CN105601888B - A kind of five butterflies alkene conjugated polymer and preparation method thereof and its application in quick detection nitro arene explosive substance - Google Patents

A kind of five butterflies alkene conjugated polymer and preparation method thereof and its application in quick detection nitro arene explosive substance Download PDF

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CN105601888B
CN105601888B CN201610015706.4A CN201610015706A CN105601888B CN 105601888 B CN105601888 B CN 105601888B CN 201610015706 A CN201610015706 A CN 201610015706A CN 105601888 B CN105601888 B CN 105601888B
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陈传峰
韩莹
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Abstract

The present invention provides a kind of five butterflies alkene conjugated polymer and preparation method thereof and its application in quick detection nitro arene explosive substance.The conjugated polymer its general structure is shown in formula I：The present invention efficiently obtains the conjugated polymer with five butterfly alkene fragments by Sonogashira coupling reactions, rigid five butterflies alkene structure has sufficient hole, form molecular channel, responded so that the polymer of electron rich is easy to produce by electrostatic interaction with the nitro-aromatic quasi-molecule of electron deficient, show high sensitivity.The five butterflies alkene conjugated polymer has higher molecular weight, launch wavelength more red shift, and has more preferable selectivity and sensitivity.The response time for the polymer reported than Swager groups shortens 2/3.The conjugated polymer of the present invention can carry out high selectivity to the nitro arene explosive substance in gas phase and rapidly recognize.

Description

A kind of five butterfly alkene conjugated polymers and preparation method thereof are with it in quick detection nitro virtue Application in hydro carbons explosive
Technical field
The invention belongs to polymeric material field, and in particular to a kind of five butterflies alkene conjugated polymer and preparation method thereof and its Application in quick detection nitro arene explosive substance.
Background technology
In the last few years, with the application in war of the threat of terrorism, CB weapons, nonmetallic mine detection, The increase of the demands such as environmental quality monitoring, research of the countries in the world to all kinds of high performance thin film sensors is more and more paid attention to.Nitro Arene compounds are the important explosives of a class, and residual yet with the threat of terrorism and its in the environment is to organism Murder by poisoning so that the detection to this kind of explosive receives common concern.Up to the present, it is fast to nitro arene explosive substance Although speed, sensitive detection have been achieved for major progress, but huge challenge are just remained to its recognition detection. Between past 10 years, from the angle of investigation of materials, the type of polymer available for explosive detection includes triptycene, fluorenes class, virtue Amine, aryne class and metallole birds of the same feather flock together compound etc..Wherein butterfly alkene is the earliest material that fluorescence sense is studied that is used for, and this is It is to determine sense film due to permeability of the explosive vapors in sense film and its with the binding ability of Sensing elements molecule Response speed, sensitivity and reversible principal element, and butterfly alkene has butterfly-like Three-dimensional Rigidity by what multiple phenyl ring were constituted The molecule of structure, just with it is such the characteristics of.1998, it is poly- that Swager groups have obtained five butterfly alkene conjugation by coupling reaction Compound material.The characteristics of such polymer is that have the three-dimensional structure that 5 phenyl ring are formed in each repeat unit of strand, This rigid molecular channel reduces diffusional resistance of the analyte in film, hence improves the sensing capabilities of film, improves The permeabilities of explosive vapors wherein.
At present in the field, the detection that representative conjugated polymer is used for nitro arene explosive substance mainly has (a)J.S.Yang and T.M.Swager,J.Am.Chem.Soc.,1998,120,11864-11873；(b)J.S.Yang and T.M.Swager,J.Am.Chem.Soc.,1998,120,5321-5322；(c)H.Sohn,Sailor,M.J.Sailor, D.Magde and W.C.Trogler,J.Am.Chem.Soc.,2003,125,3821-3830；(d)Y.Y.Long, H.B.Chen,Y.Yang,H.M.Wang,Y.F.Yang,N.Li,K.Li,J.Pei and F.Liu,Macromolecules, 2009,42,6501-6509；(e)B.Xu,X.Wu,H.Li,H.Tong and L.Wang,Macromolecules,2011,44, 5089-5092；(f)L.-L.Zhou,M.Li,H.-Y.Lu and C.-F.Chen,Polym.Chem.,2016,7,310-318. Deng.
The five butterfly alkene conjugated polymer materials that Swager groups obtain, structure is novel, but yield is general, and to explosive Response it is slower, so the conjugated polymer for efficiently synthesizing high selectivity and sensitivity has great importance.Up to the present, Although major progress is had been achieved for the detection of nitro arene explosive substance based on conjugated polymer, but its sensitivity and choosing Selecting property need to be improved.Therefore a kind of conjugated polymer for being used for enzyme rapidly and sensitively detection nitro arene explosive substance is explored to have There is very high scientific research value and application value.
The content of the invention
An object of the present invention is to provide a kind of five butterflies alkene conjugated polymer and preparation method thereof.
Five butterflies alkene conjugated polymer provided by the present invention, its general structure is shown in formula I：
In Formulas I, R is C1-C20 alkyl, concretely myristyl.
In Formulas I, n is the natural number between 100 to 10000, and preferably n is the natural number between 200 to 600.
The number-average molecular weight of five butterfly alkene conjugated polymers shown in above-mentioned Formulas I is 200,000 to 500,000.
Five butterfly alkene conjugated polymers are prepared by the method comprising the following steps shown in above-mentioned Formulas I：
Compound shown in compound shown in formula II and formula III is subjected to Sonogashira coupling reactions, obtains containing formula I The mixture of shown conjugated polymer；
In formula III, Y is selected from, but not limited to, Br, I, Cl group, preferably I groups.
R is C1-C20 alkyl, concretely myristyl.
In the above method, the mol ratio of the compound shown in formula II and the compound shown in formula III is 1:1-1.5, specifically may be used For 1:1.
In the above method, the reaction temperature of the Sonogashira coupling reactions is 70-90 DEG C, concretely 75 DEG C.
According to the differential responses of reactant activity, the reaction time of the Sonogashira coupling reactions is small for 24-120 When.
The Sonogashira coupling reactions are carried out under inert gas atmosphere, and the inert gas is nitrogen or argon Gas.
Solvent is made using triethylamine or diisopropylamine in the Sonogashira coupling reactions, toluene work can be also added Mixed solvent.
Preferably, the Sonogashira coupling reactions make solvent using the mixed solvent of toluene and diisopropylamine, its In, the volume ratio of toluene and diisopropylamine is preferably 3:2.
The Sonogashira coupling reactions make catalyst using palladium-containing catalyst and CuI, wherein the palladium-containing catalyst For PdCl2(PPh3)2Or Pd (PPh3)4。
Preferably, the Sonogashira coupling reactions use Pd (PPh3)4Make catalyst with CuI.
The above method is also included from described containing conjugation isolated formula I in the mixture of conjugated polymer shown in formula I Suo Shi The step of polymer.Concrete operations are as follows：To described containing conjugation shown in addition formula I in the mixture of conjugated polymer shown in formula I The poor solvent of polymer carries out precipitating, filtering, you can.
The poor solvent is preferably methanol.
Application of the five butterfly alkene conjugated polymers in the detection to nitro arene explosive substance shown in above-mentioned formula I fall within this The protection domain of invention.
In the application, the nitro arene explosive substance for it is following any one：2,4,6- trinitrotoluenes (TNT), 2,4-DNT (DNT), 2,4,6- trinitrophenols (PA) and 4- nitrotoleunes (NT).
It is a further object of the present invention to provide a kind of fluorescent optical sensor for being used to detect nitro arene explosive substance.
The fluorescent optical sensor provided by the present invention for being used to detect nitro arene explosive substance, including five shown in above-mentioned formula I Butterfly alkene conjugated polymer.
The fluorescent optical sensor can be used for detecting the nitro arene explosive substance in gas phase.
Another object of the present invention is to provide a kind of film-type fluorescent optical sensor and preparation method thereof.
The film-type fluorescent optical sensor, including solid matrix and the institute of above-mentioned formula I that is carried on the solid matrix Show the film of five butterfly alkene conjugated polymers.
The solid matrix for it is following any one：Glass, quartz plate and silicon chip.
The film-type fluorescent optical sensor is prepared by the method comprising the following steps：By shown in above-mentioned formula I Five butterfly alkene conjugated polymers are dissolved in the solution that five butterfly alkene conjugated polymers shown in formula I are obtained in solvent, and the solution is coated on On the solid matrix, you can.
The solvent is preferably organic solvent, such as chloroform, tetrahydrofuran and dichloromethane.
Another object of the present invention is to provide a kind of method for detecting nitro arene explosive substance.
Methods described includes：The film-type fluorescent optical sensor is contacted with the steam of determinand, the fluorescence of film is detected Spectrum, if over the growth of time of contact, fluorescence is gradually quenched, then judges that the determinand explodes as nitro-aromatic class Thing.
The present invention efficiently obtains the conjugated polymer with five butterfly alkene fragments, rigidity by Sonogashira coupling reactions Five butterfly alkene structures there is sufficient hole, form molecular channel so that the polymer of electron rich is easy to the nitre with electron deficient Base aromatic hydrocarbons quasi-molecule produces response by electrostatic interaction, shows high sensitivity.The polymerization reported compared with Swager groups Thing, five butterfly alkene conjugated polymers shown in formula I of the invention have higher molecular weight, launch wavelength more red shift, and have more Good selectivity and sensitivity.The response time for the polymer reported than Swager groups shortens 2/3.
Detected using the conjugated polymer of the present invention, it is not necessary to which analyte is pre-processed, can be with without marking Non-Destructive Testing directly is carried out to the nitro arene explosive substance of trace.
The conjugated polymer of the present invention can carry out high selectivity to the nitro arene explosive substance in gas phase and fast Recognize fastly.
Brief description of the drawings
Fig. 1 is the synthetic route chart of compound 1 in embodiment 1.
Fig. 2 is the synthetic route chart of compound 2 in embodiment 1.
The synthetic route chart that Fig. 3 is conjugated polymer P in embodiment 1.
Fig. 4 is the nucleus magnetic hydrogen spectrum for the conjugated polymer P that embodiment 1 is prepared.
Fig. 5 is the ultra-violet absorption spectrum for the conjugated polymer P that embodiment 1 is prepared.
Fig. 6 is the fluorescence emission spectrum for the conjugated polymer P that embodiment 1 is prepared.
Fig. 7 is the fluorescence curve figure of the P films that prepare of embodiment 1 at different temperatures.
Fig. 8 is the fluorescence curve figure that the P films that embodiment 1 is prepared act on different time with TNT saturated vapors.
Embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments Reagent, material etc., unless otherwise specified, are commercially obtained.
In following embodiments compound 1 be according to literature method (J.S.Yang and T.M.Swager, J.Am.Chem.Soc., 1998,120,11864-11873) (synthetic route chart is as shown in Figure 1) of synthesis, concrete operations are as follows： 1. by anthracene and 1,4-benzoquinone with 2:1 ratio is dissolved in trimethylbenzene, is heated to reflux after 24 hours, is cooled to room temperature, and filtering, filter cake is used Dimethylbenzene, glacial acetic acid, the KBr aqueous solution and the hot wash of heat, most afterwards through chromatography over CC, obtain crocus solid 3.2. in argon gas Under protection, n-BuLi is added in the tetrahydrofuran solution of trimethylsilanylethyn at 0 degree, mixed liquor continues to react After 40 minutes, 3 are added, room temperature reaction is stayed overnight.After reaction terminates, 10%HCl quenchings are added, solvent is spin-dried for, obtains compound 4； 4 are dissolved in acetone, SnCl is added dropwise2Acetum, reaction solution continues to react 24 hours, filtering, and filter cake is dissolved in chlorine Imitate and be washed with water, be spin-dried for solvent, obtain white solid 5.3. compound 5 is dissolved in potassium hydroxide aqueous solution, tetrahydrofuran and first In the mixed solution of alcohol, react at room temperature 5 hours.After filtration drying, white solid 1 is obtained.
Compound 2 be according to literature method (T.M.Swager, C.J.Gil and M.S.Wrighton, J.Phys.Chem.1995,99,4886-4893) synthesis (synthetic route chart is as shown in Figure 2), concrete operations are as follows：1. to carbon Acetone soln is added in the mixture of sour potassium, bromotetradecane and hydroquinones, the lower reaction of nitrogen protection 3 days is reacted after terminating, Toluene is added into reaction solution, insoluble matter is filtered off, is spin-dried for solution, after being recrystallized twice through acetone/toluene, white solid 6 is obtained.2. By compound 6, KIO3With I2It is dissolved in acetic acid, adds sulfuric acid and water, reacts 6 hours, add Na2S2O4Until the iodine of brown Color fade, filtering, obtain crude product, after ethanol/Gossypol recrystallized from chloroform, obtain white solid 2.
The synthesis of embodiment 1, conjugated polymer P
The synthetic route chart of conjugated polymer P according to Fig. 3 carries out conjugated polymer P synthesis.Concrete operations are such as Under：
Under argon gas protection, difference Weigh Compound 1 (40mg, 0.084mmol), 2 (62mg, 0.084mmol), Pd (PPh3)4(5mg, 0.004mmol) and CuI (6mg, 0.03mmol) are in Schlenk bottles of 25mL, and add 5mL dryings two are different Propylamine and toluene 2:3 mixed solvent is as solvent, and 75 DEG C are reacted 3 days.Reaction is cooled to room temperature after terminating, and is spin-dried for, to residue Middle addition methanol 30mL carries out precipitating, and suction filtration obtains the powdered P 80mg of glassy yellow, yield is 95.2%.
The structure detection result of the compound is as follows：
1H NMR(300MHz,CDCl3) (Fig. 4 is conjugated polymer P nucleus magnetic hydrogen spectrum):δ7.50–7.39(m,10H), 7.03(brs,8H),6.10(brs,4H),4.47(brs,4H),2.23(brs,4H),1.74-1.72(m,4H),1.28-1.21 (m,46H)。
Mn=28.8kDa, Mw=30.9kDa.
From above-mentioned testing result, the compound structure is correct.
Embodiment 2, prepared conjugated polymer P uv-visible absorption spectra and the measure of fluorescence spectrum
It is 1.0 × 10 that conjugated polymer prepared in embodiment 1 is dissolved in chloroform to be configured to concentration respectively-6Mol/L is molten Liquid, then carries out the measure of uv-visible absorption spectra and fluorescence spectrum, and corresponding test result is as shown in table 1.
Fig. 5 is the ultra-violet absorption spectrum for the conjugated polymer P that embodiment 1 is prepared.
Fig. 6 is the fluorescence emission spectrum for the conjugated polymer P that embodiment 1 is prepared.
Table 1 is conjugated polymer P uv-visible absorption spectra and the measurement result of fluorescence spectrum
The measure of embodiment 3, prepared conjugated polymer P heat endurance
P is dissolved in the solution that chloroform is configured to 1mg/mL, then in the rotating speed that rotating speed is 3000 revs/min on spin coating instrument Under be spun on quartz plate (10mm × 10mm), film is made.Then the measure of fluorescence spectrum under different temperatures is carried out.As a result such as Shown in Fig. 7.
Fig. 7 is the fluorescence curve figure of P films at different temperatures.
As shown in Figure 7：Slowly decay after strengthening by a small margin with temperature rise film fluorescence intensity, temperature reaches 50 degree When, the fluorescence intensity of film enhances 20%, continues to increase temperature afterwards to 70 degree, it is strong that fluorescence intensity decays to room temperature by a small margin Degree, tends towards stability afterwards.It is stable to temperature that this result, which demonstrates the film,.
Embodiment 4, the detection using P film to TNT explosive saturated vapors
1 gram of TNT is placed in 10mL vials, cotton is covered with above, so on the one hand analyte and film can be prevented Contact, be on the other hand conducive to maintain bottle in TNT relative saturations vapour pressure.When the TNT in bottle reaches saturated vapor pressure, Conjugated polymer P films prepared in embodiment 3 are put into bottle rapidly, the regular hour is placed, then takes it rapidly Go out to measure its fluorescence spectrum, as a result as shown in Figure 6.
Fig. 8 is the fluorescence curve figure that P films act on different time with TNT saturated vapors.
As shown in Figure 8：The time for being placed in TNT saturated vapors with film increases, and its fluorescence is gradually quenched, 3 minutes it The fluorescence of interior film can be quenched more than 99%.
Synthesized polymer P molecular weight is 280,000, and fluorescence spectrum shows that launch wavelength can reach 490nm, in yellowish green Light, and with good heat endurance and film forming.
Polymer P is exceedingly fast to TNT response time, and the fluorescence of film can be quenched completely within 3 minutes.

Claims (7)

1. five butterfly alkene conjugated polymers shown in a kind of Formulas I：
In Formulas I, R is myristyl,
The M of five butterfly alkene conjugated polymers shown in Formulas InFor 288kDa, MwFor 309kDa；
Five butterfly alkene conjugated polymer methods, comprises the steps shown in formula I：
Compound shown in compound shown in formula II and formula III is subjected to Sonogashira coupling reactions, obtained containing shown in formula I The mixture of conjugated polymer；
In formula III, Y is I；R is myristyl；
In methods described, the mol ratio of the compound shown in formula II and the compound shown in formula III is 1:1；
The reaction temperature of the Sonogashira coupling reactions is 75 DEG C；Reaction time is 72 hours；
The Sonogashira coupling reactions are carried out under inert gas atmosphere；
The Sonogashira coupling reactions make catalyst using palladium-containing catalyst and CuI, wherein, the palladium-containing catalyst is Pd(PPh3)4。
2. the answering in the detection to nitro arene explosive substance of five butterfly alkene conjugated polymers shown in the formula I described in claim 1 With.
3. application according to claim 2, it is characterised in that：The nitro arene explosive substance for it is following any one： 2,4,6- trinitrotoluenes, 2,4-DNT, 2,4,6- trinitrophenols and 4- nitrotoleunes.
4. a kind of fluorescent optical sensor for being used to detect nitro arene explosive substance, the fluorescent optical sensor includes claim 1 institute Five butterfly alkene conjugated polymer shown in the formula I stated.
5. it is used to detecting the film-type fluorescent optical sensor of nitro arene explosive substance a kind of, including solid matrix and is carried on institute The film of five butterfly alkene conjugated polymers shown in the formula I described in the claim 1 on solid matrix is stated, wherein, the solid matrix For it is following any one：Glass, quartz plate and silicon chip.
6. preparing the method for the film-type fluorescent optical sensor described in claim 5, comprise the steps：By described in claim 1 Formula I shown in five butterfly alkene conjugated polymers be dissolved in the solution that five butterfly alkene conjugated polymers shown in formula I are obtained in solvent, will be described molten Liquid is coated on the solid matrix, you can.
7. a kind of method for detecting nitro arene explosive substance, including：By the film-type fluorescent optical sensor described in claim 5 with The steam contact of determinand, detects the fluorescence spectrum of film, if over the growth of time of contact, fluorescence is gradually quenched, then Judge the determinand as nitro arene explosive substance.
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Optimization of TNT sensory polymers;Aimee Roset et al.;《Proceedings of SPIE》;20001231;第4038卷;第512-518页 *

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