CN110577644A - preparation method of triazine polyimide capable of being coated - Google Patents
preparation method of triazine polyimide capable of being coated Download PDFInfo
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- CN110577644A CN110577644A CN201910877220.5A CN201910877220A CN110577644A CN 110577644 A CN110577644 A CN 110577644A CN 201910877220 A CN201910877220 A CN 201910877220A CN 110577644 A CN110577644 A CN 110577644A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000004642 Polyimide Substances 0.000 title abstract description 14
- 229920001721 polyimide Polymers 0.000 title abstract description 14
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- 239000012046 mixed solvent Substances 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 10
- IEFWDQQGFDLKFK-UHFFFAOYSA-N 2-n,2-n-dimethyl-1,3,5-triazine-2,4,6-triamine Chemical compound CN(C)C1=NC(N)=NC(N)=N1 IEFWDQQGFDLKFK-UHFFFAOYSA-N 0.000 claims description 10
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 4
- LLOVZIWCKUWRTA-UHFFFAOYSA-N 2-n,2-n-diethyl-1,3,5-triazine-2,4,6-triamine Chemical compound CCN(CC)C1=NC(N)=NC(N)=N1 LLOVZIWCKUWRTA-UHFFFAOYSA-N 0.000 claims description 3
- CVKGSDYWCFQOKU-UHFFFAOYSA-N 2-n-butyl-1,3,5-triazine-2,4,6-triamine Chemical compound CCCCNC1=NC(N)=NC(N)=N1 CVKGSDYWCFQOKU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005891 Cyromazine Substances 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims description 3
- LVQDKIWDGQRHTE-UHFFFAOYSA-N cyromazine Chemical compound NC1=NC(N)=NC(NC2CC2)=N1 LVQDKIWDGQRHTE-UHFFFAOYSA-N 0.000 claims description 3
- 229950000775 cyromazine Drugs 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000003918 triazines Chemical class 0.000 abstract 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 10
- 238000012719 thermal polymerization Methods 0.000 description 5
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
the invention provides a preparation method of triazine polyimide capable of being coated, which has the technical key points that: aromatic dianhydride and triazine compounds are mixed in a volume ratio of 1:1, then putting the mixture solution into a reaction kettle with a polytetrafluoroethylene lining for continuous temperature and time control reaction to obtain the triazine imide capable of being coated, washing, drying and drying a reaction product in the reaction kettle to obtain the triazine imide for photocatalytic decomposition of organic matters and visible light catalysis hydrogen production and carbon dioxide reduction.
Description
Technical Field
the invention relates to the field of energy material preparation and photocatalysis, in particular to a preparation method of triazine polyimide capable of being coated.
Background
With the rapid development of society, the demand of human society for energy is more and more increased, but the energy materials used by people at present are mainly fossil fuels, and the problem of energy shortage is more and more prominent due to the non-renewable nature of the fossil fuels; on the other hand, environmental problems caused by the combustion of fossil fuels also seriously affect the health and quality of life of people, so that the search for renewable clean energy becomes a hot topic of people's attention. Solar energy is an energy source of all living beings on the earth, and the abundant resources are ideal sustainable renewable resources. In 1972, Fujishima and Honda in Japan realize hydrogen production by photolysis of water by illuminating TiO2 electrodes, so that hydrogen production by catalytic decomposition of water by solar energy becomes a solar energy utilization mode with great potential. The graphite-phase carbon nitride with the triazine structure is firstly reported to have the capacity of absorbing visible light catalytic cracking water to produce hydrogen by 2009 Wangxinchen and the like, C atoms and N atoms of the material are orderly and alternately arranged, the material has proper forbidden bandwidth and side band positions, and has the capacity of absorbing visible light catalytic cracking water to produce hydrogen, but the graphite-phase carbon nitride with the triazine structure is mostly prepared by a high-temperature thermal polymerization method at present, and the efficiency of photocatalytic cracking water to produce hydrogen is very low; therefore, there is an urgent need to develop a new material with simple and economical preparation method to improve the efficiency of photocatalytic water splitting to produce hydrogen, so as to improve the utilization of solar energy.
Polyimide (PI) has the unique properties of high mechanical strength, good thermal stability, good chemical resistance and the like, and is widely applied to the industries of separation, coating, aerospace, microelectronics, photoelectrons and the like. Hitherto, polyimide is usually synthesized by condensation of appropriate amine and anhydride through a solution polymerization process, but the condensation degree is improved by removing water generated in the reaction through azeotropic distillation with xylene or a heating method, so that the synthesis process is very complicated; another method is to directly heat and polymerize an amine and anhydride mixture with equal molar ratio in a semi-closed system, but the process often requires very high temperature (. gtoreq.300 ℃). In addition, although conventional polyimides, such as those synthesized from p-phenylenediamine and pyromellitic anhydride, do not have the ability to catalytically decompose water to produce hydrogen by absorbing visible light, aromatic Polyimides (PIs) are an important class of high-performance polymers that have excellent mechanical properties and thermochemical resistance, adopt an interlayer conformation, have strong intermolecular pi-pi interactions, and have good light absorption ability and photocarrier pair migration and separation ability. Therefore, if the advantages of the triazine structure and the polyimide can be combined, the efficiency of producing hydrogen by photocatalytic water splitting can be greatly improved, and the utilization of solar energy is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of triazine polyimide capable of coating, the method does not need complicated steps, does not need high temperature and has higher yield, the prepared material combines the characteristics of graphite-phase carbon nitride and aromatic polyimide, has good thermal stability and proper mechanical strength, can be used for coating processing, has high efficiency of producing hydrogen by photocatalytic water splitting, and is greatly improved compared with the simple graphite-phase carbon nitride and aromatic polyimide.
the purpose of the invention is realized by the following technical scheme:
a preparation method of a film-coated triazine imide comprises the following steps:
S1, completely dissolving the monomer A in a mixed solvent under nitrogen atmosphere, adding the monomer B, keeping the reaction temperature in the mixed solvent at 10-30 ℃, and reacting for 12 hours, so that the monomer A and the monomer B are subjected to polycondensation reaction according to the stoichiometric molar ratio of functional group chemical reaction, and the oligomer primarily polymerized by the monomer A and the monomer B is obtained after the reaction;
s2, under nitrogen atmosphere, controlling the reaction time and the reaction temperature of the preliminary oligomer obtained in the step S1, performing gradient heating reaction, performing further polycondensation reaction on the monomer A and the monomer B according to the stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by the monomer A and the monomer B after the reaction;
S3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
s4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
further, in step S1, the monomer a is pyromellitic anhydride; the monomer B is one of ammeline, 2, 4-diamino-1, 3, 5-triazine, 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine, cyromazine, melamine, 2, 4-diamino-6-butylamino-1, 3, 5-triazine, 2, 4-diamino-6-methyl-1, 3, 5-triazine and 2, 4-diamino-6-diethylamino-1, 3, 5-triazine.
further, in step S1, the mixed solvent is a mixed solution of N, N-dimethylformamide and ethylene glycol; and the volume ratio of the N, N-dimethylformamide to the ethylene glycol is 1: 1.
further, in step S1, the molar ratio of the monomer A to the monomer B in the mixed solvent is calculated according to the chemical reaction of the functional group
1:1, wherein the solid content of the system is 10-33%.
Further, in step S2, the reaction temperature and time of the gradient temperature rise are respectively: reflux reaction at 40 deg.C for 5-6 hr, 60 ℃
Condensing and refluxing at the temperature for 5-6 hours; the reaction was refluxed with condensation at 80 ℃ for 12 hours.
the invention has the beneficial effects that: the reaction substrate of the invention is diverse and simple and easy to obtain, the reaction technology related by the invention is simple, no complex operation is needed, the reaction condition temperature is less than or equal to 180 ℃, the obtained triazine imide solution without post-treatment can be subjected to film coating processing, the triazine imide solution is washed by acetone, hot water and ethanol and then dried to obtain the triazine imide solid, the mechanical strength is high, the thermal stability is good, the triazine imide solid is insoluble in any solvent, and the triazine imide solid has excellent performances of degrading harmful organic matters in water, decomposing water by visible light to produce hydrogen and reducing carbon dioxide.
Drawings
FIG. 1 is a reaction equation of example 2 of the present invention;
FIG. 2 is a graph showing the solid UV-VIS absorption spectrum of the triazine imide of the present invention prepared in example 2;
FIG. 3 is a graph showing the hydrogen production performance by visible light decomposition and water production of the triazine imide prepared by example 2;
FIG. 4 is a reaction equation of example 3 of the present invention;
FIG. 5 is a graph showing the solid UV-VIS absorption spectrum of the triazine imide of the present invention prepared in example 3;
FIG. 6 is a graph showing the hydrogen production performance by visible light decomposition and water production of the triazine imide prepared by example 3;
FIG. 7 is a reaction equation of example 4 of the present invention;
FIG. 8 is a graph showing the solid UV-VIS absorption spectrum of the triazine imide of the present invention prepared in example 4;
FIG. 9 is a graph showing the hydrogen production performance by visible light decomposition and water production of the triazine imide prepared by example 4 according to the present invention;
FIG. 10 is a graph showing hydrogen production performance by visible light decomposition of graphite-phase carbon nitride obtained by solid-state thermal polymerization.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
Example 1:
the invention relates to a preparation method of triazine imide capable of being coated, which comprises the following steps:
s1, completely dissolving the monomer A in a mixed solvent under nitrogen atmosphere, adding the monomer B, keeping the reaction temperature in the mixed solvent at 10-30 ℃, and reacting for 12 hours, so that the monomer A and the monomer B are subjected to polycondensation reaction according to the stoichiometric molar ratio of functional group chemical reaction, and the oligomer primarily polymerized by the monomer A and the monomer B is obtained after the reaction;
S2, under nitrogen atmosphere, controlling the reaction time and the reaction temperature of the preliminary oligomer obtained in the step S1, performing gradient heating reaction, performing further polycondensation reaction on the monomer A and the monomer B according to the stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by the monomer A and the monomer B after the reaction;
s3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
S4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
Further, in step S1, the monomer a is pyromellitic anhydride; the monomer B is one of ammeline, 2, 4-diamino-1, 3, 5-triazine, 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine, cyromazine, melamine, 2, 4-diamino-6-butylamino-1, 3, 5-triazine, 2, 4-diamino-6-methyl-1, 3, 5-triazine and 2, 4-diamino-6-diethylamino-1, 3, 5-triazine.
Further, in step S1, the mixed solvent is a mixed solution of N, N-dimethylformamide and ethylene glycol; and the volume ratio of the N, N-dimethylformamide to the ethylene glycol is 1: 1.
Further, in step S1, the molar ratio of the monomer A to the monomer B in the mixed solvent is calculated according to the chemical reaction of the functional group
1:1, wherein the solid content of the system is 10-33%.
further, in step S2, the reaction temperature and time of the gradient temperature rise are respectively: carrying out condensation reflux reaction at 40 ℃ for 5-6 hours and at 60 ℃ for 5-6 hours; the reaction was refluxed with condensation at 80 ℃ for 12 hours.
The present invention is described below by way of examples with reference to the accompanying drawings, which are intended to illustrate the present invention and not to limit the present invention, and materials, reagents and the like used in the following examples are commercially available without specific reference.
Example 2:
The triazine imide with the solid content of 33 percent is prepared from pyromellitic anhydride and ammeline.
preparation of triazine imide with solid content of 33% by using pyromellitic anhydride and ammeline is carried out according to the reaction equation shown in the attached figure-1.
obtaining the triazine imide according to the following steps:
S1, under nitrogen atmosphere, completely dissolving 15mmol of pyromellitic anhydride in 10ml (volume ratio of 1:1) of mixed solvent of N, N-dimethylformamide and ethylene glycol, adding 15mmol of ammeline, keeping the reaction temperature in the mixed solvent at 10-30 ℃, reacting for 12 hours, carrying out polycondensation reaction on pyromellitic anhydride and ammeline according to the stoichiometric molar ratio of functional group chemical reaction, and obtaining oligomers preliminarily polymerized by pyromellitic anhydride and ammeline after reaction;
s2, under a nitrogen atmosphere, controlling the reaction time and the reaction temperature of the preliminary oligomer obtained in the step S1, carrying out gradient heating reaction, carrying out further polycondensation reaction on pyromellitic dianhydride and ammeline according to a stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by pyromellitic dianhydride and ammeline after the reaction;
s3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
s4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
FIG. 2 is a graph showing the solid UV-visible absorption spectrum of the triazine imide prepared in example 2, from which it can be seen that the material has an absorption peak in the 519nm visible region, which shows that the material has the ability to absorb visible light.
the triazine imide prepared in the embodiment 2 of the invention is used for photocatalytic water decomposition to produce hydrogen, and the method comprises the following specific steps: the photolytic water reaction is carried out under the illumination of a 300W xenon lamp (more than or equal to 420nm), a 20 mg target sample is placed in 90ml deionized water and 10ml triethanolamine, 80 mul of H2PtCl6 is added, wherein triethanolamine is an electronic sacrificial agent, chloroplatinic acid is a cocatalyst, platinum ions are reduced into platinum by full exposure for 30 minutes under the 300W xenon lamp, then an optical filter with the cut-off wavelength of 420nm is added, the photolytic water reaction is carried out under the illumination of the 300W xenon lamp (more than or equal to 420nm), the temperature of the whole reaction system is maintained at 5 ℃ through circulating condensed water, and the generated hydrogen is monitored through gas chromatography.
FIG. 3 is a graph showing the hydrogen production performance by visible light decomposition water of the triazine imide prepared in example 2 of the present invention, and it can be seen that the material can stably decompose water to produce hydrogen in 8.5 hours, the hydrogen production rate is 1076. mu. mol h-1g-1, which is 6 times that of the graphite-phase carbon nitride (176. mu. mol h-1g-1) prepared by solid thermal polymerization in FIG. 10.
example 3:
The triazine imide with the solid content of 18 percent is prepared from pyromellitic anhydride and 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine.
Pyromellitic anhydride and 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine the preparation of triazine imide with a solid content of 18% was carried out in the manner shown in the attached FIG. 4.
Obtaining the triazine imide according to the following steps:
S1, under nitrogen atmosphere, completely dissolving 5mmol of pyromellitic anhydride in 8ml (volume ratio is 1:1) of mixed solvent of N, N-dimethylformamide and ethylene glycol, then adding 5mmol of 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine monomer, keeping the reaction temperature in the mixed solvent at 10-30 ℃ and the reaction time at 12 hours, so that the pyromellitic anhydride and the 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine are subjected to polycondensation reaction according to the stoichiometric molar ratio of functional group chemical reaction, and after the reaction, the oligomer of the preliminary polymerization of the pyromellitic anhydride and the 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine is obtained;
s2, under nitrogen atmosphere, controlling the reaction time and the reaction temperature of the preliminary oligomer obtained in the step S1, carrying out gradient heating reaction, carrying out further polycondensation reaction on pyromellitic dianhydride and 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine according to the stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by pyromellitic dianhydride and 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine after the reaction;
S3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
s4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
The procedure and conditions of the triazine imide for producing hydrogen by photocatalytic water decomposition are consistent with those of example 2, and figure-6 is a graph of the relationship between the hydrogen production amount and time, and the graph can calculate that the hydrogen production rate is 1474 mu mol h < -1 > g < -1 >, which is 8 times of that of graphite phase carbon nitride (176 mu mol h < -1 > g < -1 >) prepared by solid thermal polymerization shown in figure-10, and shows that the triazine imide has excellent capability of absorbing visible light to decompose water and produce hydrogen.
Example 4:
The triazine imide with the solid content of 28 percent is prepared by pyromellitic anhydride and 2, 4-diamino-1, 3, 5-triazine.
pyromellitic anhydride and 2, 4-diamino-1, 3, 5-triazine the preparation of triazine imide with a solid content of 28% was carried out according to the reaction equation shown in FIG. 7.
Obtaining the triazine imide according to the following steps:
s1, under nitrogen atmosphere, completely dissolving 5mmol of pyromellitic dianhydride in 4ml (volume ratio of 1:1) of mixed solvent of N, N-dimethylformamide and ethylene glycol, then adding 5mmol of 2, 4-diamino-1, 3, 5-triazine monomer,
keeping the reaction temperature in the mixed solvent at 10-30 ℃ and the reaction time at 12 hours, carrying out polycondensation reaction on pyromellitic dianhydride and 2, 4-diamino-1, 3, 5-triazine according to the stoichiometric molar ratio of functional group chemical reaction, and obtaining an oligomer preliminarily polymerized by pyromellitic dianhydride and 2, 4-diamino-1, 3, 5-triazine after the reaction;
S2, under nitrogen atmosphere, controlling the reaction time and the reaction temperature of the primary oligomer obtained in the step S1, carrying out gradient heating reaction, carrying out further polycondensation reaction on pyromellitic dianhydride and 2, 4-diamino-1, 3, 5-triazine according to the stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by pyromellitic dianhydride and 2, 4-diamino-1, 3, 5-triazine after the reaction;
s3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
s4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
The procedure and conditions for photocatalytic decomposition of water to produce hydrogen with this type of triazine imide were the same as those in example 2, and FIG. 9 is a graph of hydrogen production amount versus time, from which it was calculated that the hydrogen production rate was 588. mu. mol h-1g-1, which is 3.3 times that of graphite-phase carbon nitride (176. mu. mol h-1g-1) produced by solid-state thermal polymerization, although the photocatalytic effect of this type of triazine imide was not optimal, it was also greatly improved as compared with that of single graphite-phase carbon nitride.
in summary, it can be seen from examples 2-4 of the present invention that the triazine-based imide prepared by the present invention not only has the ability of absorbing visible light and is suitable for coating film processing, but also the efficiency of catalytic cracking water of the triazine-based imide photocatalyst obtained by the present invention is very high, 3-8 times that of the pure graphite phase carbon nitride material.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. A preparation method of triazine imide capable of being coated is characterized by comprising the following steps:
S1, completely dissolving the monomer A in a mixed solvent under nitrogen atmosphere, adding the monomer B, keeping the reaction temperature in the mixed solvent at 10-30 ℃, and reacting for 12 hours, so that the monomer A and the monomer B are subjected to polycondensation reaction according to the stoichiometric molar ratio of functional group chemical reaction, and the oligomer primarily polymerized by the monomer A and the monomer B is obtained after the reaction;
s2, under nitrogen atmosphere, controlling the reaction time and the reaction temperature of the preliminary oligomer obtained in the step S1, performing gradient heating reaction, performing further polycondensation reaction on the monomer A and the monomer B according to the stoichiometric molar ratio of the chemical reaction, and obtaining a prepolymer polymerized by the monomer A and the monomer B after the reaction;
s3, transferring the prepolymer obtained in the step S2 to a reaction kettle with a polytetrafluoroethylene lining, keeping the reaction temperature in the reaction kettle at 180 ℃, keeping the reaction time at 72 hours, and after the reaction is finished, naturally annealing and cooling to obtain the triazine imide for coating;
S4, naturally annealing and cooling the product after the reaction in the step S3, washing the product with acetone to enable the target product to be completely precipitated, centrifuging the product to obtain solid precipitate, centrifuging and washing the solid precipitate twice with hot water at 90 ℃, centrifuging and washing the solid precipitate once with ethanol, finally drying the solid precipitate in vacuum at 80-100 ℃ for 12-16 hours to obtain the triazine imide for photocatalytic decomposition of organic matters, visible light catalysis hydrogen production and carbon dioxide reduction.
2. the method of claim 1, wherein in step S1, the monomer a is pyromellitic dianhydride; the monomer B is one of ammeline, 2, 4-diamino-1, 3, 5-triazine, 2, 4-diamino-6-dimethylamino-1, 3, 5-triazine, cyromazine, melamine, 2, 4-diamino-6-butylamino-1, 3, 5-triazine, 2, 4-diamino-6-methyl-1, 3, 5-triazine and 2, 4-diamino-6-diethylamino-1, 3, 5-triazine.
3. The method of claim 1, wherein in step S1, the mixed solvent is a mixed solution of N, N-dimethylformamide and ethylene glycol; and the volume ratio of the N, N-dimethylformamide to the ethylene glycol is 1: 1.
4. The method of claim 1, wherein in step S1, the monomer A and the monomer B are copolymerized in a mixed solvent according to a stoichiometric molar ratio of 1:1, wherein the solid content of the system is 10-33%.
5. The method of claim 1, wherein in step S2, the temperature and time of the gradient temperature rise are respectively: carrying out condensation reflux reaction at 40 ℃ for 5-6 hours and at 60 ℃ for 5-6 hours; the reaction was refluxed with condensation at 80 ℃ for 12 hours.
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