CN110156988B - Phenanthroimidazolyl triazine polymer and preparation method and application thereof - Google Patents
Phenanthroimidazolyl triazine polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a phenanthroimidazolyl triazine polymer and a preparation method thereof. Brominating 9, 10-phenanthrenequinone, protecting carbonyl, making substitution reaction with cyanate, oxidizing into 3, 6-dicyano-9, 10-phenanthrenequinone, then cyclizing with p-cyanobenzaldehyde imidazole to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole (CDPI), finally ZnCl is passed through with this as building block2The phenanthrene imidazolyl triazine polymer is obtained by the ionic thermal polymerization reaction. The phenanthroimidazolyl triazine polymer provided by the invention has the advantages of high specific surface area, abundant pore structures, good thermal stability and the like, and is simple to prepare, low in cost and excellent in CO under the 273K condition2And (4) adsorption performance.
Description
Technical Field
The invention relates to a triazine polymer, in particular to a phenanthroimidazolyl triazine polymer for gas adsorption and a preparation method thereof, and belongs to the field of gas adsorbents.
Background
It is well known that the large emission of carbon dioxide is a significant cause of the greenhouse effect on earth, and thus carbon dioxide is also called greenhouse gas. Based on the current situation of increasing fossil fuel demand, it is not practical to limit the emission of carbon dioxide. However, we can absorb the carbon dioxide during its discharge and can further use the absorbed carbon dioxide for industrial feedstock production, such as the reduction of carbon dioxide to methanol and the like.
The carbon dioxide capture technology mainly comprises liquid amine absorption, membrane separation, adsorption methods and the like. At present, liquid amine solution is mainly used for absorbing carbon dioxide, and the method has high adsorption quantity, good selectivity and high efficiency, but has inherent defects of equipment corrosion, difficult recovery, easy volatilization, poor cycle performance and the like, and limits further application of the method in industry. The membrane separation technique has low efficiency and complex operation, and is generally rarely used. The adsorption method which is developed in recent years has the advantages of high adsorption quantity, no corrosion, low cost and the like by adopting a solid adsorption material to adsorb carbon dioxide, and makes up for the defects of the two methods. Solid adsorbents are certainly a good choice for capturing carbon dioxide, converting it to a solid form during the reaction, for storage, transport and use. Fibers, ceramic materials and metal oxides, and porous materials have various characteristics in adsorbing carbon dioxide. The method has the following problems that the technology is mature, the source is wide, the adsorption capacity of the material which is easy to synthesize is generally low, the material with high adsorption capacity is harsh in the existing synthesis condition, the energy consumption is high, the cost is high, and the reaction process is not easy to control.
In recent years, porous organic polymer materials for catalysis, gas adsorption, and separation have attracted much attention. Compared with traditional activated carbon, Metal Organic Framework (MOF) and the like, the porous organic polymer material has the advantages of high adsorbability, non-metal doping, stable structure and the like. By virtue of the synthesis of specific building blocks and different connection methods, porous organic polymer materials have been developed in many categories, such as: covalent Organic Frameworks (COFs), Covalent Microporous Polymers (CMPs), hypercrosslinked polymers (HCPs), and the like.
Through a great deal of research, there still exist some problems in the research field of the solid adsorbent for adsorbing carbon dioxide: at present, the adsorption capacity for adsorbing carbon dioxide can be properly improved by adopting polyamine amination reagents, methods for increasing the specific surface area of a carrier and the like, but the improvement effect is still to be further improved; secondly, the phenomenon that the diffusion of carbon dioxide in a carrier pore channel is blocked generally exists in the process of adsorbing the carbon dioxide by the solid adsorbent, so that the adsorption capacity of the adsorbent to the carbon dioxide is reduced; moreover, the existing solid adsorbent is generally poor in heat resistance, and is not enough to meet the use requirements under specific conditions (such as high-temperature flue gas), so that the application space of the solid adsorbent is limited. Therefore, the development of a solid adsorbent having high heat resistance and strong carbon dioxide adsorption capacity is the focus of future research in this field.
Disclosure of Invention
Covalent Triazine Frameworks (CTFs) also belong to the class of porous organic polymers, the most important synthetic method of which is the ionothermal method, i.e. monomers bearing multiple cyano groups with ZnCl2After mixing, the reaction is carried out at high temperature. The covalent triazine framework obtained by the ionothermal method has ultrahigh stability and excellent carbon dioxide adsorption performance. A novel phenanthroimidazolyl building block is designed, and a novel phenanthroimidazolyl triazine polymer is obtained by an ionothermal method. The phenanthroimidazolyl triazine polymer has the advantages of high specific surface area, abundant pore structures, stable properties and the like, and particularly has excellent CO at the temperature of 0 DEG C2And (4) adsorption performance.
The technical scheme provided by the invention for solving the technical problems is as follows:
one of the objects of the present invention is to provide a phenanthroimidazolyl triazine polymer, which is a polymer having the general structural formula (I):
preferably, the polymer is prepared by the following preparation method: firstly, carrying out bromination reaction and carbonyl protection on 9, 10-phenanthrenequinone, carrying out substitution reaction with cyanate, and oxidizing a product into 3, 6-dicyano-9, 10-phenanthrenequinone; cyclizing the 3, 6-dicyano-9, 10-phenanthrenequinone with p-cyanobenzaldehyde imidazole to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole; then 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2Reacting to obtain the phenanthrene imidazolyl triazine polymer.
Preferably, the bromination reaction is a reaction of 9, 10-phenanthrenequinone and bromine (preferably liquid bromine) to obtain 3, 6-dibromo-9, 10-phenanthrenequinone; and/or
Preferably, the carbonyl protection is 3, 6-dibromo-9, 10-phenanthrenequinone and dimethyl ester, so as to obtain 3, 6-dibromo-9, 10-dimethoxyphenanthrene.
Preferably, the substitution reaction with cyanate is to react 3, 6-dibromo-9, 10-dimethoxyphenanthrene with cyanate to obtain 3, 6-dicyano-9, 10-dimethoxyphenanthrene; and/or
Preferably, the oxidation of the product to 3, 6-dicyano-9, 10-phenanthrenequinone is carried out by reacting 3, 6-dicyano-9, 10-dimethoxyphenanthrene with an oxidant to obtain 3, 6-dicyano-9, 10-phenanthrenequinone.
Another object of the present invention is to provide a method for preparing a phenanthroimidazolyl triazine polymer or a method for preparing the phenanthroimidazolyl triazine polymer, the method comprising the steps of:
1) preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole: carrying out bromination reaction, carbonyl protection and substitution reaction with cyanate on the 9, 10-phenanthrenequinone, and oxidizing a product into 3, 6-dicyano-9, 10-phenanthrenequinone; cyclizing the 3, 6-dicyano-9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole;
(2) synthesis of phenanthroimidazolyl triazine polymer: reacting 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2Uniformly mixing, heating and reacting to obtain the phenanthroimidazole group triazine polymer.
Preferably, the step (1) is specifically: preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole:
preparation of 3, 6-dibromo-9, 10-phenanthrenequinone:
dissolving 9, 10-phenanthrenequinone and an initiator (preferably dibenzoyl peroxide) in a solvent (preferably nitrobenzene), dropwise adding a bromine solution (preferably liquid bromine), heating the mixture to 90-150 ℃ (preferably 95-140 ℃, more preferably 100-; the reaction formula is as follows:
b, preparing 3, 6-dibromo-9, 10-dimethoxyphenanthrene:
dissolving 3, 6-dibromo-9, 10-phenanthrenequinone and a catalyst (preferably tetrabutylammonium bromide and/or sodium dithionite) in a solvent (preferably a THF solution), uniformly mixing, then adding dimethyl ester (preferably dimethyl sulfate and/or dimethyl carbonate), adjusting the pH to be alkaline (preferably adjusting the pH to 10-14 by using a sodium hydroxide solution), uniformly mixing (preferably shaking for 1-5min), cooling (preferably adding ice water into the reaction system), separating out a solid (preferably adding deionized water into the reaction system), separating (preferably filtering or suction filtering), and performing column chromatography separation (preferably performing column chromatography separation by using petroleum ether) to obtain a product 3, 6-dibromo-9, 10-dimethoxyphenanthrene; the reaction formula is as follows:
c, preparation of 3, 6-dicyano-9, 10-dimethoxyphenanthrene:
dissolving 3, 6-dibromo-9, 10-dimethoxyphenanthrene and cyanate (preferably cuprous cyanide) in a solvent (preferably DMF), heating and refluxing (preferably under nitrogen atmosphere for 12-48h), adding a precipitant (preferably ethylenediamine and/or sodium hypochlorite solution), stirring (preferably at 80-120 ℃ for 0.5-4h) for reaction, separating (preferably filtering or suction filtration), and performing column chromatography on the separated solid (preferably using a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 2-20) to obtain a product, namely 3, 6-dicyano-9, 10-dimethoxyphenanthrene; the reaction formula is as follows:
preparation of 3, 6-dicyano-9, 10-phenanthrenequinone:
dispersing 3, 6-dicyano-9, 10-dimethoxyphenanthrene in an oxidant (preferably, the oxidant is one or more of concentrated nitric acid, concentrated sulfuric acid, perchloric acid and potassium permanganate solution), stirring (preferably, the stirring time is 5-20min), and separating (preferably, filtering or suction filtering) to obtain a product, namely 3, 6-dicyano-9, 10-phenanthrenequinone; the reaction formula is as follows:
preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole:
dissolving 3, 6-dicyano-9, 10-phenanthrenequinone and p-cyanobenzaldehyde in a solvent (preferably a mixed solution of ammonium acetate in acetic acid), heating and refluxing (preferably for 6-48H), separating (preferably filtering or suction filtering), washing (preferably washing with ethanol) a solid product obtained by separation to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole; the reaction is as follows:
preferably, the step (2) is specifically: synthesis of phenanthroimidazolyl triazine polymer: 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d prepared in the step (1)]Imidazole and ZnCl2Uniformly mixing (preferably grinding and mixing), adding into a closed reactor, vacuumizing the reactor, and heating to react (preferably, heating to 600 ℃ and more preferably to 500 ℃ and 300 ℃ by adopting a muffle furnace, wherein the reaction time is 1-5d, preferably 2-4d) to obtain the phenanthroimidazolyl triazine polymer; the reaction formula is as follows:
preferably, the obtained phenanthroimidazolyl triazine polymer is washed by dilute hydrochloric acid, DMF and deionized water in sequence, and dried (preferably dried under vacuum at 100-150 ℃ for 4-24h) to obtain the purified phenanthroimidazolyl triazine polymer.
Preferably, in step a, the molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1:1-3, preferably 1: 1.2-2.5.
Preferably, in step a, the mass concentration of the 9, 10-phenanthrenequinone dissolved in the solvent is 0.10-0.20g/ml, preferably 0.12-0.18 g/ml.
Preferably, in step a, the mass concentration of the initiator dissolved in the solvent is 0.01-0.10mol/L, preferably 0.02-0.08 mol/L.
Preferably, in step b, the molar ratio of 3, 6-dibromo-9, 10-phenanthrenequinone to dimethyl ester (preferably dimethyl sulfate and/or dimethyl carbonate) is 1:1 to 3, preferably 1:1.2 to 2.5, more preferably 1:1.5 to 2.
Preferably, in step b, the catalyst is added in an amount of 0.01 to 0.20g/ml, preferably 0.02 to 0.10 g/ml.
Preferably, in the step b, the mass concentration of the 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.01 to 0.10g/ml, and preferably 0.015 to 0.080 g/ml.
Preferably, in step c, the molar ratio of 3, 6-dibromo-9, 10-dimethoxyphenanthrene to cyanate is 1:0.2 to 3, preferably 1:0.5 to 2.5.
Preferably, in the step c, the 3, 6-dibromo-9, 10-dimethoxyphenanthrene is dissolved in the solvent at a mass concentration of 0.01 to 0.20g/ml, preferably 0.05 to 0.15 g/ml.
Preferably, in step c, the molar ratio of 3, 6-dibromo-9, 10-dimethoxyphenanthrene to ethylenediamine is 1:5 to 40, preferably 1:8-35, more preferably 1: 10-25.
Preferably, in step d, the 3, 6-dicyano-9, 10-dimethoxyphenanthrene is dispersed in the oxidant at a mass concentration of 0.01-0.10g/ml, preferably 0.015-0.080 g/ml.
Preferably, in step e, the molar ratio of 3, 6-dicyano-9, 10-phenanthrenequinone to p-cyanobenzaldehyde is 1:0.5-3, preferably 1: 0.8-2.
Preferably, in step e, the mass concentration of 3, 6-dicyano-9, 10-phenanthrenequinone dissolved in the solvent is 0.002-0.100g/ml, preferably 0.005-0.050 g/ml.
Preferably, in step e, the solvent is a mixed solution of ammonium acetate dissolved in acetic acid, wherein the mass concentration of the ammonium acetate is 0.01-0.10g/ml, and preferably 0.02-0.08 g/ml.
Preferably, in step (2), 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2Is 1:1 to 10, preferably 1:2 to 8, more preferably 1:3 to 6.
It is a further object of the present invention to provide a use of the phenanthroimidazolyl triazine polymer or of the phenanthroimidazolyl triazine polymer prepared according to the above-mentioned process, for gas adsorption.
Preferably, phenanthroimidazolyl triazine polymers are used for CO2And (4) adsorbing.
It should be noted that, in the present invention, in the dibenzoyl peroxide nitrobenzene solution in step a, the dibenzoyl peroxide functions as an initiator: and initiating liquid bromine to attack Sn1 of hydrogen at 3 and 6 positions on the phenanthrene ring of the 9, 10-phenanthrenequinone to obtain a target product.
In the present invention, nitrobenzene functions as a solvent.
In the present invention, tetrabutylammonium bromide in step b functions as a phase transfer catalyst; the reactants in the two-phase solvent can be fully contacted, so that the reaction keeps higher yield.
It should be noted that in step b, sodium dithionite functions as a promoter. The carbonyl group in the 3, 6-dibromophenanthrenequinone is promoted to be converted into a hydroxyl group serving as an intermediate, so that the protection reaction can be smoothly carried out.
In the present invention, the purpose of adjusting the pH to alkaline in step b is that the dimethyl ester protection reaction needs to be carried out smoothly under alkaline conditions and the reaction yield is high.
In the invention, the effect of adding ice water is that ice water is added to adjust the temperature of the system to keep the temperature at room temperature because the dimethyl ester protects the violent heat release in the reaction process, thereby ensuring the smooth reaction.
In the present invention, the effect of adding deionized water is to precipitate out the product. Water and the solvent of the reaction can be mutually soluble, and the product is insoluble in water, so that a large amount of water is added to facilitate the separation of the target product.
In the present invention, in step c, the addition of ethylenediamine serves to precipitate the target product. The cyano on the product can be partially coordinated with copper ions in the system to generate a complex, and the coordination of the ethylenediamine and the copper ions is greater than that of the cyano, so that the copper ions in the complex can be replaced to precipitate the product. The ethylenediamine can be replaced by sodium hypochlorite.
In the present invention, in step d, 3, 6-dicyano-9, 10-dimethoxyphenanthrene is dispersed in an oxidant (preferably, the oxidant is one or more of concentrated nitric acid, concentrated sulfuric acid, perchloric acid and potassium permanganate solution) for the purpose of removing methyl protection. Ether linkages are not very stable chemical bonds and deprotection reactions can occur under strongly acidic conditions or under specific catalytic conditions.
In the present invention, ammonium acetate is a key compound for providing a nitrogen source in the ring closure reaction in step e, and thus its sufficient amount is ensured to obtain the target product.
In the present invention, in step (2), ZnCl is used2Acts as a lewis base catalyst and solvent. The zinc chloride is in a molten state at high temperature and can act as a solvent. In addition, only under the catalysis of zinc chloride, the cyano groups can be trimerized to form polymers.
The phenanthroimidazolyl triazine polymer prepared by the method has high BET specific surface area, excellent adsorption performance on carbon dioxide under the 273K condition, and the adsorption capacity of 4.5mmol g-1。
Compared with the prior art, the phenanthroimidazolyl triazine polymer provided by the invention has the following advantages:
1. the polymer monomer is 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Synthesis of imidazole with ZnCl2The polymerization to form triazine ring under high temperature condition is the first time.
2. The polymer has a large specific surface area and has certain advantages in the aspect of gas adsorption.
3. The polymer has active functional groups such as imidazole ring, triazine ring and the like, which are beneficial to the adsorption of carbon dioxide.
Drawings
FIG. 1 is a diagram showing the synthesis of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole according to the present invention.
FIG. 2 is a nuclear magnetic representation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole prepared in example 3 of the present invention.
FIG. 3 is a diagram showing the synthesis of phenanthroimidazolyl triazine polymer prepared in example 4 of the present invention.
FIG. 4 is a nitrogen adsorption and desorption curve of phenanthroimidazolyl triazine polymer prepared in example 4 of the present invention.
FIG. 5 shows the CO at 273K of phenanthroimidazolyl triazine polymer in example 4 of the present invention2Adsorption profile.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
Example 1
A process for preparing a phenanthroimidazolyl triazine polymer, the process comprising the steps of:
(1) preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ]:
preparation of 3, 6-dibromo-9, 10-phenanthrenequinone:
dripping 10.2ml of liquid bromine into 20.4g of 9, 10-phenanthrenequinone and dibenzoyl peroxide nitrobenzene solution, heating the mixture to 110 ℃ after finishing dripping, treating for 16h, washing the crude product with n-hexane, and filtering to obtain a brown product, namely 3, 6-dibromo-9, 10-phenanthrenequinone;
b, preparing 3, 6-dibromo-9, 10-dimethoxyphenanthrene:
11.12g of 3, 6-dibromo-9, 10-phenanthrenequinone, 2.85g of tetrabutylammonium bromide were dissolved in 100ml of THF and 100ml of H2And O is mixed in a separating funnel by shaking for 5 minutes, then 15ml of dimethyl sulfate is added, 30ml of 14.1M sodium hydroxide aqueous solution is added, the mixture is mixed by shaking for 3 minutes, 100g of ice cooling is added, a large amount of deionized water is added into a reaction system, and the mixture is filtered, separated by column chromatography, and the product of 3, 6-dibromo-9, 10-dimethoxyphenanthrene is obtained.
c, preparation of 3, 6-dicyano-9, 10-dimethoxyphenanthrene:
placing 1.584g of 3, 6-dibromo-9, 10-dimethoxyphenanthrene, 1.076g of CuCN and 20ml of DMF in a round-bottom flask, heating and refluxing for 36h under nitrogen atmosphere, then suspending the reaction system in 200ml of water and adding 3ml of ethylenediamine, stirring for 2h at 100 ℃ for reaction, filtering, and performing column chromatography separation by using a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:8 to obtain the product of 3, 6-dicyano-9, 10-dimethoxyphenanthrene.
Preparation of 3, 6-dicyano-9, 10-phenanthrenequinone:
dispersing 3, 6-dicyan-9, 10-dimethoxy phenanthrene 1g in 20ml of concentrated nitric acid, stirring for 10min, and carrying out suction filtration to obtain a product 3, 6-dicyan-9, 10-phenanthrenequinone.
Preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole:
3, 6-dicyano-9, 10-phenanthrenequinone 1.215g, p-cyanobenzaldehyde 0.615g, ammonium acetate 3.525g were dissolved in 50ml of acetic acid, heated under reflux for 24 hours, filtered with suction, and the solid product obtained by separation was washed with ethanol to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole.
(2) Preparation of phenanthroimidazolyl triazine Polymer:
0.122g of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole with 0.23g anhydrous ZnCl2Grinding, uniformly mixing, adding into a sealed tube, vacuumizing the sealed tube, putting into a muffle furnace, heating to 400 ℃, reacting for 72 hours, taking out a sample in the sealed tube, grinding into powder, washing with dilute hydrochloric acid, DMF (dimethyl formamide) and deionized water in sequence, and vacuum drying at 120 ℃ for 12 hours to obtain the phenanthroimidazolyl triazine polymer.
The phenanthroimidazolyl triazine polymer prepared by the method has a high BET specific surface area, has excellent adsorption performance on carbon dioxide under a 273K condition, and the adsorption amount reaches 4.5 mmol/g.
Example 2
Example 1 was repeated, except that 2.85g of tetrabutylammonium bromide were replaced by 16.018g of sodium dithionate.
Example 3
Example 1 was repeated, except that in step a sodium dithionate was also added, 2.85g of tetrabutylammonium bromide was exchanged for 2.85g of tetrabutylammonium bromide and 16.018g of sodium dithionate.
Example 4
Examples 1 to 3 were repeated, except that in step b 15ml of dimethyl sulfate were replaced by 35ml of dimethyl carbonate
Example 5
Examples 1-4 were repeated except that in step c the ethylenediamine was replaced with a sodium hypochlorite solution.
Example 6
Examples 1 to 5 were repeated except that in step d the concentrated nitric acid was changed to concentrated sulfuric acid.
The polymer prepared by the invention is measured for N in the polymer pair under the conditions of 77K and 1.0p/po pressure, when the pressure is increased from 0 to 1p/po, and under the specific pressure value2When the pressure reaches a maximum, the polymer pair N2The adsorption value of (A) is also maximized, which represents the N of the polymer under 77K conditions2Adsorption capacity; when the pressure was decreased from 1p/po to 0, the N of the polymer was measured at a specific pressure2A desorption value; further from N of the polymer2And (3) obtaining important parameters such as the surface area of the polymer according to a BET algorithm by using an adsorption-desorption curve. The results are shown in FIG. 4.
Secondly, the polymer of the invention is measured for CO at 273K under the condition of 1bar pressure, the pressure is increased from 0mbar to 1000mbar, and the polymer is measured for CO at a specific pressure value2When the pressure reaches a maximum, the polymer has a value of adsorption for CO2The adsorption value of (A) is also maximized, which represents the CO at 273K of the polymer2Adsorption capacity. The results are shown in FIG. 5.
Claims (18)
1. A phenanthroimidazolyl triazine polymer, which is a polymer having the general structural formula (I):
2. the phenanthroimidazolyl triazine polymer of claim 1, wherein: the polymer is prepared by the following preparation method: firstly, the 9, 10-phenanthrenequinone is passed through bromineCarrying out a reaction, protecting carbonyl, carrying out a substitution reaction with cyanate, and oxidizing a product into 3, 6-dicyano-9, 10-phenanthrenequinone; cyclizing the 3, 6-dicyano-9, 10-phenanthrenequinone with p-cyanobenzaldehyde imidazole to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole; then 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2Reacting to obtain the phenanthrene imidazolyl triazine polymer.
3. The phenanthroimidazolyl triazine polymer of claim 2, wherein: the bromination reaction is a reaction of 9, 10-phenanthrenequinone and bromine to obtain 3, 6-dibromo-9, 10-phenanthrenequinone; and/or
The carbonyl protection is that 3, 6-dibromo-9, 10-phenanthrenequinone reacts with dimethyl ester to obtain 3, 6-dibromo-9, 10-dimethoxyphenanthrene.
4. The phenanthroimidazolyl triazine polymer of claim 2 or 3, wherein: the substitution reaction with cyanate is to react 3, 6-dibromo-9, 10-dimethoxyphenanthrene with cyanate to obtain 3, 6-dicyano-9, 10-dimethoxyphenanthrene; and/or
The product is oxidized into 3, 6-dicyano-9, 10-phenanthrenequinone, namely 3, 6-dicyano-9, 10-dimethoxyphenanthrene, and the 3, 6-dicyano-9, 10-phenanthrenequinone is obtained by reacting with an oxidant.
5. A process for preparing a phenanthroimidazolyl triazine polymer according to any of claims 1 to 4, comprising the following steps:
(1) preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole: carrying out bromination reaction, carbonyl protection and substitution reaction with cyanate on the 9, 10-phenanthrenequinone, and oxidizing a product into 3, 6-dicyano-9, 10-phenanthrenequinone; cyclizing the 3, 6-dicyano-9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole;
(2) synthesis of phenanthroimidazolyl triazine polymer: reacting 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2Uniformly mixing, heating and reacting to obtain the phenanthroimidazole group triazine polymer.
6. The method of claim 5, wherein: the step (1) is specifically as follows: preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole:
preparation of 3, 6-dibromo-9, 10-phenanthrenequinone:
dissolving 9, 10-phenanthrenequinone and an initiator in a solvent, dropwise adding a bromine solution, heating the mixture to 90-150 ℃ after dropwise adding is finished, treating for 8-24h, washing, and separating to obtain a brown product 3, 6-dibromo-9, 10-phenanthrenequinone;
b, preparing 3, 6-dibromo-9, 10-dimethoxyphenanthrene:
dissolving 3, 6-dibromo-9, 10-phenanthrenequinone and a catalyst in a solvent, uniformly mixing, then adding dimethyl ester, adjusting the pH value to be alkaline, uniformly mixing, cooling, separating out a solid, separating, and performing column chromatography separation to obtain a product, namely 3, 6-dibromo-9, 10-dimethoxyphenanthrene;
c, preparation of 3, 6-dicyano-9, 10-dimethoxyphenanthrene:
dissolving 3, 6-dibromo-9, 10-dimethoxyphenanthrene and cyanate in a solvent, heating and refluxing, adding a precipitating agent, stirring for reaction, separating, and carrying out column chromatography on the separated solid to obtain a product, namely 3, 6-dicyano-9, 10-dimethoxyphenanthrene;
preparation of 3, 6-dicyano-9, 10-phenanthrenequinone:
dispersing 3, 6-dicyan-9, 10-dimethoxyphenanthrene in an oxidant, stirring and separating to obtain a product 3, 6-dicyan-9, 10-phenanthrenequinone;
preparation of 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole:
dissolving 3, 6-dicyano-9, 10-phenanthrenequinone and p-cyanobenzaldehyde in a solvent, heating and refluxing, separating, and washing a solid product obtained by separation to obtain 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d ] imidazole.
7. The method of claim 6, wherein: in the step a, the initiator is dibenzoyl peroxide, the solvent is nitrobenzene, the bromine solution is liquid bromine, the washing adopts n-hexane for washing, and the separation adopts filtration, suction filtration or column analysis;
in the step b, the catalyst is tetrabutylammonium bromide and/or sodium hydrosulfite, the solvent is a THF solution, the dimethyl ester is dimethyl sulfate and/or dimethyl carbonate, the pH is adjusted to be alkaline by adopting a sodium hydroxide solution, the pH is adjusted to 10-14, the cooling is to add ice water into the reaction system, the separation adopts filtration or suction filtration, and the column chromatography separation adopts petroleum ether for column chromatography separation;
in the step c, the cyanate is cuprous cyanide, the solvent is DMF, the heating reflux is heating reflux for 12-48h under the nitrogen atmosphere, the precipitating agent is an ethylenediamine and/or sodium hypochlorite solution, the stirring is stirring for 0.5-4h at 80-120 ℃, the separation adopts filtration or suction filtration, and the column chromatography adopts a mixed solution of ethyl acetate and petroleum ether with the volume ratio of 1:2-20 to carry out column chromatography;
in the step d, the oxidant is one or more of concentrated nitric acid, concentrated sulfuric acid, perchloric acid and potassium permanganate solution, the stirring time is 5-20min, and the separation adopts filtration or suction filtration;
in the step e, the solvent is a mixed solution of ammonium acetate dissolved in acetic acid, the heating reflux time is 6-48h, the separation adopts filtration or suction filtration, and the washing adopts ethanol washing.
8. The method of claim 5, wherein: the step (2) is specifically as follows: synthesis of phenanthroimidazolyl triazine polymer: 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d prepared in the step (1)]Imidazole and ZnCl2And uniformly mixing, adding the mixture into a closed reactor, vacuumizing the reactor, and heating to react to obtain the phenanthroimidazole group triazine polymer.
9. The method of claim 8, wherein: in the step (2), grinding and mixing are adopted for uniform mixing; the heating reaction is carried out by heating to 600 ℃ in a muffle furnace, and the reaction time is 1-5 d.
10. The method of claim 9, wherein: in the step (2), the heating is carried out by heating to 500 ℃ in a muffle furnace, and the reaction time is 2-4 d.
11. The method of claim 8, wherein: and washing the obtained phenanthroimidazolyl triazine polymer with dilute hydrochloric acid, DMF (dimethyl formamide) and deionized water in sequence, and drying to obtain the refined phenanthroimidazolyl triazine polymer.
12. The method of claim 11, wherein: the drying is vacuum drying at 100-150 ℃ for 4-24 h.
13. The method of claim 7, wherein: in the step a, the molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1: 1-3; the mass concentration of the 9, 10-phenanthrenequinone dissolved in the solvent is 0.10-0.20 g/ml; the initiator is dissolved in the solvent, and the molar concentration of the initiator is 0.01-0.10 mol/L;
in the step b, the molar ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the dimethyl ester is 1: 1-3; the adding amount of the catalyst is 0.01-0.20 g/ml; the mass concentration of 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.01-0.10 g/ml;
in the step c, the molar ratio of the 3, 6-dibromo-9, 10-dimethoxyphenanthrene to the cyanate is 1: 0.2-3; the mass concentration of 3, 6-dibromo-9, 10-dimethoxyphenanthrene dissolved in the solvent is 0.01-0.20 g/ml; the molar ratio of the 3, 6-dibromo-9, 10-dimethoxyphenanthrene to the precipitating agent is 1: 5-40;
in the step d, the mass concentration of 3, 6-dicyano-9, 10-dimethoxyphenanthrene dispersed in the oxidant is 0.01-0.10 g/ml;
in the step e, the molar ratio of the 3, 6-dicyano-9, 10-phenanthrenequinone to the p-cyanobenzaldehyde is 1: 0.5-3; the mass concentration of 3, 6-dicyan-9, 10-phenanthrenequinone dissolved in the solvent is 0.002-0.100 g/ml; and dissolving ammonium acetate in the mixed solution of acetic acid, wherein the mass concentration of the ammonium acetate is 0.01-0.10 g/ml.
14. The method of claim 7, wherein: in the step a, the molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1: 1.2-2.5; the mass concentration of the 9, 10-phenanthrenequinone dissolved in the solvent is 0.12-0.18 g/ml; the initiator is dissolved in the solvent, and the molar concentration of the initiator is 0.02-0.08 mol/L;
in the step b, the mol ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the dimethyl ester is 1: 1.2-2.5; the adding amount of the catalyst is 0.02-0.10 g/ml; the mass concentration of 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.015-0.08 g/ml;
in the step c, the molar ratio of the 3, 6-dibromo-9, 10-dimethoxyphenanthrene to the cyanate is 1: 0.5-2.5; the mass concentration of 3, 6-dibromo-9, 10-dimethoxyphenanthrene dissolved in the solvent is 0.05-0.15 g/ml; the molar ratio of the 3, 6-dibromo-9, 10-dimethoxyphenanthrene to the precipitating agent is 1: 8-35;
in the step d, the mass concentration of 3, 6-dicyano-9, 10-dimethoxyphenanthrene dispersed in the oxidant is 0.015-0.080 g/ml;
in the step e, the molar ratio of the 3, 6-dicyano-9, 10-phenanthrenequinone to the p-cyanobenzaldehyde is 1: 0.8-2; the mass concentration of 3, 6-dicyan-9, 10-phenanthrenequinone dissolved in the solvent is 0.005-0.050 g/ml; and dissolving ammonium acetate in the mixed solution of acetic acid, wherein the mass concentration of the ammonium acetate is 0.02-0.08 g/ml.
15. The method of claim 8, wherein: in the step (2), 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2The molar ratio of (A) to (B) is 1: 1-10.
16. The method of claim 8, wherein: in the step (2), 2- (4-cyanophenyl) -6, 9-dicyano-1H-phenanthro [9,10-d]Imidazole and ZnCl2The molar ratio of (A) to (B) is 1: 2-8.
17. Use of the phenanthroimidazolyl triazine polymer according to any of claims 1 to 4 or prepared according to the process of any of claims 5 to 16, characterized in that: the phenanthroimidazolyl triazine polymer is used for gas adsorption.
18. Use according to claim 17, characterized in that: will phenanthroUse of imidazolyl triazine polymers for CO2And (4) adsorbing.
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