CN102569657A - Preparation for photo-response Pyr-AZO non-covalent decorating carbon nano tube material - Google Patents

Preparation for photo-response Pyr-AZO non-covalent decorating carbon nano tube material Download PDF

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CN102569657A
CN102569657A CN2011104315365A CN201110431536A CN102569657A CN 102569657 A CN102569657 A CN 102569657A CN 2011104315365 A CN2011104315365 A CN 2011104315365A CN 201110431536 A CN201110431536 A CN 201110431536A CN 102569657 A CN102569657 A CN 102569657A
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azobenzene
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CN102569657B (en
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封伟
刘红坡
冯奕钰
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Tianjin University
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Abstract

The invention discloses a preparation method for photo-response pyrene-azobenzene non-covalent decorating carbon nano tube material. The method comprises the following main processes: a few-walled carbon nano tube is added into sulfuric acid and nitric acid mixed solution so as to obtain the few-walled carbon nano tube with better dispersity; N-hydroxy sulfo-Sulfo-NHS and 1- ethyl-3-(3-Trimetlylamine propyl group) EDC HCl catalytic pyrenebutanoic acid are used for condensation reaction to nitro linear alkyl amido-azobenzene so as to obtain Pyr-AZO; then photo-response pyrene-azobenzene non-covalent decorating carbon nano tube body can be composed by using the adsorption of a pyrene structure and pi-pi electronic conjugated bonds on the surface of the carbon nano tube. In the method, through non-covalent interaction, the obtained carbon nano tube-azobenzene composite has an excellent dissolubility and has an excellent photo-response character.

Description

The preparation of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material
Technical field
The invention belongs to the preparation method of optical Response carbon nano-tube material in the technical field of nano material, be specifically related to the preparation of a kind of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material.
Background technology
CNT has good conjugated system, high electron affinity energy, and photostability is strong, and mechanical performance and photoelectric properties etc. make it that huge application potential arranged aspect photoelectric device preferably.The optical Response azobenzene derivatives has unique optical isomerization characteristic; Functionalization through nano materials such as itself and organic conjugate body, polymer, CNTs is compound, can obtain the photoresponse functional material of desirable optical tunable control microstructure or photoelectric properties.
Recently, because the development of novel photoelectric device improves constantly the requirement of photoelectric material, the photoresponse nano material becomes the focus of this area research.The research purpose is exactly that its reversible cis-trans isomerization in the illumination process of research changes the material internal conjugated system that the change of the steric configuration that caused or dipole moment causes and the variation of microscopic appearance.The preparation of optical Response CNT and research are one of them important branch.On CNT, introduce azobenzene chromophore through chemical means, then be expected to utilize the photoisomerization characteristic of azobenzene to change the performance of the optics electricity aspect of CNT.
Pyrene can firmly be adsorbed onto carbon nano tube surface through noncovalent interaction as an organic molecule with big pi-conjugated system.In azobenzene molecule, introducing pyrenyl can utilize non-covalent composite action azobenzene chromophore to be incorporated into the surface of CNT; The introducing of pyrenyl simultaneously also can make the photoresponse performance of azobenzene chromophore change, and is a kind of preparation method of optical Response carbon nano-tube material of simple possible.
At present not about utilizing non-covalent suction-operated between pyrenyl and the CNT to prepare the report and the patent of optical Response carbon nano-tube material and photoelectric properties aspect thereof.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material, the optical Response CNT dissolubility that this method makes is good, has good response characteristics to light, and its preparation technology is simple.
Technical scheme of the present invention is following: the preparation method of a kind of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material is characterized in that comprising following process:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are 65% red fuming nitric acid (RFNA) and are (1-3) by volume that CNT is joined mass fraction: in 1 the mixed acid; Make CNT concentration be (0.5-2) mg/ml; Make dispersion liquid 50 ℃ of-90 ℃ of refluxed reactions of temperature 30-120 minute, reclaim CNT, use deionized water wash to cleaning solution to be pH and be 6-7; Vacuumize 12-72 hour, obtain the acidification CNT;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: under agitation, paranitroanilinum is dissolved in the 3mol/L HCl aqueous solution, being mixed with concentration is the HCl solution of 0.2-1.2mol/L paranitroanilinum, is designated as A solution; Natrium nitrosum is added in the deionized water, be mixed with the 1.5-2.5mol/L sodium nitrite in aqueous solution, be designated as B solution; Press the volume ratio (1-12.5) of A solution and B solution: 1 mixes, and reaction is 15-90 minute under the condition of ice bath, is designated as C solution; Phenol is dissolved in the 3.5-6mol/L NaOH aqueous solution, and being mixed with concentration is the NaOH aqueous solution of 0.2-1.2mol/L phenol, is designated as D solution; Will be under ice bath reacted C solution and D solution (2-13.5) by volume: 1 mixes, and the ice bath reaction is after 30-180 minute, and using mass fraction is that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7; Separate out a large amount of depositions; Suction filtration is precipitated to the cleaning solution clarification with deionized water wash, with 50% ethanol water recrystallization; Suction filtration obtains nitro-azo phenol; To be dissolved in 0.05-0.2mol/L 1 to nitro-azo phenol, the anhydrous propanone solution of 6-dibromo-hexane adds potash in this mixed solution; Make nitro-azo phenol, 1, the ratio of 6-dibromo-hexane, potash three molal weight successively is 1: (1-4): (1-3), in mixed solution, add KI; Making its concentration is 0.0083-0.415mg/ml, and reflux stirred 12-48 hour under nitrogen protection, filters out the residue of reaction system while hot; Revolve the inspissation reactant liquor that contracts; Add absolute methanol, produce orange deposition, column chromatography obtains 1-bromo-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-Br) after purifying; AZO-Br is dissolved in the anhydrous DMF solution of 0.01-0.25mol/L potassium phthalimide; Being mixed with concentration is the potassium phthalimide anhydrous DMF solution of 0.02-0.03mol/L AZO-Br, heating reflux reaction 6-24 hour, stops reaction; Revolve the inspissation reaction solution that contracts; Adding distil water makes its deposition, waits to precipitate complete back suction filtration and with the deionized water wash deposition, will precipitate to dry to obtain orange red solid.With mass fraction is that 85% hydrazine hydrate adds ethanol, and the mass ratio that makes ethanol and hydrazine hydrate is 1: (6.3-25.3), will precipitate to dry and obtain orange red solid and be dissolved in this mixed solution; Under nitrogen protection heating reflux reaction 8-24 hour, drip the 1mol/LHCl aqueous solution, regulating the pH value is 2-6; Continue backflow 30-180 minute; Be cooled to room temperature, leave standstill and separate out the white needles deposition, suction filtration is removed the white needles solid; Revolve then and do filtrating, column chromatography obtains 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-NH2);
3) pyrene-azobenzene organic molecule is synthetic: take by weighing the pyrene butyric acid and be dissolved in the dry DMF; Being mixed with concentration is 0.005-0.022mol/L perylene butyric acid DMF solution, adds N-hydroxy thiosuccinimide (Sulfo-NHS) and 4-dimethylamino naphthyridine (DMAP), make pyrene butyric acid, Sulfo-NHS, DMAP successively the ratio of molal weight be 1: (1-1.5): (1-1.5); Mixed solution adds 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) under in ice bath, constantly stirring; Making pyrene butyric acid and the molal weight ratio of EDCHCl is 1: (1-1.2), keep ice-water bath reaction 30-240 minute, continued room temperature reaction 8-24 hour; Stop the reaction back and in system, add ethyl acetate; With saturated common salt water washing organic facies, separate the anhydrous sodium sulfate drying organic facies with separatory funnel; Revolve driedly after the filtration, in products therefrom, add dry DMF and AZO-NH 2, the 1-2ml triethylamine makes AZO-NH 2Concentration is 16-22mg/ml, stirring at room reaction 8-24 hour.Stop to react the back and add ethyl acetate, wash organic facies with deionized water, separatory use ethyl acetate extraction after merging water, revolve after the anhydrous sodium sulfate drying organic facies dried, acquisition pyrene-azobenzene (Pyr-AZO);
4) take by weighing the pyrene-azobenzene of step 3) preparation and be dissolved in DMF respectively through the CNT that step 1) is handled and obtain isocyatic two kinds of solution; With these two kinds of solution according to volume ratio (1-3): (3-1) mix; Room temperature sonic oscillation 2 hours, solution take off layer deposition after separating 13000r/m with supercentrifuge; Add among the DMF, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).
The invention has the advantages that: this method is introduced pyrenyl in azobenzene molecule; The pyrenyl that the azobenzene molecule utilization has big pi-conjugated system firmly is adsorbed onto the carbon nano tube surface with good conjugated system through noncovalent interaction; Make optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material; The dissolubility of this material is good; In organic solvents such as nitrogen dimethylformamide, acetone, dimethyl sulfoxide (DMSO), methyl alcohol, have fine solubility, its preparation technology is simple, has good response characteristics to light; Light, electrical property can be regulated and control through regulating the azobenzene derivatives kind, are expected to be used to prepare the photoresponse functional material of optical tunable control microstructure or photoelectric properties.
Description of drawings:
Fig. 1 is the nmr spectrum of the pyrene-azobenzene (Pyr-AZO) of preparation.
Among the figure: the unimodal peak that does not replace residual H for deuterated reagent fully at chemical shift δ=7.2ppm place.Be positioned at the multiplet at 6.9～8.4ppm place of low: δ=8.36 (d, 2H); 7.97 (m, 4H); 7.02 (d, branch is split in the coupling that 2H) comes from the H on two phenyl ring of azobenzene, and (m 9H) splits branch from the coupling of H on the pyrenyl, and (s 1H) is under the jurisdiction of in the amide group coupling of H and splits branch in δ=8.03 in δ=8.14.4.07 (t, (t, branch is split in the coupling that the peak of 2H) locating is under the jurisdiction of the H on the carbon that hexyl long alkyl chain two ends connect oxygen atom and nitrogen-atoms respectively 2H) with 3.41.1.3 several groups of multiplets between 1.9 split branch from the coupling of the H on several carbon in the middle of on two alkyl chains, and lay respectively at 2.18 with the peak of hydrogen on carbonyl and the carbon that pyrenyl links to each other (t, 2H) and 2.92 (t, 2H).
Fig. 2 is the pyrene-azobenzene (Pyr-AZO) of preparation and the absorption spectrum of the compound front and back of few-wall carbon nanotube (FWCNT).
Pyr-AZO 266,277,328 and the 344nm place have the chromophoric absworption peak of condensed-nuclei aromatics, shown the existence of the pi-electron conjugated system of pyrenyl among the Pyr-AZO.In addition, the absworption peak of a broad appears in Pyr-AZO at the 376nm place, and this is the π → π by trans azobenzene chromophore *Transition causes.After compound, occur the absworption peak of Pyr-AZO on the spectrogram of Pyr-AZO/FWNT, and the absorption baseline is compared obvious raising with Pyr-AZO; Show that both combine closely; Simultaneously the Pyr-AZO absworption peak of going up pyrenyl with compound before compare, takes place slight red shift (1～2nm), show the electron conjugated structure change of compound back system; The delocalization degree improves, π → π *Transition institute energy requirement decreases.
Embodiment
Providing 5 embodiment of the present invention below, is to further specify of the present invention, rather than limits scope of the present invention.
Embodiment 1:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are in 3: 1 the mixed solution of 65% red fuming nitric acid (RFNA) volume ratio that the 20mg few-wall carbon nanotube is joined the 20ml mass fraction, makes mixed liquor 70 ℃ of refluxed reactions of temperature 40 minutes.With filtered and recycled filter cake behind the deionized water dilution mixed acid solution, use the deionized water wash filter cake to be 6-7, vacuumize 48 hours to the pH that filtrates;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: under agitation, the 1.38g paranitroanilinum is dissolved in the 20ml 3mol/LHCl aqueous solution, is designated as A solution; The 0.83g natrium nitrosum is added in the 5ml deionized water, be designated as B solution; Press A solution and mix, be designated as C solution with B solution; Reaction is 40 minutes under the water bath condition.0.94g phenol, 4gNaOH are dissolved in the 20ml deionized water, are designated as D solution; To under ice bath, mix with D solution by reacted C solution; The ice-water bath reaction is after 1 hour, and using mass fraction is that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7, separates out deposition.Suction filtration is precipitated to the cleaning solution clarification with deionized water wash.Get 50% ethanol water recrystallization, suction filtration obtains nitro-azo phenol 1.63g.Will be to nitro-azo phenol 486mg, 1,6-dibromo-hexane 1.464g; Potash 496mg is dissolved in the 40ml anhydrous propanone, adds the KI of 3.3mg; Reflux stirred 24 hours under nitrogen protection, filtered out the residue of reaction system while hot, revolved the inspissation reactant liquor that contracts; Add absolute methanol, produce orange deposition.Column chromatography obtains 0.53g 1-bromo-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-Br) after purifying.The sylvite 185mg that gets AZO-Br406mg and phthalimide is dissolved in the 50ml dry DMF; Heating reflux reaction 12 hours; Stop reaction, revolve the inspissation reaction solution that contracts, adding distil water makes its deposition; Wait to precipitate complete back suction filtration and, dry and obtain orange red solid with deionized water water washing solid three times.This orange red solid is dissolved in the 40ml absolute ethyl alcohol, and adding the 500mg mass fraction is 85% hydrazine hydrate, and heating reflux reaction is 16 hours under nitrogen protection; Drip rare HCl, regulating the pH value is 3, continues to reflux 1 hour; Be cooled to room temperature, leave standstill and separated out a large amount of white needles depositions in several hours, suction filtration is removed the white needles solid; Revolve then and do filtrating, column chromatography obtains 0.29g 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane (AZO-NH2);
3) pyrene-azobenzene organic molecule is synthetic: take by weighing pyrene butyric acid 128mg and be dissolved in the 40ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 120mg, 4-dimethylamino naphthyridine (DMAP) 65mg; Add 85mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) under in ice-water bath, constantly stirring; Keep ice-water bath reaction 1 hour, continued room temperature reaction 12 hours, stop the reaction back and in system, add ethyl acetate; With saturated common salt water washing organic facies 2 times; Separate with separatory funnel, the anhydrous sodium sulfate drying organic facies is revolved dried after the filtration.In products therefrom, add 10ml dry DMF, 160mgAZO-NH 2, and several triethylamines, the stirring at room reaction is spent the night.Stop to react the back and add ethyl acetate, wash organic facies twice with deionized water, separatory merges behind the water with ethyl acetate extraction once, revolves driedly after the anhydrous sodium sulfate drying organic facies, obtains 0.16g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take by weighing the Pyr-AZO solid 10mg of step 3) preparation and be dissolved in DMF respectively through the CNT 10mg that step 1) is handled and obtain concentration and be two kinds of solution of 0.5mg/ml; Above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1; Sonic oscillation is 2 hours under the room temperature, and solution takes off layer deposition after separating 13000r/m with supercentrifuge; Add among the DMF, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.059s -1
Embodiment 2:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are in 3: 1 the mixed solution of 65% red fuming nitric acid (RFNA) volume ratio that the 20mg few-wall carbon nanotube is joined the 20ml mass fraction, makes mixed liquor 70 ℃ of refluxed reactions of temperature 40 minutes.With filtered and recycled filter cake behind the deionized water dilution mixed acid solution, use the deionized water wash filter cake to be 6-7, vacuumize 48 hours to the pH that filtrates;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: with among the embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: take by weighing pyrene butyric acid 128mg and be dissolved in the 80ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 96mg, 4-dimethylamino naphthyridine (DMAP) 54mg; Add 68mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) under in ice-water bath, constantly stirring; Keep ice-water bath reaction 30 minutes, continued room temperature reaction 8 hours, stop the reaction back and in system, add ethyl acetate; With saturated common salt water washing organic facies 2 times; Separate with separatory funnel, the anhydrous sodium sulfate drying organic facies is revolved dried after the filtration.In products therefrom, add 10ml dry DMF, 150mgAZO-NH 2, and several triethylamines, the stirring at room reaction is spent the night.Stop to react the back and add ethyl acetate, wash organic facies twice with deionized water, separatory merges behind the water with ethyl acetate extraction once, revolves driedly after the anhydrous sodium sulfate drying organic facies, obtains 0.11g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take by weighing the Pyr-AZO solid 10mg of step 3) preparation and be dissolved in DMF respectively through the CNT 10mg that step 1) is handled and obtain concentration and be two kinds of solution of 0.5mg/ml, above-mentioned two kinds of solution that make mixed according to volume ratio at 1: 3,
Sonic oscillation is 2 hours under the room temperature, and solution takes off layer deposition after separating 13000r/m with supercentrifuge, adds among the DMF, and the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.047s -1
Embodiment 3:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are in 3: 1 the mixed solution of 65% red fuming nitric acid (RFNA) volume ratio that the 20mg few-wall carbon nanotube is joined the 20ml mass fraction, makes mixed liquor 70 ℃ of refluxed reactions of temperature 40 minutes.With filtered and recycled filter cake behind the deionized water dilution mixed acid solution, use the deionized water wash filter cake to be 6-7, vacuumize 48 hours to the pH that filtrates;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: with among the embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: take by weighing pyrene butyric acid 128mg and be dissolved in the 20ml dry DMF, add N-hydroxy thiosuccinimide (Sulfo-NHS) 180mg, 4-dimethylamino naphthyridine (DMAP) 98mg; Add 102mg 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride (EDCHCl) under in ice-water bath, constantly stirring; Keep ice-water bath reaction 30 minutes, continued room temperature reaction 24 hours, stop the reaction back and in system, add ethyl acetate; With saturated common salt water washing organic facies 2 times; Separate with separatory funnel, the anhydrous sodium sulfate drying organic facies is revolved dried after the filtration.In products therefrom, add 10ml dry DMF, 220mg AZO-NH 2, and several triethylamines, the stirring at room reaction is spent the night.Stop to react the back and add ethyl acetate, wash organic facies twice with deionized water, separatory merges behind the water with ethyl acetate extraction once, revolves driedly after the anhydrous sodium sulfate drying organic facies, obtains 0.14g pyrene-azobenzene organic molecule (Pyr-AZO);
4) take by weighing the Pyr-AZO solid 10mg of step 3) preparation and be dissolved in DMF respectively through the CNT 10mg that step 1) is handled and obtain concentration and be two kinds of solution of 0.5mg/ml; Above-mentioned two kinds of solution that make are mixed according to volume ratio at 3: 1; Sonic oscillation is 2 hours under the room temperature, and solution takes off layer deposition after separating (13000r/m) with supercentrifuge; Add among the DMF, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.056s -1
Embodiment 4:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are in 3: 1 the mixed solution of 65% red fuming nitric acid (RFNA) volume ratio that the 20mg few-wall carbon nanotube is joined the 10ml mass fraction, makes mixed liquor 50 ℃ of refluxed reactions of temperature 30 minutes.With filtered and recycled filter cake behind the deionized water dilution mixed acid solution, use the deionized water wash filter cake to be 6-7, vacuumize 12 hours to the pH that filtrates.
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: with among the embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: with among the embodiment 1 3) identical;
4) take by weighing the Pyr-AZO solid 10mg of step 3) preparation and be dissolved in DMF respectively through the CNT 10mg that step 1) is handled and obtain concentration and be two kinds of solution of 0.5mg/ml; Above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1; Sonic oscillation is 2 hours under the room temperature, and solution takes off layer deposition after separating 13000r/m with supercentrifuge; Add among the DMF, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.054s -1
Embodiment 5:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are in 3: 1 the mixed solution of 65% red fuming nitric acid (RFNA) volume ratio that the 20mg few-wall carbon nanotube is joined the 40ml mass fraction; Make mixed liquor 90 ℃ of refluxed reactions of temperature 120 minutes; With filtered and recycled filter cake behind the deionized water dilution mixed acid solution; Use the deionized water wash filter cake to be 6-7, vacuumize 72 hours to the pH that filtrates;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: with among the embodiment 1 2) identical;
3) pyrene-azobenzene organic molecule is synthetic: with among the embodiment 1 3) identical;
4) take by weighing the Pyr-AZO solid 10mg of step 3) preparation and be dissolved in DMF respectively through the CNT 10mg that step 1) is handled and obtain concentration and be two kinds of solution of 0.5mg/ml; Above-mentioned two kinds of solution that make are mixed according to volume ratio at 1: 1; Sonic oscillation is 2 hours under the room temperature, and solution takes off layer deposition after separating 13000r/m with supercentrifuge; Add among the DMF, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material (Pyr-AZO/FWNT).This material photoisomerization kinetic constant is 0.051s -1

Claims (1)

1. the preparation method of optical Response pyrene-azobenzene non-covalent modification carbon nano-tube material is characterized in that comprising following process:
1) CNT is handled: it is that 98.3% concentrated sulfuric acid and mass fraction are 65% red fuming nitric acid (RFNA) and are (1-3) by volume that CNT is joined mass fraction: in 1 the mixed acid; Make CNT concentration be (0.5-2) mg/ml; Make dispersion liquid 50 ℃ of-90 ℃ of refluxed reactions of temperature 30-120 minute, reclaim CNT, use deionized water wash to cleaning solution to be pH and be 6-7; Vacuumize 12-72 hour, obtain the acidification CNT;
2) 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is synthetic: under agitation, paranitroanilinum is dissolved in the 3mol/L hydrochloride aqueous solution, is mixed with the aqueous hydrochloric acid solution that concentration is the 0.2-1.2mol/L paranitroanilinum, be designated as A solution; Natrium nitrosum is added in the deionized water, be mixed with the 1.5-2.5mol/L sodium nitrite in aqueous solution, be designated as B solution; Press the volume ratio (1-12.5) of A solution and B solution: 1 mixes, and reaction is 15-90 minute under the condition of ice bath, is designated as C solution; Phenol is dissolved in the 3.5-6mol/L sodium hydrate aqueous solution, and being mixed with concentration is the NaOH aqueous solution of 0.2-1.2mol/L phenol, is designated as D solution; Will be under ice bath reacted C solution and D solution (2-13.5) by volume: 1 mixes, and the ice bath reaction is after 30-180 minute, and using mass fraction is that 20% aqueous hydrochloric acid solution adjusting pH value is 5-7; Separate out a large amount of depositions; Suction filtration is precipitated to the cleaning solution clarification with deionized water wash, with 50% ethanol water recrystallization; Suction filtration obtains nitro-azo phenol; To be dissolved in 0.05-0.2mol/L 1 to nitro-azo phenol, the anhydrous propanone solution of 6-dibromo-hexane adds potash in this mixed solution; Make nitro-azo phenol, 1, the ratio of 6-dibromo-hexane, potash three molal weight successively is 1: (1-4): (1-3), in mixed solution, add KI; Making its concentration is 0.0083-0.415mg/ml, and reflux stirred 12-48 hour under nitrogen protection, filters out the residue of reaction system while hot; Revolve the inspissation reactant liquor that contracts; Add absolute methanol, produce orange deposition, column chromatography obtains 1-bromo-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane after purifying; 1-bromo-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane is dissolved in the anhydrous nitrogen dimethylformamide solution of 0.01-0.25mol/L potassium phthalimide, and being mixed with concentration is the anhydrous nitrogen dimethylformamide solution of potassium phthalimide of 0.02-0.03mol/L 1-bromo-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane, heating reflux reaction 6-24 hour; Stop reaction, revolve the inspissation reaction solution that contracts, adding distil water makes its deposition; Waiting to precipitate complete back suction filtration and with the deionized water wash deposition, will precipitate oven dry and obtain orange red solid, is 85% hydrazine hydrate adding ethanol with mass fraction; The mass ratio that makes ethanol and hydrazine hydrate is 1: (6.3-25.3), will precipitate oven dry and obtain orange red solid and be dissolved in this mixed solution, under nitrogen protection heating reflux reaction 8-24 hour; Drip the 1mol/LHCl aqueous solution; Regulating the pH value is 2-6, continues backflow 30-180 minute, is cooled to room temperature; Leave standstill and separate out the white needles deposition; Suction filtration is removed the white needles solid, revolves then to do filtrating, and column chromatography obtains 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane;
3) pyrene-azobenzene organic molecule is synthetic: take by weighing the pyrene butyric acid and be dissolved in the anhydrous nitrogen dimethylformamide, being mixed with concentration is 0.005-0.022mol/L perylene butyric acid nitrogen dimethylformamide solution, adds N-hydroxy thiosuccinimide and 4-dimethylamino naphthyridine; Make pyrene butyric acid, N-hydroxy thiosuccinimide, 4-dimethylamino naphthyridine successively the ratio of molal weight be 1: (1-1.5): (1-1.5), mixed solution constantly stirs adding 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride down in ice bath, and making the molal weight ratio of pyrene butyric acid and 1-ethyl-3-(3-front three aminopropyl) carbodiimide hydrochloride is 1: (1-1.2); Keep ice-water bath reaction 30-240 minute; Continued room temperature reaction 8-24 hour, and stopped the reaction back and in system, add ethyl acetate, with saturated common salt water washing organic facies; Separate with separatory funnel; The anhydrous sodium sulfate drying organic facies is revolved driedly after the filtration, in products therefrom, add anhydrous nitrogen dimethylformamide and 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane; The 1-2ml triethylamine; Making 1-amino-6-[4-(4 '-nitrobenzophenone azo) phenoxy group] hexane concentration is 16-22mg/ml, and stirring at room reaction 8-24 hour stops to react the back and adds ethyl acetate; Wash organic facies with deionized water; Separatory use ethyl acetate extraction after merging water, revolve after the anhydrous sodium sulfate drying organic facies dried, acquisition pyrene-azobenzene organic molecule;
4) take by weighing the pyrene-azobenzene of step 3) preparation and be dissolved in nitrogen dimethylformamide respectively through the CNT that step 1) is handled and obtain isocyatic two kinds of solution; With these two kinds of solution according to volume ratio (1-3): (3-1) mix; Room temperature sonic oscillation 2 hours, solution take off layer deposition after separating 13000r/m with supercentrifuge; Add in the nitrogen dimethylformamide, the dissolving part is optical Response pyrene-azobenzene organic molecule non-covalent modification carbon nano-tube material.
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CN111393551A (en) * 2020-04-09 2020-07-10 天津大学 Photoresponse polymer based on styryl pyrene dimer and preparation method thereof
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