CN107629222A - A kind of preparation method of super crosslinking polyaniline - Google Patents
A kind of preparation method of super crosslinking polyaniline Download PDFInfo
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- CN107629222A CN107629222A CN201711098012.2A CN201711098012A CN107629222A CN 107629222 A CN107629222 A CN 107629222A CN 201711098012 A CN201711098012 A CN 201711098012A CN 107629222 A CN107629222 A CN 107629222A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 104
- 238000004132 cross linking Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 41
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000010276 construction Methods 0.000 claims description 6
- -1 stirred Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 235000011167 hydrochloric acid Nutrition 0.000 description 19
- 239000012153 distilled water Substances 0.000 description 15
- 239000012065 filter cake Substances 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- AZUCPFMKPGFGTB-UHFFFAOYSA-N 2,2-diiodopropane Chemical compound CC(C)(I)I AZUCPFMKPGFGTB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a kind of preparation method of super crosslinking polyaniline, polyaniline, eight vinyl silsesquioxanes and aluminum trichloride (anhydrous) are added in 1,2 dichloroethanes; nitrogen is protected, and is reacted, is heated to reflux by Friedel-Crafts; filter, washing is dry must to surpass crosslinking polyaniline.The present invention is using eight vinyl silsesquioxanes as crosslinking agent, by controlling the mass ratio of eight vinyl silsesquioxanes and polyaniline to realize the regulation and control of super crosslinking polyaniline pore structure, with the raising of the mass ratio of eight vinyl silsesquioxanes, the specific surface area of the super crosslinking polyaniline of gained gradually increases, and specific surface area maximum is up to 481 m2 g- 1。
Description
Technical field
The present invention relates to a kind of preparation method of super crosslinking polyaniline, belongs to synthesis of polymer material technical field.
Background technology
Super crosslinking polyaniline (hypercrosslinkedpolyaniline, HCPANI) is that one kind has highly cross-linked knot
New organic poromerics of structure.Since American scientist Frantisek Svec in 2007 prepare excess of export crosslinking polyaniline,
Due to containing substantial amounts of microcellular structure and N exotic atoms in super crosslinking polyaniline, and in H2And CO2Absorption and storage, super capacitor
The application aspects such as device show the great attention that good performance receives numerous scientific workers, are current field of new materials
Study hotspot.At present, the preparation method for surpassing crosslinking polyaniline uses N- alkylation process, i.e., with eigenstate or reduction-state linear
Polyaniline is construction unit, using the high polyhalo alkane of the reactivities such as diiodomethane and diiodo propane or paraformaldehyde as crosslinking
Agent, N- alkylated reaction systems are carried out in high-temperature solvent (DMF (DMF), N, N- dimethyl sulfoxide (DMSO)s (DMSO))
For what is come out.In this course of reaction, high energy consumption (reaction temperature height is all higher than 120 DEG C), operation complexity be present, react bar
The problems such as part harshness (reaction needs high pressure).Such as：Sharma etc. adds a certain amount of polyaniline in eigenstate and Anhydrous potassium carbonate
Enter into appropriate DMF ultrasonic 10min, add a certain amount of diiodomethane to reaction system, reactant is then placed in microwave
In reactor, 15min is reacted under the conditions of 130 DEG C, is filtered, then puts the precipitate in appropriate DMF backflow (DMF boiling points is
154 DEG C) 72h, by N- alkylated reactions prepare excess of export be crosslinked polyaniline (V.Sharma, A.Sahoo, Y.Sharma,
P.Mohanty.RSC Adv.,2015,5,45749-45754).A certain amount of polyaniline in eigenstate is added to suitable by sharma etc.
First ultrasonic 1h, adds appropriate Anhydrous potassium carbonate ultrasonic 0.5h again, different amounts of diiodo- is added into reaction system in the DMF of amount
Methane, obtained reactant is placed in high-temperature high-pressure reaction kettle, respectively at different temperatures (120 DEG C, 140 DEG C, 160 DEG C and
180 DEG C) reaction 24h, filtering, then put the precipitate in appropriate DMF the 72h that flows back and one system is prepared by N- alkylated reactions
Super crosslinking polyaniline (V.Sharma, S.Khilari, D.Pradhanb, the P.Mohanty.RSC Adv., 2016,6,56421- of row
56428).Super crosslinking polyaniline is prepared by the above method, operation is cumbersome, and reaction temperature is high, reaction time consumption length, reacts bar
Part is harsh, reaction time consumption length, and polyaniline synthesis cost is high.
Therefore, a kind of side of the super crosslinking polyaniline of preparation simple to operate, inexpensive, that reaction condition is gentle is needed badly at present
Method.
The content of the invention
The technical problems to be solved by the invention are to overcome the existing existing reaction temperature of super crosslinking method for preparing polyaniline
The problems such as spending height, complex operation, long severe reaction conditions and reaction time consumption, there is provided a kind of simple to operate, inexpensive prepare surpasses friendship
Join the method for polyaniline.
To solve above technical problem, the technical scheme that the present invention takes is：
A kind of preparation method of super crosslinking polyaniline, this method include：Using polyaniline as construction unit, with eight vinyl times
Half siloxanes is that crosslinking agent prepares super crosslinking polyaniline by Friedel-Crafts alkylation.
The present invention also provides the super crosslinking polyaniline being prepared using the above method.
Compared with prior art, technical scheme has the advantages that：
(1) present invention passes through friedel-craft alkyl using polyaniline as construction unit using eight vinyl silsesquioxanes as crosslinking agent
Change to react and prepare super crosslinking polyaniline, solve reaction temperature height, reaction behaviour existing for existing super crosslinking method for preparing polyaniline
Make the problems such as complicated, reaction time consumption is long, preparation cost height, a kind of new thinking is provided to prepare super crosslinking polyaniline.
(2) preparing super crosslinking polyaniline in the process of the present invention can be by adjusting eight vinyl silsesquioxanes and polyaniline
Mass ratio come regulate and control it is super crosslinking polyaniline specific surface area size.With polyaniline and eight vinyl silsesquioxane mass ratioes
Increase, the specific surface area for the super crosslinking polyaniline prepared gradually increase.
(3) present invention is without special consersion unit, without the catalyst of costliness, without carrying out special place to raw material
Reason, reaction is simple, and reaction condition is gentle, has the advantages that simple, pollution-free, the easy large-scale production of low production cost, technique.
Brief description of the drawings
The Figure of description for forming the part of the present invention is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not form inappropriate limitation of the present invention.
Fig. 1 is the field emission scanning electron microscope (FESEM) of super crosslinking polyaniline prepared by case study on implementation 3；
Fig. 2 is the field emission scanning electron microscope (FESEM) of super crosslinking polyaniline prepared by case study on implementation 4；
Fig. 3 is the field emission scanning electron microscope (FESEM) of super crosslinking polyaniline prepared by case study on implementation 5；
Fig. 4 is the high-resolution-ration transmission electric-lens (HRTEM) of super crosslinking polyaniline prepared by case study on implementation 4；
Fig. 5 is the N of super crosslinking polyaniline prepared by case study on implementation 42Adsorption and desorption isotherms.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the present invention.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with general technical staff of the technical field of the invention
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation and/or combinations thereof.
As background technology is introduced, surpass in the prior art crosslinking polyaniline preparation method exist reaction temperature it is high,
The problems such as complex operation, long severe reaction conditions and reaction time consumption, in order to solve technical problem as above, the present invention proposes a kind of
The preparation method of super crosslinking polyaniline, this method include：Using polyaniline as construction unit, using eight vinyl silsesquioxanes as friendship
Join agent and super crosslinking polyaniline is prepared by Friedel-Crafts alkylation.
The construction unit polyaniline of the super crosslinking polyaniline of the present invention can pass through conventional method for those skilled in the art
It is prepared, different synthesis conditions can control the degree of oxidation of polyaniline.But farthest to improve the present invention
The performance of prepared super crosslinking polyphenyl amine product, the present invention preferably select following preparation method：
Aniline is added in hydrochloric acid solution, ammonium persulfate ((NH is slowly added dropwise4)2S2O8) solution prepares polyaniline.Specifically
Preparation method it is as follows：
Under the conditions of ice-water bath, aniline is added in hydrochloric acid solution, stirred, then adds ammonium persulfate ((NH4)2S2O8)
Solution makees initiator, reacts 4~5h, and product is filtered, washed, obtains polyaniline after drying；Wherein, aniline, hydrochloric acid solution, mistake
The volume ratio of ammonium sulfate is (4~5):(50~55):(20~30), the concentration of hydrochloric acid solution is 0.5~4mol L- 1,
The concentration of ammonium persulfate solution is 1~3mol L- 1。
In further preferred embodiment of the present invention, concentration of hydrochloric acid solution is 2.0mol L- 1；Ammonium persulfate it is dense
Spend for 2.0mol L- 1。
What the eight vinyl silsesquioxanes of the present invention can be prepared by a conventional method to obtain for those skilled in the art,
In a preferred embodiment of the present invention, there is provided a kind of preparation method of eight vinyl silsesquioxanes (OVS), by vinyl three
Methoxy silane is placed in hydrolysis in the mixed solution of acetone, hydrochloric acid and water and prepares eight vinyl silsesquioxanes.Wherein, hydrochloric acid
For concentrated hydrochloric acid (mass fraction 36%).
Specific preparation method is as follows：
30mL vinyltrimethoxy silanes are added in 150mL acetone, sequentially add 80mL concentrated hydrochloric acids and 80mL
Water, 48~72h (preferably 72h) being reacted at room temperature, being filtered, repeatedly washing obtains eight vinyl times for filter cake acetone, absolute ethyl alcohol
Half siloxanes (OVS).
In a preferred embodiment of the present invention, the Friedel-Crafts alkylation comprises the following steps：By polyaniline, eight
Vinyl silsesquioxane and aluminum trichloride (anhydrous) (AlCl3) be added in 1,2- dichloroethanes, disperse to form uniform mix
Compound, 12~36h is reacted at 60~120 DEG C, the product containing super crosslinking polyaniline is prepared；Then obtained product is taken out
Filter and make solvent surname extraction with methanol, tetrahydrofuran, be dried to obtain super crosslinking polyaniline.By verification experimental verification, in the reaction
Under the conditions of, yield and the performance (specific surface area) for surpassing crosslinking polyaniline are higher.
In further preferred embodiment of the present invention, successfully to prepare super crosslinking polyaniline, improving super crosslinking polyphenyl
The yield of amine and from the perspective of improving the specific surface area of super crosslinking polyaniline, polyaniline and eight vinyl silsesquioxanes
Mass ratio is 1:0.1~0.862, optimal proportion 1:0.862.If less crosslinking agent, it can produce during the course of the reaction easily
The polymer of the branched structure of dissolving, causes the yield of the super crosslinking polyaniline of product to reduce, and reduces super crosslinking polyaniline
Specific surface area.
In further preferred embodiment of the present invention, the mass ratio of polyaniline and aluminum trichloride (anhydrous) is 1：2.
In further preferred embodiment of the present invention, Friedel-Crafts alkylation condition is：24h is reacted at 80 DEG C.Through
Overtesting verifies that under the reaction conditions, yield and the performance (specific surface area) for surpassing crosslinking polyaniline are optimal.
In further preferred embodiment of the present invention, drying condition is：60 DEG C of vacuum drying 24h.
In order that technical scheme can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes technical scheme in detail.
Wherein, quality (polyaniline and eight second of quality/reaction raw materials of yield of the present invention=super crosslinking polyaniline
Alkenyl silsesquioxane) × 100%.
Embodiment 1
(1) preparation of polyaniline adds 4.6mL aniline and 50mL (2mol into the 250mL round-bottomed flasks for be placed in ice-water bath
L- 1) hydrochloric acid solution, magnetic agitation 10min, 25mL (2mol L are slowly added dropwise into reaction system- 1) ammonium persulfate aqueous solution, instead
4h is answered, is filtered, filter cake is washed with distilled water to neutrality, obtains polyaniline.
The preparation of (2) eight vinyl silsesquioxanes adds 30mL vinyl front threes into 500mL round-bottomed flask successively
TMOS, 150mL acetone, 80mL concentrated hydrochloric acids and 80mL distilled water.72h is stirred at room temperature, is filtered, filter cake acetone and ethanol
Washing is multiple, and 24h is dried in vacuo at 60 DEG C and obtains eight vinyl silsesquioxanes.
(3) preparation for surpassing crosslinking polyaniline under nitrogen protection, added into 50mL round-bottomed flasks 1.00g polyanilines,
The vinyl silsesquioxanes of 0.10g eight, the anhydrous AlCl of 2.00g3And 20mL1,2- dichloroethanes, magnetic agitation 1h, it is warming up to 80
DEG C and keep this thermotonus 24h, filter, product washs with distilled water, absolute ethyl alcohol successively, and product then is placed in into Soxhlet carries
Take in device, made solvent with methanol, tetrahydrofuran respectively and respectively purified 48h, 24h is dried in vacuo at 60 DEG C, obtain super crosslinking polyaniline,
Yield is 79%.
Embodiment 2
(1) preparation of polyaniline adds 4.6mL aniline and 50mL (2mol into the 250mL round-bottomed flasks for be placed in ice-water bath
L- 1) hydrochloric acid solution, magnetic agitation 10min, 25mL (2mol L are slowly added dropwise into reaction system- 1) ammonium persulfate aqueous solution, instead
4h is answered, is filtered, filter cake is washed with distilled water to neutrality, obtains polyaniline.
The preparation of (2) eight vinyl silsesquioxanes adds 30mL vinyl front threes into 500mL round-bottomed flask successively
TMOS, 150mL acetone, 80mL concentrated hydrochloric acids and 80mL distilled water.72h is stirred at room temperature, is filtered, filter cake acetone and ethanol
Washing is multiple, and 24h is dried in vacuo at 60 DEG C and obtains eight vinyl silsesquioxanes.
(3) preparation for surpassing crosslinking polyaniline under nitrogen protection, added into 50mL round-bottomed flasks 1.00g polyanilines,
The vinyl silsesquioxanes of 0.2g eight, the anhydrous AlCl of 2.00g3And 20mL1,2- dichloroethanes, magnetic agitation 1h, it is warming up to 80 DEG C
And this thermotonus 24h is kept, filter, product is washed with distilled water, absolute ethyl alcohol successively, and product then is placed in into surname extraction
In device, made solvent with methanol, tetrahydrofuran respectively and respectively purified 48h, 24h is dried in vacuo at 60 DEG C, obtain super crosslinking polyaniline, produced
Rate is 73%.
Embodiment 3
(1) preparation of polyaniline adds 4.6mL aniline and 50mL into the 250mL round-bottomed flasks being placed in ice-water bath
(2mol L- 1) hydrochloric acid solution, magnetic agitation 10min, 25mL (2mol L are slowly added dropwise into reaction system- 1) ammonium persulfate water
Solution, 4h is reacted, filtered, filter cake is washed with distilled water to neutrality, obtains polyaniline.
The preparation of (2) eight vinyl silsesquioxanes adds 30mL vinyl front threes into 500mL round-bottomed flask successively
TMOS, 150mL acetone, 80mL concentrated hydrochloric acids and 80mL distilled water.72h is stirred at room temperature, is filtered, filter cake acetone and ethanol
Washing is multiple, and 24h is dried in vacuo at 60 DEG C and obtains eight vinyl silsesquioxanes.
(3) preparation for surpassing crosslinking polyaniline under nitrogen protection, added into 50mL round-bottomed flasks 1.00g polyanilines,
The vinyl silsesquioxanes of 0.3g eight, the anhydrous AlCl of 2.00g3And 20mL1,2- dichloroethanes, magnetic agitation 1h, it is warming up to 80 DEG C
And this thermotonus 24h is kept, filter, product is washed with distilled water, absolute ethyl alcohol successively, and product then is placed in into surname extraction
In device, made solvent with methanol, tetrahydrofuran respectively and respectively purified 48h, 24h is dried in vacuo at 60 DEG C, obtain super crosslinking polyaniline, produced
Rate is 100%, as shown in Figure 1.
Embodiment 4
(1) preparation of polyaniline adds 4.6mL aniline and 50mL (2mol into the 250mL round-bottomed flasks for be placed in ice-water bath
L- 1) hydrochloric acid solution, magnetic agitation 10min, 25mL (2mol L are slowly added dropwise into reaction system- 1) ammonium persulfate aqueous solution, instead
4h is answered, is filtered, filter cake is washed with distilled water to neutrality, obtains polyaniline.
The preparation of (2) eight vinyl silsesquioxanes adds 30mL vinyl front threes into 500mL round-bottomed flask successively
TMOS, 150mL acetone, 80mL concentrated hydrochloric acids and 80mL distilled water.72h is stirred at room temperature, is filtered, filter cake acetone and ethanol
Washing is multiple, and 24h is dried in vacuo at 60 DEG C and obtains eight vinyl silsesquioxanes.
(3) preparation for surpassing crosslinking polyaniline under nitrogen protection, added into 50mL round-bottomed flasks 1.00g polyanilines,
The vinyl silsesquioxanes of 0.509g eight, the anhydrous AlCl of 2.00g3And 20mL1,2- dichloroethanes, magnetic agitation 1h, it is warming up to 80
DEG C and keep this thermotonus 24h, filter, product washs with distilled water, absolute ethyl alcohol successively, and product then is placed in into Soxhlet carries
Take in device, made solvent with methanol, tetrahydrofuran respectively and respectively purified 48h, 24h is dried in vacuo at 60 DEG C, obtain super crosslinking polyaniline,
Yield is 100%, as shown in Fig. 2,4 and 5.
Embodiment 5
(1) preparation of polyaniline adds 4.6mL aniline and 50mL (2mol into the 250mL round-bottomed flasks for be placed in ice-water bath
L- 1) hydrochloric acid solution, magnetic agitation 10min, 25mL (2mol L are slowly added dropwise into reaction system- 1) ammonium persulfate aqueous solution, instead
4h is answered, is filtered, filter cake is washed with distilled water to neutrality, obtains polyaniline.
The preparation of (2) eight vinyl silsesquioxanes adds 30mL vinyl front threes into 500mL round-bottomed flask successively
TMOS, 150mL acetone, 80mL concentrated hydrochloric acids and 80mL distilled water.72h is stirred at room temperature, is filtered, filter cake acetone and ethanol
Washing is multiple, and 24h is dried in vacuo at 60 DEG C and obtains eight vinyl silsesquioxanes.
(3) preparation for surpassing crosslinking polyaniline under nitrogen protection, added into 50mL round-bottomed flasks 1.00g polyanilines,
The vinyl silsesquioxanes of 0.862g eight, the anhydrous AlCl of 2.00g3And 20mL1,2- dichloroethanes, magnetic agitation 1h, it is warming up to 80
DEG C and keep this thermotonus 24h, filter, product washs with distilled water, absolute ethyl alcohol successively, and product then is placed in into Soxhlet carries
Take in device, made solvent with methanol, tetrahydrofuran respectively and respectively purified 48h, 24h is dried in vacuo at 60 DEG C, obtain super crosslinking polyaniline,
Yield is 100%, as shown in Figure 3.
The super crosslinking polyaniline that embodiment 1~5 is prepared, with polyaniline and eight vinyl silsesquioxane mass ratioes
Increase, specific surface area gradually increase.When mass ratio is respectively 1:0.1、1:0.2、1:0.3、1:0.509、1:When 0.862, prepare
The specific surface area of the super crosslinking polyaniline gone out is respectively 22,27,59,297,481m2g-1。
Although above-mentioned specific embodiments of the present invention are described, not to the limit of the scope of the present invention
System, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art need not pay
Go out various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of super crosslinking polyaniline, it is characterized in that, this method includes：Using polyaniline as construction unit, with eight
Vinyl silsesquioxane is that crosslinking agent prepares super crosslinking polyaniline by Friedel-Crafts alkylation.
2. preparation method as claimed in claim 1, it is characterized in that：The preparation method of the polyaniline includes：
Aniline is added in hydrochloric acid solution, ammonium persulfate solution is slowly added dropwise and prepares polyaniline.
3. preparation method as claimed in claim 2, it is characterized in that：The specific preparation method of the polyaniline includes：Ice-water bath
Under the conditions of, aniline is added in hydrochloric acid solution, stirred, ammonium persulfate solution is added and makees initiator, 4 ~ 5h is reacted, by product mistake
Filter, washing, obtain polyaniline after drying；Wherein, aniline, hydrochloric acid solution, the volume ratio of ammonium persulfate solution are (4 ~ 5):(50
~55):(20 ~ 30), the concentration of hydrochloric acid solution is 0.5 ~ 4 mol L- 1, the concentration of ammonium persulfate solution is 1 ~ 3mol L- 1。
4. preparation method as claimed in claim 3, it is characterized in that：Concentration of hydrochloric acid solution is 2.0 mol L- 1；Ammonium persulfate
Concentration is 2.0 mol L- 1。
5. preparation method as claimed in claim 1, it is characterized in that：By vinyltrimethoxy silane be placed in acetone, hydrochloric acid and
Eight vinyl silsesquioxanes are prepared in hydrolysis in the mixed solution of water.
6. preparation method as claimed in claim 1, it is characterized in that：The Friedel-Crafts alkylation comprises the following steps：Will
Polyaniline, eight vinyl silsesquioxanes and aluminum trichloride (anhydrous) (AlCl3) be added in 1,2- dichloroethanes, disperse to be formed
Uniform mixture, 12 ~ 36 h are reacted at 60 ~ 120 °C, the product containing super crosslinking polyaniline is prepared.
7. preparation method as claimed in claim 6, it is characterized in that：Obtained product is filtered and uses methanol, tetrahydrofuran work
Solvent surname extraction, it is dried to obtain super crosslinking polyaniline.
8. preparation method as claimed in claim 6, it is characterized in that：The mass ratio of polyaniline and eight vinyl silsesquioxanes is
1:0.1 ~ 0.862, optimal proportion 1:0.862.
9. preparation method as claimed in claim 6, it is characterized in that：The mass ratio of polyaniline and aluminum trichloride (anhydrous) is 1：2；
Friedel-Crafts alkylation condition is：24 h are reacted at 80 °C.
10. the super crosslinking polyaniline being prepared using the method any one of claim 1 ~ 9.
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| CN109320732A (en) * | 2018-10-17 | 2019-02-12 | 齐鲁工业大学 | A kind of high specific area adamantyl porous polymer and preparation method thereof |
| CN109517211A (en) * | 2018-09-28 | 2019-03-26 | 浙江工业大学 | A kind of amino porous polymer and the preparation method and application thereof |
| CN115090269A (en) * | 2022-06-02 | 2022-09-23 | 齐鲁工业大学 | Application of super-crosslinked polyaniline with good chemical stability in wastewater treatment |
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| CN108503829A (en) * | 2018-03-28 | 2018-09-07 | 东华大学 | A kind of method of modifying of high nitrogen-containing microporous polymer and application |
| CN109517211A (en) * | 2018-09-28 | 2019-03-26 | 浙江工业大学 | A kind of amino porous polymer and the preparation method and application thereof |
| CN109517211B (en) * | 2018-09-28 | 2021-10-15 | 浙江工业大学 | Amino porous polymer and preparation method and application thereof |
| CN109320732A (en) * | 2018-10-17 | 2019-02-12 | 齐鲁工业大学 | A kind of high specific area adamantyl porous polymer and preparation method thereof |
| CN109320732B (en) * | 2018-10-17 | 2021-01-12 | 齐鲁工业大学 | Adamantyl porous polymer with high specific area and preparation method thereof |
| CN115090269A (en) * | 2022-06-02 | 2022-09-23 | 齐鲁工业大学 | Application of super-crosslinked polyaniline with good chemical stability in wastewater treatment |
| CN115090269B (en) * | 2022-06-02 | 2023-09-19 | 齐鲁工业大学 | Application of super-crosslinked polyaniline with good chemical stability in wastewater treatment |
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