CN110372862B - Triphenylphenanthroimidazole triazine polymer and preparation method and application thereof - Google Patents

Triphenylphenanthroimidazole triazine polymer and preparation method and application thereof Download PDF

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CN110372862B
CN110372862B CN201910687768.3A CN201910687768A CN110372862B CN 110372862 B CN110372862 B CN 110372862B CN 201910687768 A CN201910687768 A CN 201910687768A CN 110372862 B CN110372862 B CN 110372862B
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phenanthrenequinone
triphenylphenanthroimidazole
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bisphenylnitrile
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黎华明
文继开
陈红飙
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Xiangtan University
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Abstract

The invention discloses a triphenylphenanthroimidazole triazine polymer and a preparation method and application thereof. Firstly, brominating 9, 10-phenanthrenequinone, protecting carbonyl, then making substitution reaction with p-cyanobenzene boronic acid, then oxidizing it into 3, 6-di (4,4 '-bisphenylnitrile group) -9, 10-phenanthrenequinone, then cyclizing with p-cyanobenzaldehyde imidazole to obtain 2,6, 9-tri (4,4' -triphenylnitrile group) -1H-phenanthro [9,10-d ]]Imidazole (TBPI), finally ZnCl is passed through using this as building block2The triphenylphenanthroimidazole triazine polymer is obtained by the ionic thermal polymerization reaction. The triphenylphenanthroimidazole triazine polymer provided by the invention has the advantages of high specific surface area, abundant pore structures, good thermal stability and the like, is simple to prepare and low in cost, and has excellent CO under the condition of 273K2And (4) adsorption performance.

Description

Triphenylphenanthroimidazole triazine polymer and preparation method and application thereof
Technical Field
The invention relates to a triphenylphenanthroimidazole triazine polymer, in particular to a triphenylphenanthroimidazole triazine polymer for gas adsorption and a preparation method thereof, and belongs to the field of gas adsorbents.
Background
With the development of economy in recent years, problems regarding our living environment have arisen, and global warming is one of the major issues that we must pay attention to. This phenomenon is due to the large emission of carbon dioxide gas. Efficient carbon dioxide capture and storage (CCS) has received high attention from researchers worldwide in order to reduce the concentration of greenhouse gases in the atmosphere. Unlike amine scrubbing and cryogenic cooling techniques, it requires harsh and even toxic conditions of CO2The solid physical adsorbent is expected to realize CO capture2Practical methods of storage and separation of (e.g. porous carbon materials, Metal Organic Frameworks (MOFs), Porous Organic Polymers (POPs) etc. may mention persistent organic pollutants because the organic building blocks are bound to covalent bonds rather than coordination bonds, both in terms of low density and high thermal and chemical stabilityThe noodles have advantages. Persistent organic pollutants are believed to have other advantages such as non-metal doping, ease of modification, design diversification of components, driving their development in catalysis, gas capture and separation, sensing and electrochemistry.
On the other hand, covalent triazine backbones (CTFs) as subclasses of Porous Organic Polymers (POPs) are usually prepared by ionothermal triazine polymerization at high temperatures, wherein ZnCl2Acting as a solvent and catalyst. As one of the classical nitrogen-rich materials, CTF is believed to be naturally applicable to CO2Absorption and storage, high surface area, high thermal and chemical stability. In addition, various kinds of hydrophilic CO2Partial incorporation into CTF can increase CO2The absorption capacity.
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 triphenylphenanthroimidazole building block is designed, and a novel triphenylphenanthroimidazole triazine polymer is obtained by an ionothermal method. The triphenylphenanthroimidazole triazine polymer has the advantages of high specific surface area, abundant pore structures, stable property 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:
according to a first embodiment of the present invention, there is provided a triphenylphenanthroimidazole triazine polymer characterized in that: the polymer is a polymer having the general structural formula (I):
Figure BDA0002146909790000021
preferably, the polymer is prepared by: firstly, 9, 10-phenanthrenequinoneAfter the perbromination reaction and the carbonyl protection, the reaction product and the p-cyanobenzene boric acid are subjected to substitution reaction. Then oxidizing the product obtained by the substitution reaction into 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone. Then cyclizing 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d]Imidazole. Finally, 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2And reacting to obtain the triphenylphenanthroimidazole triazine polymer.
Preferably, the bromination reaction is specifically to react 9, 10-phenanthrenequinone with bromine (preferably liquid bromine) to obtain 3, 6-dibromo-9, 10-phenanthrenequinone.
Preferably, the molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1:1-3, preferably 1:1.2-2.5, and more preferably 1: 1.8-2.0. And/or
Preferably, the carbonyl protection is specifically to react 3, 6-dibromo-9, 10-phenanthrenequinone with bromohexane to obtain 3, 6-dibromo-9, 10-dihexyloxyphenanthrene.
Preferably, the molar ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the n-bromohexane is 1:1.5 to 4, preferably 1:1.8 to 3, and more preferably 1:2.0 to 2.5. And/or
Preferably, the substitution reaction with the p-cyanobenzene boric acid is to react 3, 6-dibromo-9, 10-dihexyloxyphenanthrene with the p-cyanobenzene boric acid to obtain the 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene.
Preferably, the molar ratio of the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene to the p-cyanobenzene boric acid is 1.2 to 3, preferably 1:1.5 to 2.5, and more preferably 1:1.8 to 2.0. And/or
Preferably, the oxidizing of the product is specifically to react 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-dihexyloxyphenanthrene with an oxidant (preferably one or more of concentrated nitric acid, concentrated sulfuric acid, perchloric acid and potassium permanganate solution) to obtain 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone.
Preferably, the molar ratio of the 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone to the p-cyanobenzaldehyde is 1:0.8-2.5, preferably 1:1-1.8, more preferably 1: 1.2-1.5.
In accordance with a second embodiment of the present invention, there is provided a method for preparing a triphenylphenanthroimidazole triazine polymer or a method for preparing the triphenylphenanthroimidazole triazine polymer in the first embodiment, the method comprising the steps of:
1) preparation of 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole: carrying out bromination reaction and carbonyl protection on 9, 10-phenanthrenequinone, then carrying out substitution reaction on the phenanthrenequinone and p-cyanobenzene boronic acid, and oxidizing a product into 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone; and finally, cyclizing the 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain the 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole.
2) Synthesis of triphenylphenanthroimidazole triazine polymer: 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2Mixing evenly, heating and reacting to obtain the triphenylphenanthroimidazole triazine polymer.
Preferably, step 1) is specifically:
a) 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 80-200 ℃ (preferably 90-180 ℃, more preferably 100-140 ℃) after the dropwise adding is finished, treating for 5-24h (preferably 8-22h, more preferably 10-20h), washing (preferably washing by using n-hexane), and separating (preferably by filtering, suction filtration or column analysis) to obtain the brown product 3, 6-dibromo-9, 10-phenanthrenequinone.
b) 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 n-bromo-hexane, 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), washing (preferably adding deionized water into the reaction system), extracting (preferably using dichloro or ethyl acetate as the solvent), and performing column chromatography separation (preferably using petroleum ether for column chromatography separation) to obtain the product 3, 6-dibromo-9, 10-dihexyloxyphenanthrene.
c) Dissolving 3, 6-dibromo-9, 10-dihexyloxyphenanthrene and p-cyanobenzene boric acid in a solvent (preferably toluene), heating (preferably heating to 60-90 ℃ under nitrogen atmosphere, refluxing for 8-48h), adding water, stirring, extracting (preferably adopting dichloro or ethyl acetate as the solvent), separating the obtained solid, and performing column chromatography (preferably adopting mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 2-20) to obtain the product 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene.
d) Dispersing 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-dihexyloxyphenanthrene 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 the product, namely the 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone.
e) Dissolving 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde in a solvent (preferably the solvent is a mixed solution of ammonium acetate in acetic acid), heating and refluxing (preferably to 60-100 ℃ and refluxing time of 6-48H), separating (preferably filtering or suction filtration), washing a solid product obtained by separation (preferably washing by ethanol) to obtain 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole.
Preferably, step 2) is specifically: 2,6, 9-tris (4,4' -triphenylnitrile) -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 perform reaction (preferably heating to 800 ℃ and 200 ℃ by adopting a muffle furnace, more preferably heating to 700 ℃ and 300 ℃ and the reaction time is 1-5d, preferably 2-4d) to obtain the triphenylphenanthroimidazole triazine polymer.
Preferably, the obtained triphenylphenanthroimidazole 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 refined triphenylphenanthroimidazole triazine polymer.
Preferably, in step a, the molar ratio of 9, 10-phenanthrenequinone to liquid bromine is 1:1 to 3, preferably 1:1.2 to 2.5, more preferably 1:1.8 to 2.0. 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. The mass concentration of the initiator dissolved in the solvent is 0.01-0.10mol/L, preferably 0.02-0.08 mol/L. And/or
Preferably, in the step b, the molar ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the n-bromohexane is 1:1.5 to 4, preferably 1:1.8 to 3, and more preferably 1:2.0 to 2.5. The adding amount of the catalyst is 0.05-0.22g/ml, preferably 0.08-0.15 g/ml; the mass concentration of the 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.02 to 0.12g/ml, and preferably 0.015 to 0.100 g/ml. And/or
Preferably, in step c, the molar ratio of 3, 6-dibromo-9, 10-dihexyloxyphenanthrene to p-cyanophenylboronic acid is 1:1.2 to 3, preferably 1:1.5 to 2.5, more preferably 1:1.8 to 2.0. The mass concentration of the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene dissolved in the solvent is 0.02 to 0.22g/ml, and preferably 0.05 to 0.18 g/ml. And/or
Preferably, in step d, 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene is dispersed in the oxidizing agent in a mass concentration of 0.01 to 0.80g/ml, preferably 0.02 to 0.5 g/ml. And/or
Preferably, in step e, the molar ratio of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone to p-cyanobenzaldehyde is from 1:0.8 to 2.5, preferably from 1:1 to 1.8, more preferably from 1:1.2 to 1.5. The mass concentration of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone dissolved in the solvent is 0.001-0.120g/ml, preferably 0.005-0.080 g/ml; the solvent is a mixed solution of ammonium acetate dissolved in acetic acid, wherein the mass concentration of the ammonium acetate is 0.01-0.15g/ml, and preferably 0.02-0.10 g/ml.
Preferably, in the step (2), 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2Is 1:1 to 15, preferably 1:2 to 12, more preferably 1:3 to 10.
According to a third embodiment of the invention, there is provided the use of a triphenylphenanthroimidazole triazine polymer, or a triphenylphenanthroimidazole triazine polymer prepared according to the process of the second embodiment of the invention, for gas adsorption.
Preferably, triphenylphenanthroimidazole 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, the monomer 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]The imidazole is synthesized for the first time, and the monomer is used in ZnCl2In the presence of a polymer which polymerizes under high temperature conditions to form new triazine rings. The polymer has the advantages of high specific surface area, abundant pore structures, good thermal stability and the like, and has excellent CO under the condition of 273K2And (4) adsorption performance.
In the present invention, nitrobenzene is used for the purpose of acting as a solvent, creating conditions for the reaction to proceed smoothly.
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 invention, in step c, the cyanophenyl group of the p-cyanobenzene boronic acid successfully replaces the bromo group on the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene,
in the invention, the purpose of adjusting the pH value to be alkaline in the step b is that the protection reaction of the n-bromohexane can be smoothly carried out under the alkaline condition, and the reaction yield is high.
In the present invention, in step d, 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene 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 hexyl 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 BET specific surface area of the triphenylphenanthroimidazole triazine polymer prepared by the method is up to 1183m2g-1. Under the condition of 273K, the triphenylphenanthroimidazole triazine polymer has excellent adsorption performance on carbon dioxide, and the prepared triphenylphenanthroimidazole triazine polymer can be used for CO through reasonable regulation and control of temperature and catalyst proportion2The adsorption capacity can reach 4.5mmol g-1。
Compared with the prior art, the triphenylphenanthroimidazole triazine polymer provided by the invention has the following advantages:
1. the polymer monomer is 2,6, 9-tri (4,4' -triphenyl nitrile) -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 synthetic diagram of the present invention for preparing 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole.
FIG. 2 is a nuclear magnetic representation of 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole prepared in example 1 of the present invention.
FIG. 3 is a diagram showing the synthesis of triphenylphenanthroimidazole triazine polymer in example 1 of the present invention.
FIG. 4 is a nitrogen adsorption and desorption curve of triphenylphenanthroimidazole triazine polymer prepared in example 1 of the present invention.
FIG. 5 is a CO at 273K of triphenylphenanthroimidazole triazine polymer in example 1 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 method for preparing triphenylphenanthroimidazole triazine polymer, which comprises the following steps:
1) preparation of 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole:
a) preparation of 3, 6-dibromo-9, 10-phenanthrenequinone:
dripping 11.5ml of liquid bromine into 20.8g of nitrobenzene solution of 9, 10-phenanthrenequinone and dibenzoyl peroxide, 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) preparation of 3, 6-dibromo-9, 10-dihexyloxyphenanthrene:
11.12g of 3, 6-dibromo-9, 10-phenanthrenequinone and 3.22g of tetrabutylammonium bromide were dissolved in 100ml of THF and 100ml of H2And O, uniformly stirring, adding 14ml of n-bromo-hexane, adding 30ml of 14.1M sodium hydroxide aqueous solution, reacting for 2 days at room temperature, adding a large amount of deionized water into a reaction system, extracting, and performing column chromatography separation to obtain the product 3, 6-dibromo-9, 10-dihexyloxyphenanthrene.
c) Preparation of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene:
2.7g of 3, 6-dibromo-9, 10-dihexyloxyphenanthrene and 1.47g of p-cyanobenzene boronic acid and a palladium catalyst, 45ml of toluene and 45ml of water are placed in a round-bottom flask, the flask is heated to 80 ℃ under a nitrogen atmosphere, then the reaction system is suspended in 200ml of water, extraction is carried out, and column chromatography separation is carried out by using a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:20 to obtain the product of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene.
d) Preparation of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone:
dispersing 1.45g of 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-dihexyloxyphenanthrene in 20ml of concentrated nitric acid, stirring for 10min, and carrying out suction filtration to obtain the product 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene.
e) Preparation of 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole:
1.025g of 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone, 0.655g of p-cyanobenzaldehyde and 2.31g of ammonium acetate were dissolved in 60ml 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 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole.
2) Preparation of triphenylphenanthroimidazole triazine polymer:
0.1042g of 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole with 0.272g anhydrous ZnCl2Grinding, mixing uniformly, adding the mixture into a sealed tube, vacuumizing the sealed tube, putting the sealed tube into a muffle furnace, heating to 400 ℃, reacting for 72 hours, taking out a sample in the sealed tube, grinding the sample into powder, washing the powder with dilute hydrochloric acid, DMF (dimethyl formamide) and deionized water in sequence, and performing vacuum drying at 120 ℃ for 12 hours to obtain the triphenylphenanthroimidazole triazine polymer.
The triphenylphenanthroimidazole triazine polymer prepared by the invention has a higher BET specific surface area, has excellent adsorption performance on carbon dioxide under a 273K condition, and the adsorption amount reaches 4.8 mmol/g.
Example 2
Example 1 was repeated except that 3.22g of tetrabutylammonium bromide was replaced by 16.94g of sodium dithionate.
Example 3
Example 1 was repeated, except that in step a sodium dithionate was also added, 3.22g of tetrabutylammonium bromide was exchanged for 3.22g of tetrabutylammonium bromide and 16.94g of sodium dithionate.
Example 4
Example 3 was repeated except that in step d the concentrated nitric acid was changed to concentrated sulfuric acid.
The polymer prepared by the invention is at 77K and the pressure is 1.0p/poUnder the condition that the pressure is increased from 0 to 1p/poDetermining the polymer pair N at a 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 is from 1p/poDropping to 0, the N of the polymer is 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 (20)

1. A triphenylphenanthroimidazole triazine polymer characterized by: the polymer is a polymer having the general structural formula (I):
Figure FDA0002971703400000011
2. triphenylphenanthroimidazole triazine polymer according to claim 1 wherein: the polymer is prepared by the following method: firstly, carrying out bromination reaction and carbonyl protection on 9, 10-phenanthrenequinone, then carrying out substitution reaction on the phenanthrenequinone and p-cyanobenzene boronic acid, and oxidizing a product obtained by the substitution reaction into 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone; then cyclizing 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d]Imidazole; finally, 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2And reacting to obtain the triphenylphenanthroimidazole triazine polymer.
3. Triphenylphenanthroimidazole triazine polymer according to claim 2 characterised in that: the bromination reaction is specifically to react 9, 10-phenanthrenequinone with bromine to obtain 3, 6-dibromo-9, 10-phenanthrenequinone; and/or
The carbonyl protection is specifically to react 3, 6-dibromo-9, 10-phenanthrenequinone with bromohexane to obtain 3, 6-dibromo-9, 10-dihexyloxyphenanthrene; and/or
The substitution reaction with the p-cyanobenzene boric acid is specifically to react 3, 6-dibromo-9, 10-dihexyloxyphenanthrene with the p-cyanobenzene boric acid to obtain 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene; and/or
And the oxidation of the product is specifically to react 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-dihexyloxyphenanthrene with an oxidant to obtain 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone.
4. Triphenylphenanthroimidazole triazine polymer according to claim 3 wherein: the oxidant is one or more of concentrated nitric acid, concentrated sulfuric acid, perchloric acid and potassium permanganate solution; and/or
The molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1: 1-3; and/or
The molar ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the n-bromohexane is 1: 1.5-4; and/or
The molar ratio of the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene to the p-cyanobenzene boric acid is 1: 1.2-3; and/or
The molar ratio of the 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone to the p-cyanobenzaldehyde is 1: 0.8-2.5.
5. Triphenylphenanthroimidazole triazine polymer according to claim 3 wherein: the molar ratio of the 9, 10-phenanthrenequinone to the liquid bromine is 1: 1.2-2.5; and/or
The molar ratio of the 3, 6-dibromo-9, 10-phenanthrenequinone to the n-bromohexane is 1: 1.8-3; and/or
The molar ratio of the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene to the p-cyanobenzene boric acid is 1: 1.5-2.5; and/or
The molar ratio of the 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone to the p-cyanobenzaldehyde is 1: 1-1.8.
6. A process for preparing triphenylphenanthroimidazole triazine polymers of any one of claims 1 to 5, characterized in that: the method comprises the following steps:
1) preparation of 2,6, 9-tris (4,4',4 "-triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole: carrying out bromination reaction and carbonyl protection on 9, 10-phenanthrenequinone, then carrying out substitution reaction on the phenanthrenequinone and p-cyanobenzene boronic acid, and oxidizing a product into 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone; finally, cyclizing 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde imidazole to obtain 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole;
2) synthesis of triphenylphenanthroimidazole triazine polymer: 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2Mixing evenly, heating and reacting to obtain the triphenylphenanthroimidazole triazine polymer.
7. The method of claim 6, wherein: the step 1) is specifically as follows:
a) dissolving 9, 10-phenanthrenequinone and an initiator in a solvent, dropwise adding a bromine solution, heating the mixture to 80-200 ℃ after dropwise adding, treating for 5-24h, washing, and separating to obtain a brown product 3, 6-dibromo-9, 10-phenanthrenequinone;
b) dissolving 3, 6-dibromo-9, 10-phenanthrenequinone and a catalyst in a solvent, uniformly mixing, then adding n-bromohexane, adjusting the pH value to be alkaline, uniformly mixing, cooling, washing, extracting, and performing column chromatography separation to obtain a product, namely 3, 6-dibromo-9, 10-dihexyloxyphenanthrene;
c) dissolving 3, 6-dibromo-9, 10-dihexanyloxyphenanthrene and p-cyanobenzene boric acid in a solvent, heating, adding water, stirring, extracting, and carrying out column chromatography on the separated solid to obtain a product 3, 6-bis (4,4' -bisphenonitrile) -9, 10-dihexanyloxyphenanthrene;
d) dispersing 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-dihexyloxyphenanthrene in an oxidant, stirring and separating to obtain a product, namely 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone;
e) dissolving 3, 6-bis (4,4 '-bisphenylnitrile) -9, 10-phenanthrenequinone and p-cyanobenzaldehyde in a solvent, heating and refluxing, separating, and washing a solid product obtained by separation to obtain 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d ] imidazole.
8. The method of claim 7, 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; 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; adjusting the pH to be alkaline, and adjusting the pH to 10-14 by using a sodium hydroxide solution; the extraction adopts dichloro or ethyl acetate; the column chromatography separation adopts petroleum ether to carry out column chromatography separation;
in step c), the solvent is toluene; the heating is carried out under the nitrogen atmosphere to 60-90 ℃, and the reflux is carried out for 8-48 h; the extraction adopts dichloro or ethyl acetate; 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 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 is heating to 60-100 ℃, and the reflux time is 6-48 h; the separation adopts filtration or suction filtration; the washing is performed by ethanol.
9. The method of claim 6, wherein: the step 2) is specifically as follows: 2,6, 9-tris (4,4' -triphenylnitrile) -1H-phenanthro [9,10-d prepared in the step 1)]Imidazole and ZnCl2Mixing evenly, adding the mixture into a closed reactor, vacuumizing the reactor, and heating the reactor for reaction to obtain the triphenylphenanthroimidazole triazine polymer.
10. The method of claim 9, wherein: in the step 2), grinding and mixing are adopted for uniform mixing; the reaction is heated to 800 ℃ by adopting a muffle furnace, and the reaction time is 1-5 d.
11. The method of claim 10, wherein: in the step 2), the reaction is heated to 700 ℃ by adopting a muffle furnace, and the reaction time is 2-4 d.
12. The method of claim 9, wherein: and washing the obtained triphenylphenanthroimidazole triazine polymer with dilute hydrochloric acid, DMF (dimethyl formamide) and deionized water in sequence, and drying to obtain the refined triphenylphenanthroimidazole triazine polymer.
13. The method of claim 12, wherein: the drying is vacuum drying at 100-150 ℃ for 4-24 h.
14. The method of claim 8, wherein: in the step a, 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; and/or
In the step b, the adding amount of the catalyst is 0.05-0.22 g/ml; the mass concentration of 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.02-0.12 g/ml; and/or
In the step c, the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene is dissolved in the solvent, and the mass concentration of the solution is 0.02 to 0.22 g/ml; and/or
In the step d, the mass concentration of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene dispersed in the oxidant is 0.01-0.80 g/m; and/or
In the step e, the mass concentration of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone dissolved in the solvent is 0.001-0.120 g/ml; and dissolving ammonium acetate in the mixed solution of acetic acid, wherein the mass concentration of the ammonium acetate is 0.01-0.15 g/ml.
15. The method of claim 8, wherein: in the step a, 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; and/or
In the step b, the adding amount of the catalyst is 0.08-0.15 g/ml; the mass concentration of 3, 6-dibromo-9, 10-phenanthrenequinone dissolved in the solvent is 0.015-0.100 g/ml; and/or
In the step c, the 3, 6-dibromo-9, 10-dihexyloxyphenanthrene is dissolved in the solvent, and the mass concentration of the solution is 0.05-0.18 g/ml; and/or
In the step d, the mass concentration of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-dihexyloxyphenanthrene dispersed in the oxidant is 0.02-0.5 g/ml; and/or
In the step e, the mass concentration of 3, 6-bis (4,4' -bisphenylnitrile) -9, 10-phenanthrenequinone dissolved in the solvent is 0.005-0.080 g/ml; and dissolving ammonium acetate in the mixed solution of acetic acid, wherein the mass concentration of the ammonium acetate is 0.02-0.10 g/ml.
16. The method of claim 9, wherein: in the step (2), 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2The molar ratio of (A) to (B) is 1: 1-15.
17. The method of claim 9, wherein: in the step (2), 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2The molar ratio of (A) to (B) is 1: 2-12.
18. The method of claim 9, wherein: in the step (2), 2,6, 9-tris (4,4' -trityl) -1H-phenanthro [9,10-d]Imidazole and ZnCl2The molar ratio of (A) to (B) is 1: 3-10.
19. Use of triphenylphenanthroimidazole triazine polymer according to any one of claims 1 to 5 or prepared according to the process of any one of claims 6 to 18, characterized in that: the triphenylphenanthroimidazole triazine polymer is used for gas adsorption.
20. Use according to claim 19, characterized in that: use of triphenylphenanthroimidazole triazine polymers for CO2And (4) adsorbing.
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