cost, yield is higher, provides a kind of new way for coping with global warming issue.
Detailed description of the invention
Fig. 1 is benzoxazine porous polymer T and the microcosmic shape based on the poromeric micro-pore carbon material of benzoxazine
Looks phenogram, wherein Fig. 1 a is the SEM figure of benzoxazine porous polymer T, and Fig. 1 b is the SEM figure of microporous carbon BMC, and Fig. 1 c is
The TEM of benzoxazine porous polymer T schemes, and Fig. 1 d is the HRTEM figure of microporous carbon BMC；
Fig. 2 is the nitrogen adsorption curve graph of benzoxazine porous polymer T and microporous carbon BMC；
Fig. 3 is the graph of pore diameter distribution of benzoxazine porous polymer T and microporous carbon BMC；
Fig. 4 is the CO of benzoxazine porous polymer T and microporous carbon BMC2Adsorption isothermal curve figure (273K, 1bar)；
Fig. 5 is the change based on the poromeric seven carbon dioxide recycle adsorbances of micro-pore carbon material BMC of benzoxazine
Change result figure.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Following embodiment master instrument to be used and reagent are as follows: transmission electron microscope (JEM-1011, JEOL, Japan)；
Scanning electron microscope (SSX-550, Shimadzu, Japan)；Spectrometer, Bruker)；Quick specific surface and hole
Rate tests (AutoChem II 2920, Micromeritics, America).Main agents used are purchased from purchase traditional Chinese medicines collection
Group chemical reagent Co., Ltd (Sinopharm Chemical Reagent Co., Ltd.).
Embodiment 1
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol1,3,5- tri- (4- aminophenyl) benzene, 12.5mmol CH2O is added in 5mL mesitylene, room temperature
25 DEG C, 0.5h is stirred, it is rear that 1.25mmol '-biphenyl diphenol is added, while it is 8 that sodium hydroxide solution regulation system pH, which is added, is warming up to
60 DEG C, it is stirred at reflux 4h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium hydroxide 1g is taken to be added in the distilled water of 20mL, room temperature (25 DEG C) is stirred
It mixes for 24 hours；The adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, the solid after taking freeze-drying by mixing
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 20mL/min, 500 DEG C are warming up to the rate of 1 DEG C/min,
Constant temperature activates 1h at 500 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 2
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 1,3,5- tri- (4- aminophenyl) benzene, 25mmol CH2O is added in 50mL toluene, and 25 DEG C of room temperature,
0.5h is stirred, it is rear that 5mmol 1,5- dihydroxy naphthlene is added, while it is 10 that triethylamine regulation system pH, which is added, is warming up to 60 DEG C, stirs
Mix reflux 10h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T1g, sodium hydroxide 2g is taken to be added in the distilled water of 20mL, room temperature (25 DEG C) is stirred
It mixes for 24 hours；The adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, the solid after taking freeze-drying by mixing
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 600 DEG C are warming up to the rate of 5 DEG C/min,
Constant temperature activates 1h at 600 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 3
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 1,3,5- tri- (4- aminophenyl) benzene, 50mmol CH2O is added in 250mL tetrahydrofuran, room temperature
25 DEG C, 0.5h is stirred, it is rear that 12.5mmol hydroquinone is added, while it is 13 that ammonia water conditioning system pH, which is added, is warming up to 60 DEG C, stirs
Mix reflux 16h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, zinc chloride 3g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 200mL/min, 700 DEG C are warming up to the rate of 10 DEG C/min,
Constant temperature activates 1h at 700 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 4
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol1,3,5- tri- (4- aminophenyl) benzene, 25mmol CH2O is added in 5mL dioxane, room temperature 25
DEG C, 0.5h is stirred, it is rear that 1.25mmol resorcinol is added, while it is 13 that sodium carbonate liquor regulation system pH, which is added, is warming up to 100
DEG C, it is stirred at reflux 22h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium carbonate 4g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 20mL/min, 800 DEG C are warming up to the rate of 1 DEG C/min, 800
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 5
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 50mmol CH2O is added to 50mL chloroform
In, 25 DEG C of room temperature, 0.5h is stirred, it is rear that 5mmol '-biphenyl diphenol is added, while it is 8 that potassium hydroxide solution regulation system pH, which is added, is risen
Temperature is stirred at reflux 28h to 100 DEG C；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymeric
Object T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, sodium carbonate 1g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 900 DEG C are warming up to the rate of 5 DEG C/min, 900
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 6
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 12.5mmol CH2It is equal to be added to 250mL by O
The in the mixed solvent that trimethylbenzene and volume of toluene ratio are 1: 1, stirs 0.5h by 25 DEG C of room temperature, rear that 12.5mmol 1,5- dihydroxy is added
Base naphthalene, while the mixed solution regulation system pH that sodium hydroxide and ammonium hydroxide is added is 10, is warming up to 100 DEG C, is stirred at reflux 34h；
After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium hydroxide and each 1g of sodium hydroxide are taken, is added in the distilled water of 20mL,
(25 DEG C) of room temperature stirrings are for 24 hours；By mixing, the adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, is taken
Solid after freeze-drying is in tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 200mL/min, with the rate of 10 DEG C/min
600 DEG C are warming up to, constant temperature activates 1h at 600 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then use distilled water
Washing obtains black powder after dry to neutrality.
Embodiment 7
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 50mmol CH2O is added to the equal front three of 5mL
The in the mixed solvent that benzene and tetrahydrofuran volume ratio are 1:1, stirs 0.5h by 25 DEG C of room temperature, rear that 1.25mmol hydroquinone is added,
The mixed solution regulation system pH that sodium hydroxide and sodium carbonate are added simultaneously is 10, is warming up to 130 DEG C, is stirred at reflux 40h；Reaction
After, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g is taken, potassium hydroxide 2g, potassium carbonate 1g are added in the distilled water of 20mL, room
(25 DEG C) stirrings of temperature are for 24 hours；By mixing, the adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, takes jelly
Solid after dry is in tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 200mL/min, with the rate liter of 1 DEG C/min
Temperature to constant temperature at 700 DEG C, 700 DEG C activates 1h；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then is washed with distillation
It washs to neutrality, obtains black powder after dry.
Embodiment 8
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, 12.5mmol CH2It is equal to be added to 50mL by O
The in the mixed solvent that trimethylbenzene and dioxane volume ratio are 1: 1, stirs 0.5h by 25 DEG C of room temperature, rear that 5mmol isophthalic two is added
Phenol, while the mixed solution regulation system pH that sodium hydroxide and potassium hydroxide is added is 13, is warming up to 130 DEG C, is stirred at reflux
46h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, zinc chloride 4g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 800 DEG C are warming up to the rate of 5 DEG C/min, 800
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 9
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol tri- (4- aminophenyl) amine, 25mmol CH2O is added to 250mL mesitylene and chloroform volume ratio
For 1: 1 in the mixed solvent, 25 DEG C of room temperature, 0.5h is stirred, it is rear that 12.5mmol '-biphenyl diphenol is added, while triethylamine adjusting is added
System pH is 8, is warming up to 130 DEG C, is stirred at reflux 52h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzo
Oxazines porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, sodium carbonate 1g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 20mL/min, 500 DEG C are warming up to the rate of 1 DEG C/min, 500
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 10
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol tri- (4- aminophenyl) amine, 12.5mmol CH2O is added to 5mL toluene and tetrahydrofuran volume ratio
For the in the mixed solvent of 1:1,25 DEG C of room temperature, 0.5h is stirred, it is rear that 1.25mmol 1,5- dihydroxy naphthlene is added, while ammonium hydroxide is added
Mixed solution regulation system pH with sodium carbonate is 8, is warming up to 60 DEG C, is stirred at reflux 58h；After reaction, it is sufficiently washed with THF
It washs, is dried in vacuo, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium hydroxide 2g is taken to be added in the distilled water of 20mL, room temperature (25 DEG C) is stirred
It mixes for 24 hours；The adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, the solid after taking freeze-drying by mixing
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 500 DEG C are warming up to the rate of 1 DEG C/min,
Constant temperature activates 1h at 500 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 11
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol tri- (4- aminophenyl) amine, 25mmol CH2O, is added to 50mL toluene and dioxane ratio is 1: 1
In the mixed solvent, 25 DEG C of room temperature, stir 0.5h, it is rear that 5mmol hydroquinone is added, while the mixed of ammonium hydroxide and potassium hydroxide is added
Closing solution regulation system pH is 10, is warming up to 60 DEG C, is stirred at reflux 64h；After reaction, it is sufficiently washed with THF, vacuum is dry
It is dry, obtain benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g is taken, potassium carbonate 1g, sodium carbonate 2g are added in the distilled water of 20mL, room temperature
(25 DEG C) stirrings are for 24 hours；By mixing, the adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, takes freeze-drying
Solid afterwards, in the case where gas flow rate is the high pure nitrogen atmosphere of 200mL/min, is heated up in tube furnace with the rate of 5 DEG C/min
Constant temperature activates 1h to 700 DEG C, 700 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water
To neutrality, black powder is obtained after dry.
Embodiment 12
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol tri- (4- aminophenyl) amine, 50mmol CH2O, being added to 250mL toluene and chloroform volume ratio is 1:
1 in the mixed solvent, stirs 0.5h by 25 DEG C of room temperature, and afterwards plus 12.5mmol enters resorcinol, while sodium carbonate and hydroxide is added
The mixed solution regulation system pH of potassium is 13, is warming up to 60 DEG C, is stirred at reflux 68h；After reaction, it is sufficiently washed with THF, very
Sky is dry, obtains benzoxazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, sodium hydroxide 4g is taken to be added in the distilled water of 20mL, room temperature (25 DEG C) is stirred
It mixes for 24 hours；The adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, the solid after taking freeze-drying by mixing
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 20mL/min, 800 DEG C are warming up to the rate of 10 DEG C/min,
Constant temperature activates 1h at 800 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 13
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol melamine, 25mmol CH2O, is added to 5mL tetrahydrofuran and dioxane volume ratio is 1:1
In the mixed solvent, 25 DEG C of room temperature, stir 0.5h, it is rear that 1.25mmol '-biphenyl diphenol is added, while sodium hydroxide solution tune is added
Section system pH is 13, is warming up to 100 DEG C, is stirred at reflux 70h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzene
And oxazines porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium carbonate 1g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 200mL/min, 900 DEG C are warming up to the rate of 1 DEG C/min, 900
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 14
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol melamine, 50mmol CH2O, is added to 50mL tetrahydrofuran and chloroform volume ratio is the mixed of 1:1
In bonding solvent, 25 DEG C of room temperature, 0.5h is stirred, it is rear that 5mmol 1,5- dihydroxy naphthlene is added, while sodium carbonate liquor is added and adjusts body
Be pH be 8, be warming up to 100 DEG C, be stirred at reflux 72h；After reaction, it is sufficiently washed, is dried in vacuo with THF, obtain benzo evil
Piperazine porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium hydroxide 2g is taken to be added in the distilled water of 20mL, room temperature (25 DEG C) is stirred
It mixes for 24 hours；The adequately benzoxazine porous polymer T dispersion liquid freeze-drying containing potassium hydroxide, the solid after taking freeze-drying by mixing
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 20mL/min, 500 DEG C are warming up to the rate of 5 DEG C/min,
Constant temperature activates 1h at 500 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 15
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol melamine, 12.5mmol CH2O, is added to 250mL dioxane and chloroform volume ratio is 1: 1
In the mixed solvent, 25 DEG C of room temperature, stir 0.5h, it is rear that 12.5mmol hydroquinone is added, while triethylamine regulation system is added
PH is 10, is warming up to 100 DEG C, is stirred at reflux 8h；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzoxazine
Porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T1g, zinc chloride 3g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 600 DEG C are warming up to the rate of 10 DEG C/min,
Constant temperature activates 1h at 600 DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, is done
Black powder is obtained after dry.
Embodiment 16
It is based on the poromeric micro-pore carbon material of benzoxazine the preparation method is as follows:
1) benzoxazine porous polymer T is prepared
Take 2.5mmol melamine, 50mmol CH2O, is added to 50mL mesitylene and dioxane volume ratio is 1:1
In the mixed solvent, 25 DEG C of room temperature, stir 0.5h, it is rear that 1.25mmol resorcinol is added, while potassium hydroxide solution tune is added
Section system pH is 10, is warming up to 130 DEG C, is stirred at reflux for 24 hours；After reaction, it is sufficiently washed with THF, is dried in vacuo, obtains benzene
And oxazines porous polymer T.
2) preparation is based on the poromeric micro-pore carbon material of benzoxazine
Benzoxazine porous polymer T 1g, potassium carbonate 4g is taken to be added in the distilled water of 20mL, (25 DEG C) of room temperature stirrings
24h；Will mixing adequately containing potassium hydroxide benzoxazine porous polymer T dispersion liquid freeze-drying, take freeze-drying after solid in
In tube furnace, in the case where gas flow rate is the high pure nitrogen atmosphere of 100mL/min, 700 DEG C are warming up to the rate of 5 DEG C/min, 700
Constant temperature activates 1h at DEG C；Product is taken out, is washed three times with the hydrochloric acid solution of 1mol/L, then be washed with distilled water to neutrality, it is dry
After obtain black powder.
Embodiment 17
Material prepared by above-described embodiment 1-16, with scanning electron microscope and transmission electron microscope to polymer T and microporous carbon BMC into
Row morphology characterization, as a result as shown in Figure 1, wherein Fig. 1 a is the SEM figure of benzoxazine porous polymer T, and Fig. 1 b is microporous carbon
The SEM of BMC schemes, and Fig. 1 c is the TEM figure of benzoxazine porous polymer T, and Fig. 1 d is the HRTEM figure of microporous carbon BMC；The result shows that
The polymer has the pattern of irregular particle shape, and micro-pore carbon material is then conventional activated carbon pattern.
Carbon dioxide adsorption capability representation based on the poromeric micro-pore carbon material of benzoxazine: titanium dioxide at zero DEG C
Carbon adsorption amount measures (Merck & Co., Inc, U.S. AutoChem II 2920) by Staticadsorption experiment on automatic gas adsorption instrument,
Sample is in 300 DEG C of deaerated under vacuum 3h before measuring.Fig. 2 is that the nitrogen adsorption of benzoxazine porous polymer T and microporous carbon BMC is bent
Line chart；Fig. 3 is the graph of pore diameter distribution of benzoxazine porous polymer T and microporous carbon BMC；Fig. 4 is benzoxazine porous polymer T
With the CO of microporous carbon BMC2Adsorption isothermal curve figure (273K, 1bar)；Fig. 5 is based on the poromeric microporous carbon of benzoxazine
The result of variations figure of seven carbon dioxide recycle adsorbances of material BMC.The result shows that the poromeric specific surface of benzoxazine
Product is 50~500m2/ g, the specific surface area of micro-pore carbon material are 601~2167m2/ g, the carbon dioxide at 0 DEG C, 1bar are inhaled
Attached amount is 4.02~7.06mmol/g, and seven circulation absorptions are without being decreased obviously.
Claims (10)
1. a kind of preparation method based on the poromeric micro-pore carbon material of benzoxazine, which is characterized in that including walking as follows
It is rapid:
1) amine, phenol and paraformaldehyde back flow reaction synthesize benzoxazine porous polymer, are denoted as T；
2) above-mentioned benzoxazine porous polymer T and activator are subjected to liquid impregnation；
3) above-mentioned liquid phase mixture is lyophilized, obtained solid carries out chemical activation processing, pickling, washing, obtains described micro-
Hole carbon material, is denoted as BMC；Specific reaction equation is as follows:
。
2. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
Be, in step 1), used amine be 1,3,5- tri- (4- aminophenyl) benzene, 2,4,6- tri- (4- aminophenyl) -1,3,5- tri-
One or more inside piperazine, three (4- aminophenyl) amine and melamine, phenol are '-biphenyl diphenol, 1,5- dihydroxy naphthlene, to benzene
One or more inside diphenol and resorcinol；The molar ratio of amine, phenol and paraformaldehyde is 1: (0.5-5): (5-20)；Reaction
Time is 4-72h；Selected organic solvent is one kind or several inside mesitylene, toluene, tetrahydrofuran, dioxane and chloroform
Kind；The concentration of selected amine in organic solvent is 0.01~0.5mol L-1, reaction temperature is 60-130 DEG C, using basic species
One or more inside matter sodium hydroxide, triethylamine, ammonium hydroxide, sodium carbonate and potassium hydroxide are come to adjust reaction system pH be 8-
13。
3. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, in step 2), the mass ratio of the activator and benzoxazine porous polymer T are 1~4: 1, and selected activator is hydrogen
One or more inside potassium oxide, sodium hydroxide, zinc chloride, potassium carbonate and sodium carbonate.
4. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, in step 3), described be activated is carried out in high pure nitrogen atmosphere, and gas flow rate is 20~200mL/min.
5. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, in step 3), the activation temperature is 500~900 DEG C, and heating rate is 1~10 DEG C/min, activation time 1h.
6. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, it is described to be cleaned based on the poromeric micro-pore carbon material of benzoxazine with dilute hydrochloric acid and deionized water in step 3), with
Just remaining inorganic matter is removed.
7. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, the poromeric specific surface area of presoma benzoxazine is 50~500m2/ g, total pore volume be 0.15~
0.66cm3/g。
8. the preparation method according to claim 1 based on the poromeric micro-pore carbon material of benzoxazine, feature
It is, the specific surface area of microporous carbon obtained by the activation is 601~2167m2/ g, micropore size are 0.6~2nm；Total pore volume
For 0.31~1.34cm3/g。
9. obtained by the described in any item preparation methods based on the poromeric micro-pore carbon material of benzoxazine of claim 1-8
Micro-pore carbon material or benzoxazine porous polymer.
10. the application in absorption carbon dioxide of micro-pore carbon material as claimed in claim 9.
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