CN110372862A - A kind of triphenyl phenanthro- imidazoles aerotex and its preparation method and application - Google Patents

A kind of triphenyl phenanthro- imidazoles aerotex and its preparation method and application Download PDF

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CN110372862A
CN110372862A CN201910687768.3A CN201910687768A CN110372862A CN 110372862 A CN110372862 A CN 110372862A CN 201910687768 A CN201910687768 A CN 201910687768A CN 110372862 A CN110372862 A CN 110372862A
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bis
imidazoles
phenanthro
phenanthrenequione
triphenyl
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CN110372862B (en
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黎华明
文继开
陈红飙
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Xiangtan University
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • 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
    • C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0677—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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Abstract

The present invention discloses a kind of triphenyl phenanthro- imidazoles aerotex and its preparation method and application.9,10- phenanthrenequione is passed through into bromination first, substitution reaction occurs again and to cyanophenylboronic acid after carbonyl-protection; then it is reoxidised into 3,6- bis- (4,4'- bis- cyanophenyl bases) -9; 10- phenanthrenequione; then 2,6,9- tri- (4 are obtained with to cyanobenzaldehyde imidazoles cyclization; 4'; 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles (TBPI), finally pass through ZnCl as construction unit2Ion heat polymerization obtains triphenyl phenanthro- imidazoles aerotex.Triphenyl phenanthro- imidazoles aerotex provided by the invention has many advantages, such as that high-specific surface area, pore structure abundant and thermostabilization are good, while preparing simply, low in cost, has excellent CO under the conditions of 273K2Absorption property.

Description

A kind of triphenyl phenanthro- imidazoles aerotex and its preparation method and application
Technical field
The present invention relates to a kind of triphenyl phenanthro- imidazoles aerotexes, and in particular to a kind of triphen for gas absorption Base phenanthro- imidazoles aerotex and preparation method thereof, belongs to adsorbent field.
Background technique
With expanding economy in recent years, the problem of about our living environments, there have been global warming is that we must One of the main problem that must be paid close attention to.This phenomenon is a large amount of discharges due to carbon dioxide gas.In order to reduce atmospheric greenhouse The concentration of gas, effective carbon dioxide capture and storage (CCS) receive the great attention of researcher all over the world.With amine Class washing is different with sub-cooled technology, needs the CO of harsh even toxic conditions2Capture, solid-phase physical adsorbent are expected to As realization CO2Storage and isolated practical approach, such as porous carbon materials, metal organic framework (MOF), porous organo polysilica Closing object (POPs) etc. can be mentioned that persistence organic pollutant, because of organic structure ele and Covalent bonding together rather than coordinate bond, The two all has advantage in terms of low-density and high thermal stability and chemical stability.Persistence organic pollutant is considered having Have other advantages, such as nonmetal doping, facilitate modification, the design diversification of component pushes it being catalyzed, gas entrapment and point From, sensing and electrochemistry in terms of development.
On the other hand, as the covalent triazine skeleton (CTF) of the subclass of porous organic polymer (POPs) usually by Prepared by the hot triazine polymerization of ion under high temperature, wherein ZnCl2Serve as solvent and catalyst.One of rich nitrogen material as classics, CTF is believed to be applied to CO naturally2It absorbs and stores, there is high surface area, high thermal stability and chemical stability.This Outside, by various parent CO2Part, which is integrated in CTF, can be improved CO2Absorbability.
Summary of the invention
Covalent triazine frame (CTFs) is also the one kind for belonging to porous organic polymer, a kind of most important synthetic method It is exactly ionothermal synthesis, i.e., will has the monomer and ZnCl of multiple cyano2It is reacted at high temperature after mixing.Ionothermal synthesis obtains Covalent triazine frame have superelevation stability and excellent carbon dioxide adsorption performance.We devise a kind of new herein The triphenyl phenanthro- imidazoles construction unit of type, and a kind of novel triphenyl phenanthro- imidazoles triazine is obtained by the method for ion heat Polymer.The triphenyl phenanthro- imidazoles aerotex has both the advantages that high-specific surface area, pore structure abundant and property are stablized, Especially there is under the conditions of 0 DEG C excellent CO2Absorption property.
The present invention is that technical solution provided by the upper technical problem of solution is specific as follows:
The first embodiment according to the present invention is to provide a kind of triphenyl phenanthro- imidazoles aerotex, and feature exists In: the polymer is the polymer with general structure (I):
Preferably, the polymer is prepared by the following method: first by 9,10- phenanthrenequione by bromination reaction, Substitution reaction occurs with to cyanophenylboronic acid again after carbonyl-protection.The product that substitution reaction obtains subsequently is oxidized to 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione.Later again by (the bis- cyanophenyl bases of the 4,4'-) -9,10- phenanthrenequione of 3,6- bis- and to cyano benzene first Aldehyde imidazoles cyclization obtains 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles.Finally again by 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles and ZnCl2Reaction obtains the polymerization of triphenyl phenanthro- imidazoles triazine Object.
Preferably, the bromination reaction is specially to be reacted 9,10- phenanthrenequione with bromine (preferably bromine), 3 are obtained, The bromo- 9,10- phenanthrenequione of 6- bis-.
Preferably, the molar ratio of 9, the 10- phenanthrenequione and bromine be 1:1-3, preferably 1:1.2-2.5, more preferably 1:1.8-2.0.And/or
Preferably, the carbonyl-protection is specially to be reacted bromo- 9, the 10- phenanthrenequione of 3,6- bis- with bromo hexane, obtain It is luxuriant and rich with fragrance to obtain bromo- bis- hexyloxy of 9,10- of 3,6- bis-.
Preferably, the molar ratio of bromo- 9, the 10- phenanthrenequione of 3, the 6- bis- and bromo n-hexane is 1:1.5-4, preferably 1: 1.8-3 more preferably 1:2.0-2.5.And/or
Preferably, described occur substitution reaction specially for bromo- 9,10-, bis- hexyloxy of 3,6- bis- with to cyanophenylboronic acid Phenanthrene is reacted with to cyanophenylboronic acid, and it is luxuriant and rich with fragrance to obtain 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy.
Preferably, bromo- 9,10-, the bis- hexyloxy phenanthrene of 3, the 6- bis- and the molar ratio to cyanophenylboronic acid are as follows: 1.2-3, Preferably 1:1.5-2.5, more preferably 1:1.8-2.0.And/or
Preferably, described that product oxidation is specially luxuriant and rich with fragrance by 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy It is reacted, is obtained with oxidant (preferably one of concentrated nitric acid, the concentrated sulfuric acid, perchloric acid, liquor potassic permanganate or a variety of) 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione.
Preferably, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9, the 10- phenanthrenequione is with the molar ratio to cyanobenzaldehyde 1:0.8-2.5, preferably 1:1-1.8, more preferably 1:1.2-1.5.
Second of embodiment according to the present invention is to provide a kind of side for preparing triphenyl phenanthro- imidazoles aerotex Method or the method for preparing triphenyl phenanthro- imidazoles aerotex described in the first embodiment, this method include following step It is rapid:
1) preparation of 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles: 9,10- phenanthrenequione passes through Substitution reaction occurs with to cyanophenylboronic acid again after bromination reaction, carbonyl-protection, product is then oxidized to 3,6- bis- (4,4'- Double cyanophenyl bases) -9,10- phenanthrenequione；Finally by (the bis- cyanophenyl bases of the 4,4'-) -9,10- phenanthrenequione of 3,6- bis- with to cyanobenzaldehyde imidazoles at Ring obtains 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles.
2) synthesis of triphenyl phenanthro- imidazoles aerotex: by 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles and ZnCl2It is uniformly mixed, heating is reacted, and triphenyl phenanthro- imidazoles aerotex is obtained.
Preferably, step 1) specifically:
A) 9,10- phenanthrenequione and initiator (preferably dibenzoyl peroxide) are dissolved in solvent (preferably nitrobenzene), Be added dropwise bromine solutions (preferably bromine), after being added dropwise to complete, heat the mixture to 80-200 DEG C (preferably 90-180 DEG C, it is more excellent It is selected as 100-140 DEG C) processing 5-24h (preferably 8-22h, more preferably 10-20h), washing (preferably using n-hexane washing), Separation (preferably using filtering, suction filtration or column analysis) obtains the bromo- 9,10- phenanthrenequione of brown product 3,6- bis-.
B) the bromo- 9,10- phenanthrenequione of 3,6- bis-, catalyst (preferably tetrabutylammonium bromide and/or sodium dithionite) is molten It in solvent (preferably THF solution), mixes, bromo n-hexane is then added, adjust pH to alkalinity (preferably using sodium hydroxide Solution is to adjust pH to 10-14), is uniformly mixed (preferably shaking up 1-5min), and (ice is preferably added in cooling into reaction system Water), it washs (deionized water is preferably added into reaction system), extracts (solvent preferably uses dichloro or ethyl acetate), column layer Analysis separation (preferably carries out column chromatography for separation using petroleum ether), obtains product 3, and bromo- 9,10-, bis- hexyloxy of 6- bis- is luxuriant and rich with fragrance.
C) bromo- 9,10-, bis- hexyloxy of 3,6- bis- is luxuriant and rich with fragrance and is dissolved in solvent (preferably toluene) to cyanophenylboronic acid, heats (be preferably heated under nitrogen atmosphere 60-90 DEG C, flow back 8-48h), adds water and stirs, extraction (solvent preferably use dichloro or Ethyl acetate), the solid for separating acquisition (preferably uses ethyl acetate and petroleum ether volume ratio for the mixed of 1:2-20 by column chromatography Close solution and carry out column chromatography), product 3 is obtained, bis- hexyloxy of 6- bis- (4,4'- bis- cyanophenyl bases) -9,10- is luxuriant and rich with fragrance.
D) two hexyloxy phenanthrene of 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- is dispersed in oxidant to (preferred oxidant is One of concentrated nitric acid, the concentrated sulfuric acid, perchloric acid, liquor potassic permanganate are a variety of) in, (preferably mixing time is 5- for stirring 20min), it separates and (preferably uses filtering or filter) to get product 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10- phenanthrenequione is arrived.
E) by 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione, solvent is dissolved in cyanobenzaldehyde, and (preferred solvent is second Sour ammonium is dissolved in the mixed solution of acetic acid) in, it is heated to reflux and (is preferably heated to 60-100 DEG C, return time 6-48h), separate (preferably using filtering or suction filtration), the solid product that separation obtains is washed (preferably using ethanol washing), obtains 2,6, 9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles.
Preferably, step 2) specifically: prepare step 1) 2,6,9- tri- (4,4', 4 "-triphen itrile group)- 1H- phenanthro- [9,10-d] imidazoles and ZnCl2It is uniformly mixed (preferably ground and mixed), is added in closed reactor, will react Device is evacuated to vacuum, and heating, which is reacted, (to be preferably heated to 200-800 DEG C using Muffle furnace, be more preferably heated to 300-700 ℃；Reaction time is 1-5d, preferably 2-4d), obtain triphenyl phenanthro- imidazoles aerotex.
Preferably, successively using dilute hydrochloric acid, DMF, deionization to wash the triphenyl phenanthro- imidazoles aerotex of acquisition It washs, dry (being preferably dried in vacuo 4-24h at 100-150 DEG C) obtains the triphenyl phenanthro- imidazoles aerotex of purification.
Preferably, in step a, the molar ratio of 9,10- phenanthrenequione and bromine is 1:1-3, preferably 1:1.2-2.5, more Preferably 1:1.8-2.0.It is 0.10-0.20g/ml, preferably 0.12- that 9,10- phenanthrenequione, which are dissolved in the mass concentration in solvent, 0.18g/ml.The mass concentration that initiator is dissolved in initiator in solvent is 0.01-0.10mol/L, preferably 0.02-0.08mol/ L.And/or
Preferably, in stepb, the molar ratio of 3,6- bis- bromo- 9,10- phenanthrenequione and bromo n-hexane is 1:1.5-4, excellent It is selected as 1:1.8-3, more preferably 1:2.0-2.5.The additional amount 0.05-0.22g/ml of catalyst, preferably 0.08-0.15g/ ml；It is 0.02-0.12g/ml, preferably 0.015-0.100g/ that 3,6- bis- bromo- 9,10- phenanthrenequione, which are dissolved in the mass concentration in solvent, ml.And/or
Preferably, 3,6- bis- bromo- 9,10-, bis- hexyloxy phenanthrene are 1 with the molar ratio to cyanophenylboronic acid in step c: 1.2-3, preferably 1:1.5-2.5, more preferably 1:1.8-2.0.The bromo- bis- hexyloxy phenanthrene of 9,10- of 3,6- bis- is dissolved in solvent Mass concentration is 0.02-0.22g/ml, preferably 0.05-0.18g/ml.And/or
Preferably, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy phenanthrene is dispersed in oxidant in step d In mass concentration be 0.01-0.80g/ml, preferably 0.02-0.5g/ml.And/or
Preferably, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10- phenanthrenequione rub with to cyanobenzaldehyde in step e You are than being 1:0.8-2.5, preferably 1:1-1.8, more preferably 1:1.2-1.5.3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- is luxuriant and rich with fragrance It is 0.001-0.120g/ml, preferably 0.005-0.080g/ml that quinone, which is dissolved in the mass concentration in solvent,；Solvent uses ammonium acetate It is dissolved in the mixed solution of acetic acid, wherein the mass concentration of ammonium acetate is 0.01-0.15g/ml, preferably 0.02-0.10g/ml.
Preferably, in step (2), 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles with ZnCl2Molar ratio be 1:1-15, preferably 1:2-12, more preferably 1:3-10.
The third embodiment according to the present invention provides a kind of triphenyl phenanthro- imidazoles aerotex or according to this hair The purposes of the triphenyl phenanthro- imidazoles aerotex of bright second of embodiment the method preparation, by triphenyl phenanthro- imidazoles Aerotex is used for gas absorption.
Preferably, triphenyl phenanthro- imidazoles aerotex is used for CO2Absorption.
It should be noted that in the present invention, in step a in the nitrobenzene solution of dibenzoyl peroxide, peroxidating two The effect of benzoyl acts as initiator: cause Sn1 attack of the bromine to 3,6 hydrogen on the phenanthrene ring of 9,10- phenanthrenequione, thus To target product.
In the present invention, monomer 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles are for the first time Synthesis, while using the monomer in ZnCl2In the presence of under hot conditions polymerization form the polymer of new triazine ring.The polymerization Object has many advantages, such as that high-specific surface area, pore structure abundant and thermostabilization are good, has excellent CO under the conditions of 273K2Adsorptivity Energy.
In the present invention, solvent is acted as using the purpose of nitrobenzene, goes on smoothly and creates conditions for reaction.
In the present invention, the effect of tetrabutylammonium bromide acts as phase transfer catalyst in step b；It allows inside two-phase solvent Reactant can come into full contact with, make reaction keep higher yields.
It should be noted that in stepb, the effect of sodium dithionite acts as co-catalyst.Promote 3,6- dibromo Carbonyl in phenanthrenequione is transformed into the hydroxyl for serving as intermediate, to make protection reaction that can go on smoothly.
In the present invention, in step c, bromo- 9,10-, bis- hexyloxy of 3,6- bis- is successfully replaced to the cyanophenyl base of cyanophenylboronic acid Bromo on phenanthrene,
In the present invention, the purpose for adjusting pH to alkalinity in step b is that the protection reaction of bromo n-hexane is needed in alkalinity Under the conditions of can just go on smoothly, and reaction yield is also high.
In the present invention, in step d, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy phenanthrene is dispersed in oxidation The purpose of (preferred oxidant is one of concentrated nitric acid, the concentrated sulfuric acid, perchloric acid, liquor potassic permanganate or a variety of) is to slough in agent Hexyl protection.Ehter bond is not very stable chemical bond, and deprotection reaction can occur under strongly acidic conditions or under specific catalytic condition.
In the present invention, in step e, ammonium acetate is to provide a key compound of nitrogen source in cyclization reaction, because This will guarantee the enough to obtain target product of it.
In the present invention, in step 2), ZnCl2Effect act as Lewis-base catalyst and solvent.Zinc chloride is in height It can be in molten condition under the conditions of temperature, solvent can be played the role of.In addition only under the catalysis of zinc chloride, cyano can just occur Trimerization is to form polymer.
The BET specific surface area of the triphenyl phenanthro- imidazoles aerotex prepared through the invention is up to 1183m2g-1.? To carbon dioxide with excellent absorption property under the conditions of 273K, the Reasonable Regulation And Control through excess temperature and catalyst ratio, preparation Triphenyl phenanthro- imidazoles aerotex is to CO2Adsorbance can reach 4.5mmol g-1。
Compared with prior art, triphenyl phenanthro- imidazoles aerotex provided by the invention has the advantage that
1, the synthesis of the polymer monomer 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles, with ZnCl2Forming the polymerization of triazine ring under the high temperature conditions is for the first time.
2, the polymer has biggish specific surface area, has some superiority in terms of gas absorption.
3, there is imidazole ring, triazine ring isoreactivity functional group facilitates the absorption to carbon dioxide in the polymer.
Detailed description of the invention
Fig. 1 is the synthesis of present invention preparation 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles Figure.
Fig. 2 is that the embodiment of the present invention 1 prepares 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles Nuclear-magnetism phenogram.
Fig. 3 is the composite diagram that the embodiment of the present invention 1 prepares triphenyl phenanthro- imidazoles aerotex.
Fig. 4 is the nitrogen adsorption desorption curve that the embodiment of the present invention 1 prepares triphenyl phenanthro- imidazoles aerotex.
Fig. 5 is CO of the triphenyl phenanthro- imidazoles aerotex under 273K in the embodiment of the present invention 12Adsorption curve.
Specific embodiment
Technical solution of the present invention is illustrated below, the claimed range of the present invention include but is not limited to Lower embodiment.
Embodiment 1
A kind of method preparing triphenyl phenanthro- imidazoles aerotex method includes the following steps:
1) preparation of 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles:
A) preparation of the bromo- 9,10- phenanthrenequione of 3,6- bis-:
In 20.8g 9, the nitrobenzene solution of 10- phenanthrenequione and dibenzoyl peroxide is added dropwise 11.5ml bromine, is added dropwise to complete Afterwards, 110 DEG C of processing 16h are heated the mixture to, crude product is washed with n-hexane, and filtering obtains brown product 3, and 6- bis- is bromo- 9,10- phenanthrenequione；
B) preparation of bromo- bis- hexyloxy of the 9,10- phenanthrene of 3,6- bis-:
The bromo- 9,10- phenanthrenequione of 11.12g 3,6- bis-, 3.22g tetrabutylammonium bromide are dissolved in 100mlTHF and 100mlH2O is simultaneously It stirs evenly, 14ml bromo n-hexane is then added, add the sodium hydrate aqueous solution of 30ml 14.1M, react at room temperature 2 days, A large amount of deionized waters are added into reaction system, extract, column chromatography for separation obtains product 3, bromo- 9,10-, bis- hexyloxy of 6- bis- It is luxuriant and rich with fragrance.
C) preparation of two hexyloxy phenanthrene of 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10-:
By the bromo- bis- hexyloxy phenanthrene of 9,10- of 2.7g 3,6- bis- and 1.47g to cyanophenylboronic acid and palladium catalyst and anhydrous carbon Sour potassium and 45ml toluene and 45ml water are set in a round bottom flask, are heated to 80 DEG C under nitrogen atmosphere, are then hanged reaction system It floats in 200ml water, extracts, ethyl acetate and petroleum ether volume ratio is used to carry out column chromatography for separation for the mixed solution of 1:20, It is luxuriant and rich with fragrance to obtain two hexyloxy of product 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10-.
D) preparation of 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione:
By 1.45g 3, bis- hexyloxy phenanthrene of 6- bis- (4,4'- bis- cyanophenyl bases) -9,10- is dispersed in 20ml concentrated nitric acid, stirring 10min filters to get product 3 is arrived, and bis- hexyloxy of 6- bis- (4,4'- bis- cyanophenyl bases) -9,10- is luxuriant and rich with fragrance.
E) preparation of 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles:
By 1.025g 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione, 0.655g to cyanobenzaldehyde, 2.31g acetic acid Ammonium is dissolved in 60ml acetic acid, and being heated to reflux the time is for 24 hours, to filter, and the solid product that separation is obtained uses ethanol washing, obtains 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles.
2) preparation of triphenyl phenanthro- imidazoles aerotex:
(4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles of 0.1042g 2,6,9- tri- and 0.272g is anhydrous ZnCl2It is added in tube sealing after ground and mixed is uniform, is put into after tube sealing is vacuumized in Muffle furnace and is heated to 400 DEG C, react 72h Sample in tube sealing is taken out afterwards, is pulverized last successively with dilute hydrochloric acid, DMF and deionized water washing, then it is dry through 120 DEG C of vacuum Triphenyl phenanthro- imidazoles aerotex is obtained after dry 12h.
The triphenyl phenanthro- imidazoles aerotex BET specific surface area with higher prepared through the invention, in 273K Under the conditions of there is excellent absorption property to carbon dioxide, adsorbance reaches 4.8mmol/g.
Embodiment 2
Embodiment 1 is repeated, 3.22g tetrabutylammonium bromide is only changed to 16.94g sodium dithionate.
Embodiment 3
Embodiment 1 is repeated, only sodium dithionate is additionally added in step a, 3.22g tetrabutylammonium bromide is changed to 3.22g tetrabutylammonium bromide and 16.94g sodium dithionate.
Embodiment 4
Embodiment 3 is repeated, concentrated nitric acid is only changed to the concentrated sulfuric acid in step d.
Polymer prepared by the present invention is in 77K, pressure 1.0p/poUnder the conditions of, when pressure is raised to 1p/p from 0o, specific Pressure value under measurement polymer to N2Adsorptive value, when pressure reaches maximum value, polymer is to N2Adsorptive value also reach most Greatly, this also just represents N of polymer under the conditions of 77K2Adsorption capacity；When pressure is from 1p/po0 is dropped to, is surveyed at a particular pressure Determine the N of polymer2Desorption value；Further by the N of polymer2Adsorption-desorption curve, further according to the available polymer of BET algorithm The important parameters such as surface area.As a result as shown in Figure 4.
Secondly Inventive polymers are in 273K, and under the conditions of pressure is 1bar, pressure rises 1000mbar from 0mbar, specific Pressure value under measurement polymer to CO2Adsorptive value, when pressure reaches maximum value, polymer is to CO2Adsorptive value also reach Maximum, this just represents CO of the polymer at 273K2Adsorption capacity.As a result as shown in Figure 5.

Claims (10)

1. a kind of triphenyl phenanthro- imidazoles aerotex, it is characterised in that: the polymer is the polymerization with general structure (I) Object:
2. triphenyl phenanthro- imidazoles aerotex according to claim 1, it is characterised in that: the polymer be by with Prepared by lower method: first by 9,10- phenanthrenequione by replacing again with to cyanophenylboronic acid after bromination reaction, carbonyl-protection The product that substitution reaction obtains subsequently is oxidized to 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10- phenanthrenequione by reaction；Again will later (the bis- cyanophenyl bases of the 4,4'-) -9,10- phenanthrenequione of 3,6- bis- with to cyanobenzaldehyde imidazoles cyclization obtain 2,6,9- tri- (4,4', 4 "-three Cyanophenyl base) -1H- phenanthro- [9,10-d] imidazoles；Finally again by 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10- D] imidazoles and ZnCl2Reaction obtains triphenyl phenanthro- imidazoles aerotex.
3. triphenyl phenanthro- imidazoles aerotex according to claim 2, it is characterised in that: the bromination reaction is specific To be reacted 9,10- phenanthrenequione with bromine, bromo- 9, the 10- phenanthrenequione of 3,6- bis- is obtained；And/or
The carbonyl-protection is specially to be reacted bromo- 9, the 10- phenanthrenequione of 3,6- bis- with bromo hexane, obtains 3,6- bis- bromo- 9, Bis- hexyloxy of 10- is luxuriant and rich with fragrance；And/or
It is described that substitution reaction occurs specially by the bromo- bis- hexyloxy phenanthrene of 9,10- of 3,6- bis- and to cyano benzene with to cyanophenylboronic acid Boric acid is reacted, and it is luxuriant and rich with fragrance to obtain 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy；And/or
It is described by product oxidation be specially by two hexyloxy phenanthrene of 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- and oxidant (preferably For one of concentrated nitric acid, the concentrated sulfuric acid, perchloric acid, liquor potassic permanganate or a variety of) it is reacted, obtaining 3,6- bis-, (4,4'- is bis- Cyanophenyl base) -9,10- phenanthrenequione.
4. triphenyl phenanthro- imidazoles aerotex according to claim 3, it is characterised in that: 9, the 10- phenanthrenequione with The molar ratio of bromine is 1:1-3, preferably 1:1.2-2.5；And/or
The molar ratio of bromo- 9, the 10- phenanthrenequione of 3, the 6- bis- and bromo n-hexane is 1:1.5-4, preferably 1:1.8-3；And/or
Bromo- 9,10-, the bis- hexyloxy phenanthrene of 3, the 6- bis- is 1:1.2-3, preferably 1:1.5- with the molar ratio to cyanophenylboronic acid 2.5；And/or
3,6-, bis- (4,4'- bis- cyanophenyl bases) -9, the 10- phenanthrenequione is 1:0.8-2.5 with the molar ratio to cyanobenzaldehyde, preferably For 1:1-1.8.
5. triphen described in any one of a kind of method for preparing triphenyl phenanthro- imidazoles aerotex or preparation claim 1-4 The method of base phenanthro- imidazoles aerotex, it is characterised in that: method includes the following steps:
1) preparation of 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles: 9,10- phenanthrenequione passes through bromination Substitution reaction occurs with to cyanophenylboronic acid again after reaction, carbonyl-protection, product is then oxidized to (4, the 4'- bis- benzene of 3,6- bis- Itrile group) -9,10- phenanthrenequione；Finally (the bis- cyanophenyl bases of the 4,4'-) -9,10- phenanthrenequione of 3,6- bis- is obtained with cyclic to cyanobenzaldehyde imidazoles To 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles；
2) synthesis of triphenyl phenanthro- imidazoles aerotex: by 2,6,9- tri- (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9, 10-d] imidazoles and ZnCl2It is uniformly mixed, heating is reacted, and triphenyl phenanthro- imidazoles aerotex is obtained.
6. according to the method described in claim 5, it is characterized by: step 1) specifically:
A) 9,10- phenanthrenequione and initiator (preferably dibenzoyl peroxide) are dissolved in solvent (preferably nitrobenzene), are added dropwise Bromine solutions (preferably bromine), after being added dropwise to complete, heat the mixture to 80-200 DEG C (preferably 90-180 DEG C, more preferably 100-140 DEG C) processing 5-24h (preferably 8-22h, more preferably 10-20h), washing (preferably using n-hexane washing), separation (preferably using filtering, suction filtration or column analysis) obtains the bromo- 9,10- phenanthrenequione of brown product 3,6- bis-；
B) the bromo- 9,10- phenanthrenequione of 3,6- bis-, catalyst (preferably tetrabutylammonium bromide and/or sodium dithionite) are dissolved in molten It in agent (preferably THF solution), mixes, bromo n-hexane is then added, adjust pH to alkalinity (preferably using sodium hydroxide solution To adjust pH to 10-14), it is uniformly mixed (preferably shaking up 1-5min), cooling (ice water is preferably added into reaction system) washes It washs and (deionized water is preferably added into reaction system), extract (solvent preferably uses dichloro or ethyl acetate), column chromatography for separation (preferably carrying out column chromatography for separation using petroleum ether), obtains product 3, and bromo- 9,10-, bis- hexyloxy of 6- bis- is luxuriant and rich with fragrance；
C) bromo- 9,10-, bis- hexyloxy of 3,6- bis- is luxuriant and rich with fragrance and is dissolved in solvent (preferably toluene) to cyanophenylboronic acid, and heating is (preferably To be heated to 60-90 DEG C under nitrogen atmosphere, flow back 8-48h), it adds water and stirs, (solvent preferably uses dichloro or acetic acid second for extraction Ester), the solid for separating acquisition (preferably uses ethyl acetate and petroleum ether volume ratio for the mixed solution of 1:2-20 by column chromatography Carry out column chromatography), product 3 is obtained, bis- hexyloxy of 6- bis- (4,4'- bis- cyanophenyl bases) -9,10- is luxuriant and rich with fragrance；
D) two hexyloxy phenanthrene of 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- is dispersed in oxidant to (preferred oxidant is dense nitre One of acid, the concentrated sulfuric acid, perchloric acid, liquor potassic permanganate are a variety of) in, stirring (preferably mixing time is 5-20min), point From (preferably using filtering or filter) to get arriving product 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10- phenanthrenequione；
E) by 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione, solvent is dissolved in cyanobenzaldehyde, and (preferred solvent is ammonium acetate It is dissolved in the mixed solution of acetic acid) in, it is heated to reflux and (is preferably heated to 60-100 DEG C, return time 6-48h), separation is (preferably Using filtering or filter), the solid product that separation obtains is washed (preferably using ethanol washing), 2,6,9- tri- is obtained (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles.
7. method according to claim 5 or 6, it is characterised in that: step 2) specifically: prepare step 1) 2, (4,4', 4 "-triphen itrile group) -1H- phenanthro- [9,10-d] imidazoles of 6,9- tri- and ZnCl2It is uniformly mixed (preferably ground and mixed), It is added in closed reactor, reactor is evacuated to vacuum, heating, which is reacted, (is preferably heated to 200-800 using Muffle furnace DEG C, more preferably it is heated to 300-700 DEG C；Reaction time is 1-5d, preferably 2-4d), obtain triphenyl phenanthro- imidazoles triazine Polymer；
Preferably, the triphenyl phenanthro- imidazoles aerotex of acquisition is successively washed with dilute hydrochloric acid, DMF, deionized water, do Dry (being preferably dried in vacuo 4-24h at 100-150 DEG C) obtains the triphenyl phenanthro- imidazoles aerotex of purification.
8. according to the method described in claim 6, it is characterized by: in step a, the molar ratio of 9,10- phenanthrenequione and bromine is 1:1-3, preferably 1:1.2-2.5；It is 0.10-0.20g/ml that 9,10- phenanthrenequione, which are dissolved in the mass concentration in solvent, preferably 0.12-0.18g/ml；The mass concentration that initiator is dissolved in initiator in solvent is 0.01-0.10mol/L, preferably 0.02- 0.08mol/L；And/or
In stepb, the molar ratio of bromo- 9, the 10- phenanthrenequione of 3,6- bis- and bromo n-hexane is 1:1.5-4, preferably 1:1.8-3； The additional amount 0.05-0.22g/ml of catalyst, preferably 0.08-0.15g/ml；The bromo- 9,10- phenanthrenequione of 3,6- bis- is dissolved in solvent Mass concentration be 0.02-0.12g/ml, preferably 0.015-0.100g/ml；And/or
In step c, 3,6- bis- bromo- 9,10-, bis- hexyloxy phenanthrene are 1:1.2-3 with the molar ratio to cyanophenylboronic acid, preferably 1:1.5-2.5；It is 0.02-0.22g/ml that 3,6- bis- bromo- 9,10-, bis- hexyloxy phenanthrene, which are dissolved in the mass concentration in solvent, preferably 0.05-0.18g/ml；And/or
In step d, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10-, bis- hexyloxy phenanthrene is dispersed in the mass concentration in oxidant and is 0.01-0.80g/ml, preferably 0.02-0.5g/ml；And/or
In step e, 3,6- bis- (4,4'- bis- cyanophenyl bases) -9,10- phenanthrenequione are 1:0.8- with the molar ratio to cyanobenzaldehyde 2.5, preferably 1:1-1.8；It is 0.001- that 3,6- bis- (the bis- cyanophenyl bases of 4,4'-) -9,10- phenanthrenequione, which is dissolved in the mass concentration in solvent, 0.120g/ml, preferably 0.005-0.080g/ml；Solvent is dissolved in the mixed solution of acetic acid using ammonium acetate, wherein ammonium acetate Mass concentration is 0.01-0.15g/ml, preferably 0.02-0.10g/ml.
9. according to the method described in claim 7, it is characterized by: in step (2), 2,6,9- tri- (4,4', 4 "-three cyanophenyls Base) -1H- phenanthro- [9,10-d] imidazoles and ZnCl2Molar ratio be 1:1-15, preferably 1:2-12, more preferably 1:3-10.
10. triphenyl phenanthro- imidazoles aerotex described in any one of -4 or according to claim 5-9 according to claim 1 Any one of the method preparation triphenyl phenanthro- imidazoles aerotex purposes, it is characterised in that: by triphenyl phenanthro- Imidazoles aerotex is used for gas absorption, and triphenyl phenanthro- imidazoles aerotex is preferably used for CO2Absorption.
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