CN106366295B - A kind of water soluble fluorescent conjugated polymer and preparation method thereof - Google Patents

A kind of water soluble fluorescent conjugated polymer and preparation method thereof Download PDF

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CN106366295B
CN106366295B CN201610803314.4A CN201610803314A CN106366295B CN 106366295 B CN106366295 B CN 106366295B CN 201610803314 A CN201610803314 A CN 201610803314A CN 106366295 B CN106366295 B CN 106366295B
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water soluble
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CN106366295A (en
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崔月芝
苏熙
陶芙蓉
李天铎
李艳
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Qilu University of Technology
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Abstract

The invention discloses a kind of water soluble fluorescent conjugated polymer and preparation method thereof, the structural formula of the polymer is as shown in Equation 1：The preparation method includes, (1) monomer M and diethanol amine reaction generation monomer N；(2) using triethanolamine, palladium and triphenylphosphine as additive, monomer N and to styrene occur polymerisation obtain conjugated polymer P.The water soluble fluorescent conjugated polymer of the present invention includes water soluble group, which includes two parts：A part is with carbazoles conjugated main chain existing for the pi-conjugated systems of π, to ensure the optical property of polymer；Another part contains the water soluble group of polyhydroxy, so as to meet solubility of the polymer in water phase.Polymer chain can be dispersed substantially in aqueous environment, be conducive to analyte directly and polymer contact, realize the signal enlarge-effect of polymer.

Description

A kind of water soluble fluorescent conjugated polymer and preparation method thereof
Technical field
Present invention relates particularly to a kind of water soluble fluorescent conjugated polymer and preparation method thereof.
Background technology
Trinitrotoluene (TNT), dinitrotoluene (DNT) (DNT) are the important components of explosive.In addition, nitro-aromatic is also to people Class health has important harm.Therefore, the life to people to the onthe technology of site test of microscratch amount nitro-aromatic is explored Property safety and environmental protection have very important significance.Fluorescence conjugated polymer is due to its unique molecular wire effect Should, fluorescence signal enlarge-effect can be produced, becomes the very promising sensing material of detection nitro-aromatic.Report at present Fluorescent conjugated polymer for nitro-aromatic explosive detection is mostly hydrophobic macromolecule, is generally used for gas phase nitro-aromatic Detection.However, there is certain solubility (being respectively 130mg/L and 300mg/L) under TNT and DNT room temperature in water, at present Study the detection that more hydrophobic fluorescent conjugated polymer is difficult to meet nitro-aromatic in industrial wastewater.
In reality, the research to gas phase nitro-aromatic explosive is relatively more, fewer to the research in water phase, military Explosive used in base is preparing, is causing very big pollution during transport, deposit and use to soil and water body, while with Some industrial discharge sewage also result in some pollutions to liquid phase environments such as seawater or underground water, and environment is dirty caused by explosive Dye than it is more serious when, not only induce the danger of explosion at any time, but also the existence to the mankind and animals and plants threatens.
Therefore, the detection that water miscible fluorescent conjugated polymer is used for microscratch amount nitro-aromatic in water phase is developed, it is right In environmental protection, reduce harm of the nitro-aromatic to the mankind and have very important significance.
The content of the invention
For the above prior art, the object of the present invention is to provide a kind of water soluble fluorescent conjugated polymer and its preparation side Method, the water-soluble polymer can be completely dissolved in aqueous.
The present invention uses following technical scheme：
First purpose of the present invention is to provide a kind of water soluble fluorescent conjugated polymer, its structural formula is as shown in Equation 1：
Wherein, n is the degree of polymerization of conjugated polymer, and the n is 20~30, is preferably 25.
Second object of the present invention is to provide a kind of monomer for preparing above-mentioned water soluble fluorescent conjugated polymer, its structure Formula is as shown in Equation 3.
Third object of the present invention is to provide a kind of preparation method of above-mentioned water soluble fluorescent conjugated polymer, including with Lower step：
(1) synthesis of monomer N
The structural formula of monomer M and diethanol amine reaction generation monomer N, the monomer M and monomer N are respectively such as 2 and 3 institute of formula Show；
Wherein, X Cl, Br or I；
(2) synthesis of conjugated polymer P
Using triethanolamine, palladium and triphenylphosphine as additive, monomer N and to styrene occur polymerisation be total to Conjugated polymer P, its structural formula are as shown in Equation 1.
In step (1), the preparation method of monomer M can be obtained according to method of the prior art.For product yield, Preferably, the preparation method of the monomer M comprises the following steps：
Using potassium hydroxide, tetrabutylammonium bromide as additive, 3,6- dihalo carbazoles and monohaloalkyl acetic acid ethyl reaction will Product after reaction hydrolyzes generation monomer M in alkaline conditions, and the structural formula of the monomer M is as shown in Equation 2.
Preferably, the reaction carries out in solvent DMF.
Preferably, 3, the 6- dihalos carbazole is 3,6- dibromo carbazoles, 3,6- dichloro carbazoles or 3,6- diiodocarbazol.
Preferably, the monohaloalkyl ethyl acetate is bromoacetate, ethyl chloroacetate or ethyl iodoacetate.
Preferably, the molar ratio of 3, the 6- dihalos carbazole and monohaloalkyl ethyl acetate is 1~2：2.
It is further preferred that the molar ratio of 3, the 6- dihalos carbazole, potassium hydroxide and tetrabutylammonium bromide is (4 ~6)：(15~20)：(0.1~0.2).
Preferably, the reaction temperature of 3,6- dihalos carbazole and monohaloalkyl ethyl acetate is 80~90 DEG C, further preferably For 85 DEG C；Preferably, the reaction time is 19~21h, further preferred for 20h.
Preferably, hydrolysis generation monomer M, hydrolysis temperature are 80~90 DEG C in alkaline conditions, further preferred for 85 ℃；Preferably, hydrolysis time is 4~6h, further preferred for 5h.
It is further preferred that the preparation method of the monomer M includes step in detail below：
3,6- dihalos carbazole, potassium hydroxide, tetrabutylammonium bromide are dissolved in DMF respectively, after stirring, add monohaloalkyl Ethyl acetate, after whole mixed solution heats at 80~90 DEG C and stirs 19~21h, is cooled to room temperature, and mixing is obtained by filtration Filtrate；Sodium hydroxide is made into sodium hydrate aqueous solution, adds in filtrate, at 80~90 DEG C after 4~6h of heating stirring, will react Solution pours into distilled water and filtrate is obtained by filtration；Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo. Solid product is obtained, is monomer M, yield is about 90% or so.
In the monomer M and diethanol amine reaction generation monomer N, it is preferred that the molar ratio of monomer M and diethanol amine For 1~2：2, it is further preferred for 1：2；Preferably, the reaction temperature is 40~60 DEG C, and the time is 5~7h；It is further excellent Choosing, the reaction temperature is 45 DEG C, time 6h.
The reaction carries out in solvent DMF, after reaction, extracts form with liquid separation, DMF is washed with water, and use second Solution is obtained by extraction in acetoacetic ester, is finally purified with column tswett's chromatography methods, and monomer N is obtained after dry.Wherein, the column tswett's chromatography methods is adopted Silicagel column, eluent are ethyl acetate and the mixed liquor of petroleum ether；Ethyl acetate：The volume of petroleum ether is preferably 10：1.
In step (2), it is preferred that the monomer N and the molar ratio to styrene are (1~2)：(1~2), further Preferably 1：1.
Preferably, the additive amount ratio of the monomer N, triethanolamine, palladium and triphenylphosphine is 1mmol：(0.3~ 0.4)mL：(0.03~0.05) mmol:(0.1~0.3) mmol；It is further preferred that the monomer N, triethanolamine, palladium Additive amount ratio with triphenylphosphine is 1mmol：0.35mL：0.04mmol:0.2mmol.
Preferably, the reaction temperature is 90~100 DEG C, and the reaction time is 5~7h；It is further preferred that the reaction Temperature is 100 DEG C, reaction time 6h.
The polymerisation carries out in solvent DMF.
Preferably, the reaction is reacted under conditions of inert gas, it is further preferred that the inert gas is Nitrogen.
After polymerisation, reaction solution is added in methanol solution, obtains the crude product containing conjugated polymer P. Then DMF is respectively adopted and methanol is purified and (preferably purified twice, once refer to be purified using DMF and methanol), most (extraction time preferably 23~25h) is extracted with dichloromethane afterwards, unnecessary monomer is removed, obtains conjugated polymer P.
A technical solution in above-mentioned technical proposal has the advantages that：
(1) water soluble fluorescent conjugated polymer of the invention includes water soluble group, the water soluble fluorescent conjugated polymer Including two parts：A part is the π containing carbazole-pi-conjugated main chain, ensures the optical property of polymer；Another part contains polyhydroxy The water soluble group of base, so as to meet solubility of the polymer in water phase.Polymer chain can be dispersed substantially in water phase In environment, be conducive to nitro-aromatic determinand directly and polymer contact, realize the signal enlarge-effect of polymer.
(2) water-soluble polymer of the invention, containing substantial amounts of hydroxyl, enrichment effect can be produced to nitro-aromatic by hydrogen bond Should, so as to reduce the minimum detection limit to nitro-aromatic detection.
(3) preparation method of the invention is simple, cost is relatively low, and the synthesis for water soluble fluorescence sensor has certain Practical significance, is adapted to large-scale promotion application.
Brief description of the drawings
Fig. 1：The preparation process of water soluble fluorescent conjugated polymer P in embodiment 1.
Fig. 2：The polymer P fluorescence intensity change to the TNT and DNT of various concentrations and quenching efficiency (η in waterEP)。
Fig. 3：Efficiency (a and c) and Stern-Volmer numerical value (b and d) are quenched to TNT and DNT concentration function change curves.
Fig. 4：Fluorescent quenching research (TNT, DNT, picric acid PA, 1,4-benzoquinone BQ, nitrobenzene of the polymer to different analytes NB, chlorobenzene chlorobenzene, benzene sulfonic acid benzenesulfonic acid, phenol phenol, toluene toluene, NaCl, KOH and HCl).
Fig. 5：The nuclear magnetic spectrogram of monomer M.
Fig. 6：The nuclear magnetic spectrogram of monomer N.
Fig. 7：The nuclear magnetic spectrogram of water soluble fluorescent conjugated polymer P.
Embodiment
If reagent and instrument that the present invention uses can be obtained without specified otherwise by commercial sources.
A kind of preparation method of 1 water soluble fluorescent conjugated polymer of embodiment
Water soluble fluorescent conjugated polymer P preparation process is as shown in Figure 1：
(1) synthesis of monomer M
By 3,6- dibromos carbazole (1.63g, 5mmol), potassium hydroxide (1g, 17.8mmol), tetrabutylammonium bromide (0.05g, 0.155mmol) it is dissolved in respectively in the DMF of 40mL, after stirring 20min, adds ethyl chloroacetate (1.23g, 10mmol), it is whole mixed After conjunction solution heats at 85 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.By sodium hydroxide (0.8g, 5mL aqueous solutions 20mmol) are made into, adds in filtrate, at 85 DEG C after heating stirring 5h, reaction solution is poured into 400mL distilled water And filtrate is obtained by filtration.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.Solid product M is obtained, Yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H),7.519-7.582(q,4H),11.0 (s, 1H), as shown in Figure 5.
(2) synthesis of monomer N
After 2.8mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 6h is stirred at 45 DEG C.Reaction terminates Afterwards, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column chromatogram chromatography method (silica gel, ethyl acetate：Petroleum ether=10:1) purification obtains product, and is dried in vacuo at 60 DEG C, obtains white solid, is Monomer N, yield 42.8%；1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q, 4H), 4.810 (s, 2H), 3.538 (t, 4H), 2.840 (t, 4H), as shown in Figure 6.
(3) synthesis of conjugated polymer P
By monomer N (0.47g, 1mmol), to styrene (0.13g, 1mmol), triethanolamine (0.35mL), palladium (9.0mg, 0.04mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen, 100 At DEG C after heating stirring 6h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.Respectively with 5mL DMF and 250mL methanol purifies twice back and forth, finally with dichloromethane surname extraction 24h, removes unnecessary monomer, obtains orange solids, That is conjugated polymer P, yield 85%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620-6.476(t,12H), 4.981 (s, 2H), 3.777 (s, 4H), 3.348 (s, 4H), as shown in Figure 7.FT-IR(KBr)：3383,3100,2950, 1700cm-1。
The measure of polymer P molecular weight：Since the magnitude relationship of polymer molecular weight is to molecular wire effect, and to fluorescence The intensity at peak has an impact, and it is therefore necessary to survey the molecular weight of polymer.Due to containing substantial amounts of hydroxyl on polymer, it is impossible to use The molecular weight of polymer P in laser light scattering instrument measure tetrahydrofuran.The present invention is using to bromine cumene terminated polymer, so Afterwards by, to the number ratio of the hydrogen of bromine cumene and polymer P, the molecular weight for estimating polymer P is about 1.1 on nuclear-magnetism × 104, its structural formula as indicated with 1, n 25.
A kind of preparation method of 2 water soluble fluorescent conjugated polymer of embodiment, comprises the following steps：
(1) synthesis of monomer M
By 3,6- dichloros carbazole (1.1805g, 5mmol), potassium hydroxide (1g, 17.8mmol), tetrabutylammonium bromide (0.05g, 0.155mmol) is dissolved in the DMF of 40mL respectively, after stirring 20min, addition bromoacetate (1.23g, 7.365mmol), after whole mixed solution heats at 85 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.Will Sodium hydroxide (0.8g, 20mmol) is made into 5mL aqueous solutions, adds in filtrate, at 87 DEG C after heating stirring 5.5h, by reaction solution Pour into 400mL distilled water and filtrate is obtained by filtration.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo. Obtain solid product-monomer M, yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H), 7.519-7.582(q,4H),11.0(s,1H)。
(2) synthesis of monomer N
After 2.8mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 6.5h is stirred at 42 DEG C.Reaction knot Shu Hou, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column tswett's chromatography methods (silica gel, ethyl acetate：Petroleum ether=10:1) purification obtains product, and is dried in vacuo at 60 DEG C, and obtained white solid is Monomer N, yield 56.4%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q,4H), 4.810 (s, 2H), 3.538 (t, 4H), 2.840 (t, 4H).
(3) synthesis of conjugated polymer P
By monomer N (0.47g, 1mmol), to styrene (0.13g, 1mmol), triethanolamine (0.35mL), palladium (9.0mg, 0.04mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen, 100 At DEG C after heating stirring 6.5h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.Respectively with 5mL DMF and 250mL methanol purifies twice back and forth, finally with dichloromethane surname extraction 24.5h, removes unnecessary monomer, what is obtained is orange solid Body, that is, conjugated polymer P, its structural formula as indicated with 1, n 25.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620- 6.476(t,12H),4.981(s,2H),3.777(s,4H),3.348(s,4H).FT-IR(KBr)：3383,3100,2950, 1700cm-1。
A kind of preparation method of 3 water soluble fluorescent conjugated polymer of embodiment, comprises the following steps：
(1) synthesis of monomer M
By 3,6- dibromos carbazole (1.793g, 5.5mmol), potassium hydroxide (1.124g, 20mmol), tetrabutylammonium bromide (0.064g, 0.2mmol) is dissolved in the DMF of 40mL respectively, after stirring 20min, adds ethyl chloroacetate (1.23g, 10mmol), After whole mixed solution heats at 83 DEG C and stirs 20h, room temperature is cooled to, mixing filtrate is obtained by filtration.By sodium hydroxide (0.8g, 20mmol) is made into 5mL aqueous solutions, adds in filtrate, at 85 DEG C after heating stirring 5h, reaction solution is poured into 400mL Simultaneously filtrate is obtained by filtration in distilled water.Filtrate is adjusted to pH 2-3 with concentrated hydrochloric acid, obtains white solid, is dried in vacuo.What is obtained consolidates Body product is monomer M, yield about 90%.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.461(s,2H),7.519- 7.582(q,4H),11.0(s,1H)。
(2) synthesis of monomer N
After 3mmol monomer M and 5.6mmol diethanol amine is dissolved in 15mL DMF, 5h is stirred at 50 DEG C.Reaction terminates Afterwards, the form extracted with liquid separation, is washed with water DMF, and be extracted with ethyl acetate to obtain solution.Finally use column tswett's chromatography methods (silicon Glue, ethyl acetate：Petroleum ether=10:1) purification obtains product, and is dried in vacuo at 60 DEG C, and product is white solid-monomer N,1H NMR:(DMSO-d6,400MHz),δ(ppm):8.426(s,2H),7.726-7.431(q,4H),4.810(s,2H), 3.538 (t, 4H), 2.840 (t, 4H).
(3) synthesis of conjugated polymer P
By monomer N (0.564g, 1.2mmol), to styrene (0.13g, 1mmol), triethanolamine (0.40mL), palladium (10.125mg, 0.045mmol), triphenylphosphine (60.9mg, 0.2mmol) are dissolved in the DMF of 5mL anhydrous and oxygen-frees, lead to nitrogen, At 100 DEG C after heating stirring 6h, reaction solution is dripped in the methanol solution of 250mL, obtain crude product.5mL DMF are used respectively Purified back and forth twice with 250mL methanol, finally with dichloromethane surname extraction 25h, remove unnecessary monomer, obtain product as orange Color solid-conjugated polymer P, its structural formula as indicated with 1, n 25.1H NMR:(DMSO-d6,400MHz),δ(ppm):8.620- 6.476(t,12H),4.981(s,2H),3.777(s,4H),3.348(s,4H).FT-IR(KBr)：3383,3100,2950, 1700cm-1。
In order to better illustrate the effect of water-soluble polymer of the present invention, the water-soluble polymer sensitivities in embodiment 1 The research of energy is as follows.
Detection of 1 polymer of experimental example to DNT in water and TNT
Polymer P in embodiment 1 can preferably be explained to TNT and DNT quenching effects by the change of fluorescence spectrum Size.This experiment has measured 1.0 × 10 by F-4600 sepectrophotofluorometers-5The polymer of g/L in water phase to TNT and The fluorescence spectrum (such as Fig. 2) of DNT.As can be seen from Figure 2A, when the concentration of TNT is 1.08 × 10-4During mol/L, quenching efficiency reaches To 84.5%；When TNT concentration is 1.8 × 10-4During mol/L, the fluorescent quenching efficiency (1-I/I of polymer0) reach balance and be 93%, it was found from Fig. 2 B, when the concentration of DNT is 1.44 × 10-4During mol/L, quenching efficiency reaches 80.5%；When the concentration of DNT For 2.3 × 10-4During mol/L, it is 91% that the fluorescent quenching efficiency of polymer, which reaches balance,.Apparent polymer is to TNT and DNT exhibitions Good quenching performance is showed.As can be seen that the polymer P in embodiment 1 has preferable solubility in water phase, can be complete It is evenly distributed on entirely in water phase, so as to have higher quenching effect to two kinds of nitro-aromatics.
The measure of 2 test limit of experimental example
Since explosive causes the fields such as ocean, underground water huge environmental pollution, biotic environment and people are directly endangered Class health.TNT is again mainly one of most common explosive, and the byproduct (DNT) of simultaneously synthesizing TNT is the important chemical groups of TNT Into part, therefore TNT and DNT is selected to be detected as the representative of NACs to its fluorescence sensitivity here.
Solubility under TNT and DNT room temperature in water is 130mg/L (i.e. 5.7 × 10-4) and 300mg/L (i.e. 1.6 mol/L ×10-3mol/L).The concentration that national regulation industrial wastewater allows the maximum emission of NACs is 5mg/L, and allows surface water most Height is 0.5mg/L containing nitro-aromatic concentration.Test limit (LOD) is key index whether measurement sensor is sensitive.Therefore need Test limit of the polymer to two kinds of nitro-aromatics is calculated, so as to obtain polymer in aqueous to TNT and DNT high sensitivities Low physical quantity.
That Fig. 3 a and 3c are represented respectively is fluorescent quenching rate (η of the polymer with the TNT and DNT of various concentrationsEP=1-I/ I0) curve.As can be seen that with the increase of TNT and DNT concentration in dampening phase, fluorescence intensity gradually reduces, quenching rate η EP numerical value Increasing.These results reflect concentration dependent of the fluorescent quenching to TNT or DNT well.
Quenching process can be represented (1) by Stern-Volmer equations
I0/ I=1+Ksv [Q] (1)
I0Represent maximum fluorescence intensity, I represent when gas DNT either the fluorescence intensity Q in the presence of TNT represent DNT or The concentration of TNT.Slope represent Stern-Volmer constant (Ksv) of the film to two kinds of gas, the Stern to DNT and TNT- Volmer constants are respectively 42000M-1And 24000M-1。
Polymer passes through equation C to the test limit (LOD) of DNT in aqueous solution and TNTL=3S/Ksv is obtained, CLRepresent be The numerical value of test limit (LOD), what S was represented is the standard deviation of polymer fluorescent intensity in 15 water blanks measured.It is poly- Compound is 7.4 × 10 respectively to the test limit of TNT and DNT–7Mol/L and 1.1 × 10–6mol/L.It can draw, in embodiment 1 Water-soluble polymer it is higher to the detection sensitivity of nitro-aromatic in water.
Selectivity of 3 water-soluble polymer of experimental example to different determinands
According to the quenching mechanism of fluorescent conjugated polymer, between the material of electron deficient and the polymer of supplied for electronic, due to hair Raw electronics transfer, may result in the fluorescent quenching of conjugated polymer.Fig. 4 show common chemical substance (such as TNT, DNT, Picric acid PA, 1,4-benzoquinone BQ, nitrobenzene NB, chlorobenzene, benzene sulfonic acid, phenol, toluene) to the fluorescent quenching of water-soluble polymer P, remove Outside this, many inorganic chaff interferents (NaCl, KOH and HCl) are also put into wherein.Fig. 4 shows, TNT, DNT, nitrobenzene and bitter taste Acid has polymer obvious quenching effect, and quenching rate is 95%, 91%, 86% and 69% respectively.1,4-benzoquinone and benzene sulfonic acid pair Polymer has small quenching effect, however, other organic matters (chlorobenzene, phenol, toluene) and inorganic chaff interferent (such as HCl, NaCl and KOH etc.) to polymer almost without response.
Polymer is mainly derived from the response difference of nitro-aromatic and chaff interferent the electron-withdrawing power of determinand and with gathering The electron orbit matching degree of compound.There is higher electronics rail between carbazole polymer and TNT, DNT, nitrobenzene and picric acid Road matches, while TNT has three nitryl groups, and electron-withdrawing power is eager to excel than DNT, therefore caused quenching efficiency (95%) is more than DNT (91%), as nitrobenzene NB, only an electron withdrawing group, therefore caused quenching efficiency (86%) is lower than DNT. For picric acid PA, although there is three nitryl groups, the electron repulsion effect of hydroxyl weakens the suction of PA on molecular structure Electronic capability causes quenching rate (69%) slightly lower.For benzoquinones BQ, although electron-withdrawing power is strong, fluorescent quenching rate is low.It is former Because being that quinones has poor binding constant (K with polymerb), so as to cause quenching rate low.In contrast, benzene and its derivative (chlorobenzene, benzene sulfonic acid, phenol, toluene) quenching rate is low may be weak related with their electron-withdrawing power.For inorganic matter (NaCl, KOH, HCl) interference, fluorescence intensity do not have any change.Inorganic matter does not have matched electron orbit to receive electricity Son causes polymer to be quenched.These results indicate that the polymer P in embodiment 1 has higher quenching effect to nitro-aromatic And selectivity.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (16)

1. a kind of water soluble fluorescent conjugated polymer, it is characterized in that, its structural formula is as shown in Equation 1：
Wherein, n is 20~30.
2. the monomer of the water soluble fluorescent conjugated polymer described in claim 1 is prepared, it is characterized in that, its structural formula such as institute of formula 3 Show：
Wherein, X Cl, Br or I.
3. the preparation method of the water soluble fluorescent conjugated polymer described in claim 1, it is characterized in that, comprise the following steps：
(1) synthesis of monomer N
The structural formula of monomer M and diethanol amine reaction generation monomer N, the monomer M and monomer N are respectively as shown in formula 2 and formula 3；
Wherein, X Cl, Br or I；
(2) synthesis of conjugated polymer P
Using triethanolamine, palladium and triphenylphosphine as additive, monomer N and polymerisation occurs to styrene to obtain conjugation poly- Compound P.
4. preparation method as claimed in claim 3, it is characterized in that：In step (1), the preparation method of the monomer M include with Lower step：Using potassium hydroxide, tetrabutylammonium bromide as additive, 3,6- dihalo carbazoles and monohaloalkyl acetic acid ethyl reaction will Product after reaction hydrolyzes generation monomer M in alkaline conditions.
5. preparation method as claimed in claim 4, it is characterized in that：3, the 6- dihalos carbazole is 3,6- dibromo carbazoles, 3, 6- dichloros carbazole or 3,6- diiodocarbazols；The monohaloalkyl ethyl acetate is bromoacetate, ethyl chloroacetate or iodoacetic acid second Ester.
6. preparation method as claimed in claim 4, it is characterized in that：The 3,6- dihalos carbazole and monohaloalkyl ethyl acetate Molar ratio is 1~2：2.
7. preparation method as claimed in claim 4, it is characterized in that：3,6- dihalos carbazole, potassium hydroxide and the tetrabutyl The molar ratio of ammonium bromide is (4~6)：(15~20)：(0.1~0.2).
8. preparation method as claimed in claim 4, it is characterized in that：Hydrolysis generation monomer M, hydrolysis temperature are in alkaline conditions 80~90 DEG C, hydrolysis time is 4~6h.
9. preparation method as claimed in claim 3, it is characterized in that：In step (1), the molar ratio of monomer M and diethanol amine For 1~2：2.
10. preparation method as claimed in claim 3, it is characterized in that：In step (1), the reaction temperature is 40~60 DEG C, when Between be 5~7h.
11. preparation method as claimed in claim 10, it is characterized in that：The reaction temperature is 45 DEG C, time 6h.
12. preparation method as claimed in claim 3, it is characterized in that：In step (1), the reaction carries out in solvent DMF, After reaction, form is extracted with liquid separation, DMF is washed with water, and be extracted with ethyl acetate to obtain solution, finally analysed with column chromatograph Method purifies, and monomer N is obtained after dry.
13. preparation method as claimed in claim 3, it is characterized in that：In step (2), the monomer N and mole to styrene Ratio is (1~2)：(1~2).
14. preparation method as claimed in claim 3, it is characterized in that：In step (2), the monomer N, triethanolamine, palladium Additive amount ratio with triphenylphosphine is 1mmol：(0.3~0.4) mL：(0.03~0.05) mmol:(0.1~0.3) mmol.
15. preparation method as claimed in claim 3, it is characterized in that：In step (2), the reaction temperature is 90~100 DEG C, Reaction time is 5~7h；The reaction is reacted under conditions of inert gas.
16. preparation method as claimed in claim 15, it is characterized in that：The inert gas is nitrogen.
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