CN101885797A - A kind of functional polymer and its preparation method and application - Google Patents

Abstract

The invention discloses a functional polymer, which is a random copolymer with a weight average molecular weight of 6000-15000 composed of N-vinylimidazole structural units and 2-mercaptobenzothiazole derivative structural units; The molar percentage of the N-vinylimidazole structural unit in the regular copolymer is 20%-45%, and the molar percentage of the 2-mercaptobenzothiazole derivative structural unit is 55%-80%. The invention also discloses the preparation method and application of the functional polymer. The polymer structure contains two binding points of imidazole ring and S and N heteroatom groups that are easy to coordinate heavy metal ions, so the polymer and its film prepared by the invention can selectively adsorb and detect heavy metal ions in water.

Description

A kind of functional polymer and its preparation method and application

technical field

The invention relates to the field of organic polymer sensing materials and environmental monitoring, in particular to a functional polymer based on quartz crystal microbalance technology and its preparation and application. The functional polymer can be applied to the identification and detection of heavy metal ions in water and the field of preparing chemical sensors.

Background technique

Over the past 20 years, extensive economic growth has resulted in the rapid development of my country's national economy, but also seriously polluted the natural environment. Various environmental pollutants, especially heavy metal ions such as cadmium, cobalt, lead and copper ions produced in industrial production, enter the water and soil environment, which not only pollutes the natural environment, but also endangers human survival and health. Therefore, the identification and detection of trace heavy metal ions in water is of great significance for the recovery and reuse of metal elements and early monitoring of environmental pollution.

At present, the detection methods of heavy metal ions mainly include inductively coupled plasma mass spectrometry, atomic absorption spectroscopy, and electrochemical anodic stripping voltammetry. Although these techniques have high sensitivity and specificity, they have defects such as complicated sample pretreatment, time-consuming operation, expensive instruments and high operating costs, and offline detection, making it difficult to meet the needs of current detection work. The Chinese patent application with the publication number CN 101021515A discloses a method for in-situ sampling, separation, enrichment and measurement of heavy metal ions in water bodies, using osmosis to diffuse heavy metal ions from the inside of the membrane to react with polymer compounds, these Macromolecular compounds are mainly hydroxymethylcellulose, chitosan and sodium polyacrylate, etc., whose functional groups can combine with heavy metal ions, but in fact there is no selective adsorption performance, and the detection steps are complicated and time-consuming; and because they are The concentration of heavy metal ions is calculated by atomic absorption spectrometry, which cannot be detected in real time. Chinese patent CN200610009925.8 discloses the application of a fluorescent molecular probe in the detection of transition metals and heavy metal ions, and designed and synthesized a fluorescent material that selectively enhances the recognition of Co ²⁺ in various solutions, especially aqueous solutions. As a probe, the fluorescent molecular structure is relatively complex, and column chromatography steps are required for separation and purification. It is difficult to realize industrial application as a sensing material, and it is still impossible to achieve online real-time and simple and fast detection. Therefore, it is necessary to seek a simpler and faster qualitative and quantitative technology to identify the heavy metal ions that may exist in water.

Contents of the invention

The invention provides a functional polymer and its film, which can be used to detect trace heavy metal ions.

A functional polymer, which is composed of the N-vinylimidazole structural unit shown in the following formula M1 and the 2-mercaptobenzothiazole derivative structural unit shown in the formula M2, is a random polymer with a weight average molecular weight of 6000-15000 copolymer;

The molar percentage of N-vinylimidazole structural units in the random copolymer is 20%-45%, and the molar percentage of 2-mercaptobenzothiazole derivative structural units is 55%-80%.

The preparation method of described functional polymer, comprises the steps:

Using the N-vinylimidazole monomer represented by formula M5 and the double bond-containing 2-mercaptobenzothiazole derivative monomer represented by formula M6 as raw materials, the vinyl double bonds of the two monomers are initiated by an initiator to copolymerize Reaction, make random copolymer;

As preferred:

The initiator can be a free radical initiator commonly used in this field. In order to ensure a better effect of the synthesis reaction, azobisisobutyronitrile or benzoyl peroxide is selected.

The amount of the initiator can be adjusted through experiments, and is generally 0.01%-5%, preferably 0.2%-3%, of the total weight of the N-vinylimidazole monomer and the 2-mercaptobenzothiazole derivative monomer.

The copolymerization reaction condition is: carry out free radical copolymerization reaction in anhydrous solvent under anaerobic condition.

The oxygen-free condition can be realized by conventional methods in the art, for example: vacuum-nitrogen replacement of the reaction system to remove oxygen therein, or directly carry out the reaction in an inert gas atmosphere. The inert gas includes a wide range of inert gases in the art, such as one of nitrogen, helium and the like.

The anhydrous solvent can be an organic solvent commonly used in this field, such as 1,4-dioxane or tetrahydrofuran. The anhydrous solvent is obtained by removing traces of water from the solvent by using a common water removal method such as drying over calcium hydride and metal sodium before use.

The copolymerization reaction temperature is 60°C-90°C, and the copolymerization reaction time is 12 hours-24 hours.

After the completion of the copolymerization reaction, the reaction product can be purified, and the specific purification process includes:

Cool the reaction liquid, remove the insoluble particles suspended in the reaction liquid after centrifugation, the upper layer of light yellow clear liquid is precipitated in a large amount of acetone, and then centrifuged to obtain a light yellow precipitate, and the precipitate is dried to constant weight to obtain a functional polymer Material: poly(2-mercaptobenzothiazole derivative-co-N-vinylimidazole) random copolymer (P(MBTVBC-co-VIM)).

The preparation method of the 2-mercaptobenzothiazole derivative monomer containing a double bond shown in the formula M6 comprises the steps of:

Reaction of p-chloromethylstyrene or p-bromomethylstyrene shown in formula M3 with 2-mercaptobenzothiazole shown in formula M4 in the presence of sodium hydride and tetrahydrofuran to prepare the compound containing 2-mercaptobenzothiazole derivative monomer with double bond;

In formula M3, X is selected from Cl or Br.

The p-chloromethyl styrene or p-bromomethyl styrene monomer has a double bond and can be polymerized, and the chloromethyl or bromomethyl at the para position can be functionalized, and commercially available products can be used.

The preparation method of the 2-mercaptobenzothiazole derivative monomer containing a double bond shown in the formula M6 comprises the steps of:

(1) Dissolving 2-mercaptobenzothiazole represented by formula M4 in tetrahydrofuran, adding sodium hydride, reacting to generate a tetrahydrofuran solution of 2-mercaptobenzothiazole sodium salt;

(2) Dissolve p-chloromethylstyrene or p-bromomethylstyrene shown in formula M3 in tetrahydrofuran to form a transparent solution, mix it with the tetrahydrofuran solution of the above-mentioned 2-mercaptobenzothiazole sodium salt, and heat ℃ for 24 hours to 48 hours, and after post-treatment to prepare the double bond-containing 2-mercaptobenzothiazole derivative monomer represented by the formula M6.

The post-treatment process includes: precipitating the reaction solution in an aqueous sodium hydroxide solution (such as an aqueous sodium hydroxide solution with a mass concentration of 3‰), and drying to constant weight through suction filtration.

The polymer has an imidazole ring that is both hydrophilic and can bind metal ions, and has a hydrophobic 2-mercaptobenzothiazole derivative structural unit, wherein the S and N heteroatom groups make it possible to select Therefore, it can be used to identify and detect trace heavy metal ions in water, and can also be used to prepare chemical sensors.

The heavy metal ions include one or more of Cd ²⁺ , Pb ²⁺ , Zn ²⁺ , Cu ²⁺ , etc., especially Cu ²⁺ .

In order to improve the sensitivity of detection, functional polymers are used in the field of identification, detection and chemical sensors of trace heavy metal ions in water, which can be realized by combining quartz crystal microbalance technology. For example: the functional polymer can be dissolved in an organic solvent (such as chloroform) to make a functional polymer solution, and the functional polymer solution is added dropwise to the gold electrode surface of a blank quartz wafer, and the functional A functional polymer solution is spin-coated on the gold electrode surface of a blank quartz wafer to form a film and then dried to obtain a quartz wafer coated with a functional polymer film. When the solution containing metal ions flows through the functional polymer film on the surface of the quartz wafer, the resonant frequency response is detected by a quartz crystal microbalance to reflect the concentration of metal ions in the solution containing metal ions.

The thickness of the functional polymer film can be adjusted by controlling the concentration of the functional polymer solution. The mass percent concentration of the functional polymer solution is ideally 0.065%-0.5%, and the preparation temperature is 10°C-20°C ideal.

When the functional polymer film is used to detect the concentration of heavy metal ions in water, its thickness range is ideally 200nm-550nm; within this thickness range, the ^minimum detection of the concentration of heavy metal ions Cu in water by the functional polymer film The limit is 10ppm (mass percentage concentration 0.001%), and the corresponding frequency response value is 9Hz.

The operating conditions of the homogenizer are preferably at a low speed of 4000 rpm for 9 seconds, and at a high speed of 3000 rpm for 30 seconds.

The molecular structure of the random copolymer of the present invention can be characterized by infrared, nuclear magnetic and other means.

The principle of the present invention is: the random copolymer containing the N-vinylimidazole structural unit shown in formula M1 and the 2-mercaptobenzothiazole derivative structural unit shown in formula M2 has the ability to bind heavy metal ions on the side chain. The imidazole ring and S, N heteroatom groups (collectively referred to as functional groups) are spin-coated on the surface of the gold electrode of the quartz wafer in the form of a certain concentration solution. The strong interaction enables the film to be stably fixed on the surface of the gold electrode; when the quartz wafer of the spin-coated polymer film is in contact with the heavy metal ion solution, the functional groups on the surface of the film can combine with the heavy metal ions, making the surface of the quartz wafer The mass load of the chip changes, which in turn causes the frequency response of the chip to change, so that the heavy metal ions can be identified and detected conveniently in real time.

The present invention has following advantage:

1. The structure of the functional polymer of the present invention contains two binding points that are easy to coordinate heavy metal ions, the imidazole ring and the S and N heteroatom groups, so the polymer and its film prepared by the present invention can selectively adsorb and detect Heavy metal ions, especially Cu ²⁺ .

2. The functional polymer film of the present invention presents a porous structure, and the pore diameter ranges from 100nm to 400nm, and the average pore depth is 10nm to 20nm, which effectively increases the specific surface area and can absorb more heavy metal ions.

3. In the preparation method adopted in the present invention, the 2-mercaptobenzothiazole derivative containing a double bond is first synthesized, and then copolymerized with N-vinylimidazole to obtain a copolymer. The synthesis route is concise and clear.

4. The quartz crystal microbalance technology adopted in the present invention is used for quantitative detection of heavy metal ions due to the high-sensitivity mass effect, and the quartz wafer coated with functional polymer film has high detection sensitivity to heavy metal ions in water, and the selectivity is relatively high. Well, its detection limit for Cu ²⁺ can reach a concentration of 10 ppm (mass percentage concentration 0.001%).

5. The preparation method of the spin-coating film of the present invention has a simple and controllable process and is suitable for industrial production.

It can be seen that the preparation of the copolymer film of functional N-vinylimidazole and 2-mercaptobenzothiazole derivatives and the application of the quartz crystal microbalance technology of the present invention prove to be a good choice. The copolymer structure prepared by the present invention is relatively simple, and the synthetic route is short, and the method for copolymerization modification can endow the sensing material with excellent performance, and ensure that the copolymer can selectively adsorb heavy metal ions in water; It responds to small mass changes on the surface, has extremely high sensitivity, and realizes real-time detection.

Description of drawings

Fig. 1 is poly 2-mercaptobenzothiazole derivative homopolymer (PMBTVBC), poly (2-mercaptobenzothiazole derivative-co-N-vinylimidazole) random copolymer (P (MBTVBC-co-VIM)) and the infrared spectrum of polyvinylimidazole homopolymer (PVIM);

Fig. 2 is the atomic force microscope surface topography figure of the copolymer film before and after Cu in the adsorption ^40ppm Cu solution of embodiment ² ;

Fig. 3 is the adsorption curve of copolymer film to copper ion of different concentrations in water;

Figure 4 shows the selective adsorption of different heavy metal ions in water by the copolymer film.

Detailed ways

Example 1:

Take 6.0777g of 2-mercaptobenzothiazole and add it to the polymerization bottle, dissolve it completely with 15ml of tetrahydrofuran, then add 1.5302g of sodium hydride into the bottle, a large number of bubbles will be formed during the reaction, and fully react for half a day at room temperature after the bubbles completely disappear. hours to form 2-mercaptobenzothiazole sodium salt. Take out the supernatant sodium salt clear solution in the reaction flask with a syringe, then add it to 10.2ml of tetrahydrofuran solution containing 5.20ml of p-chloromethylstyrene and continue to react at 50°C for 24h. The reaction solution was added dropwise to a large amount of 3‰ sodium hydroxide aqueous solution to precipitate, and a filter cake was formed by suction filtration, then washed with a 3‰ sodium hydroxide aqueous solution and separated, vacuum-dried to constant weight, and prepared In 2-mercaptobenzothiazole derivatives.

Dissolve 1ml of N-vinylimidazole monomer and 0.5073g of the above-prepared 2-mercaptobenzothiazole derivative in 15ml of dioxane, stir to fully dissolve under nitrogen atmosphere, and then add 19.4mg of azobisiso Butyronitrile, fully stirred, reacted at a constant temperature in a 70°C oil bath for 24 hours under a nitrogen atmosphere, then took it out and cooled it to room temperature naturally. After the reaction was completed, it was a slightly turbid slightly yellow solution, which was centrifuged at a rate of 3500 rpm for 10 minutes to remove insoluble particles suspended in the reaction solution; A light yellow precipitate was obtained after centrifugation for 10 min, and the precipitate was dried in a vacuum oven at 60°C to constant weight to obtain 1.10 g of a functional polymer: poly(2-mercaptobenzothiazole derivative-co-N-vinylimidazole) random copolymer. The weight-average molecular weight of this random copolymer is 6200; The molar percentage of N-vinylimidazole structural unit in this random copolymer is 44.8%, and the molar percentage of 2-mercaptobenzothiazole derivative structural unit is 55.2%.

Figure 1 shows poly 2-mercaptobenzothiazole derivative homopolymer (PMBTVBC), poly(2-mercaptobenzothiazole derivative-co-N-vinylimidazole) copolymer (P(MBTVBC-co-VIM )), the infrared spectrum of polyvinylimidazole homopolymer (PVIM).

Weigh 51.9mg of P(MBTVBC-co-VIM) copolymer and completely dissolve it in 10ml of chloroform and stir for one day to prepare a solution with a mass fraction of 5.19‰. Add the solution dropwise to the gold electrode surface of the blank quartz wafer on the homogenizer, set the low speed to 400 rpm for 9 s, and the high speed to 3000 rpm for 30 s. After spin-coating the gold electrode surface of the wafer to form a film, put it in a vacuum oven for half an hour to completely volatilize the chloroform to obtain a quartz wafer with a copolymer film on the surface. The thickness of the copolymer film is 522.8nm.

Use a quartz crystal microbalance to test the resonant frequency response of a blank wafer and a quartz wafer with a copolymer film loaded on the surface, and obtain the corresponding frequency change ΔF ₃ when the overtone resonance order n=3 of the quartz wafer under the load of the copolymer film, It is the net difference between the real-time frequency response value and the baseline frequency response value; the distilled water is passed into the sample cell equipped with a quartz wafer at a flow rate of 100 μL/min, and then the Cu ²⁺ concentration is passed after a stable frequency response baseline is obtained. 10ppm (mass percentage concentration 0.001%) Cu ²⁺ aqueous solution, copper ions are coordinated with the functional groups on the surface of the copolymer film, and the resonance frequency of the quartz wafer in the adsorption process is detected in real time by a quartz crystal microbalance. The results show that The copolymer film can effectively absorb Cu ²⁺ in water. The result is shown in Figure 3.

Example 2:

Dissolve 0.5ml of N-vinylimidazole monomer and 1g of the 2-mercaptobenzothiazole derivative prepared in Example 1 in 15ml of dioxane, stir under a nitrogen atmosphere to fully dissolve, then add 10mg of azobis Isobutyronitrile, fully stirred, reacted at a constant temperature in an oil bath of 80°C under nitrogen atmosphere for 24 hours, then took it out and cooled it to room temperature naturally. After the reaction is completed, it is a slightly turbid slightly yellow solution, which is centrifuged at 3500 rpm for 10 minutes to remove the suspended insoluble particles in the reaction solution; the upper layer of light yellow supernatant is precipitated in a large amount of acetone, and is also centrifuged at 3500 rpm for 10 minutes to obtain A light yellow precipitate was dried in a vacuum oven at 60° C. to a constant weight to obtain 0.85 g of a functional polymer: poly(2-mercaptobenzothiazole derivative-co-N-vinylimidazole) random copolymer. The weight-average molecular weight of this random copolymer is 11900; In this random copolymer, the molar percentage of N-vinylimidazole structural unit is 24.9%, and the molar percentage of 2-mercaptobenzothiazole derivative structural unit is 75.1%.

Weigh 25.0 mg of the above copolymer and completely dissolve it in 10 ml of chloroform and stir for 1 day to prepare a solution with a mass fraction of 2.5‰. Add the solution dropwise to the gold electrode surface of the blank quartz wafer on the homogenizer, set the low speed to 400 rpm for 9 s, and the high speed to 3000 rpm for 30 s. After spin-coating the gold electrode surface of the wafer to form a film, put it in a vacuum oven for half an hour to completely volatilize the chloroform to obtain a quartz wafer with a copolymer film on the surface. The thickness of the copolymer film is 303.1 nm.

Use a quartz crystal microbalance to test the frequency response of a blank wafer and a quartz wafer loaded with a polymer film on the surface, and obtain the frequency change ΔF ₃ corresponding to the film load; water, after obtaining a stable frequency response baseline, the Cu ²⁺ concentration is 40ppm (mass percentage concentration 0.004%) Cu ²⁺ aqueous solution, the copper ions are coordinated with the functional groups on the surface of the polymer film, and the quartz crystal micro The balance detects frequency changes and dissipation changes during the adsorption process in real time. Figure 2 is the atomic force microscope topography of the copolymer film before and after adsorption of 40ppm Cu ²⁺ . It can be seen that the surface of the film is porous before adsorption, and there is little change after adsorption.

Example 3:

Dissolve 0.5ml of N-vinylimidazole monomer and 0.5073g of the 2-mercaptobenzothiazole derivative prepared in Example 1 in 10ml of dioxane, stir under nitrogen atmosphere to fully dissolve, then add 8mg of azo Diisobutyronitrile, fully stirred, reacted at a constant temperature in an oil bath of 80°C for 24 hours under a nitrogen atmosphere, then took it out and cooled it naturally to room temperature. After the reaction was completed, it was a slightly turbid slightly yellow solution, which was centrifuged at 3500 rpm for 10 minutes to remove suspended insoluble particles in the reaction solution; the light yellow supernatant liquid in the upper layer was precipitated in a large amount of acetone, and centrifuged at 3500 rpm for 10 minutes to obtain a light yellow precipitate. The precipitate was dried in a vacuum oven at 60° C. to a constant weight to obtain 0.75 g of a functional polymer: poly(2-mercaptobenzothiazole derivative-co-N-vinylimidazole) random copolymer. The weight-average molecular weight of this random copolymer is 15000; In this random copolymer, the molar percentage of N-vinylimidazole structural unit is 35.1%, and the molar percentage of 2-mercaptobenzothiazole derivative structural unit is 64.9%.

Weigh 35.0 mg of the above copolymer and completely dissolve it in 10 ml of chloroform and stir for 1 day to prepare a solution with a mass fraction of 3.5‰. Add the solution dropwise to the gold electrode surface of the blank quartz wafer on the homogenizer, set the low speed to 400 rpm for 9 s, and the high speed to 3000 rpm for 30 s. After spin-coating the gold electrode surface of the wafer to form a film, put it in a vacuum oven for half an hour to completely volatilize the chloroform to obtain a quartz wafer with a copolymer film on the surface. The thickness of the copolymer film is 344.3nm.

Use a quartz crystal microbalance to test the frequency response of a blank wafer and a quartz wafer loaded with a polymer film on the surface, and obtain the normalized frequency change ΔF ₃ corresponding to the film load; Distilled water, after obtaining a stable frequency response baseline, pass into Cu ²⁺ concentration and be 136.5ppm (mass percentage concentration 0.01365%) Cu ²⁺ aqueous solution, copper ions are coordinated with the functional groups on the surface of the polymer film, A quartz crystal microbalance detects frequency changes and dissipation changes during the adsorption process in real time. The result is shown in Figure 3.

Figure 3 is the adsorption curve of the copolymer film to different concentrations of copper ions in the aqueous solution, that is, the change of the frequency response with time. It can be seen that under the condition of higher copper ion concentration, the surface of the copolymer film can bind more copper ions, and has a relatively high copper ion concentration. High frequency response value, the curve will not return to the original point after washing with distilled water, indicating that the functional groups on the surface of the copolymer film form a stable combination with copper ions.

Example 4:

The copolymer synthesis and the preparation of the copolymer film are the same as the above Example 1, using a quartz crystal microbalance to test the frequency response of the blank wafer and the quartz wafer with the polymer film on the surface, and obtain the normalized frequency change _ΔF3 corresponding to the copolymer film load ; Pass into distilled water with 100 μ L/min flow rate to the sample cell that quartz wafer is housed, pass into Pb again after obtaining stable frequency response baseline and concentration is ^40ppm (mass percentage concentration 0.004%) Pb ²⁺ aqueous solution, Zn ²⁺ concentration is 40ppm (mass percentage concentration 0.004%) Zn ²⁺ aqueous solution, Cd ²⁺ concentration is 40ppm (mass percentage concentration 0.004%) Cd ²⁺ aqueous solution, Ni ²⁺ concentration is 40ppm (mass percentage concentration 0.004%) ) Ni ²⁺ aqueous solution, Co ²⁺ concentration of 40ppm (mass percent concentration 0.004%) Co ²⁺ aqueous solution or Cu ²⁺ concentration of 40ppm (mass percent concentration 0.004%) Cu ²⁺ aqueous solution, real-time detection by quartz crystal microbalance Frequency change and dissipation change during adsorption. The result is shown in Figure 4.

Figure 4 shows the results of selective adsorption of different types of heavy metal ions by copolymer films in the same film thickness range in different heavy metal ion aqueous solutions with a concentration of 40ppm (0.004% by mass). It can be seen that under the same ion concentration conditions, more copper ions can be bound to the surface of the copolymer film, which has a higher frequency response value, followed by Co ²⁺ and Cd ²⁺ , followed by pb ²⁺ and Ni ²⁺ , Zn ²⁺ with the smallest adsorption response value. The imidazole ring and S, N heteroatom groups on the molecular chain of the copolymer can effectively capture heavy metal ions, and the S, N and other atoms on the molecular chain can form a coordination bond with the empty orbital of the metal ion with a pair of lone pairs of electrons. Molecular chelates have a similar stable structure and have good coordination and complexation capabilities. Compared with other heavy metal ions, it shows strong coordination and complexation performance for Cu ²⁺ , and the adsorption effect is obvious.

The above descriptions are only some specific implementations of the present invention, and it should be pointed out that many variations and improvements can be made by those skilled in the art, and all variations or improvements that do not exceed the claims described should be considered as Be the protection scope of the present invention.

Claims (10)

1. functional polymer, the weight-average molecular weight of being made up of the 2-mercaptobenzothiazole derivant structure unit shown in N-vinyl imidazole structural unit shown in the following formula M1 and the formula M2 is the random copolymers of 6000-15000;

The molar content of N-vinyl imidazole structural unit is 20%-45% in the described random copolymers, and the unitary molar content of 2-mercaptobenzothiazole derivant structure is 55%-80%.

2. the preparation method of functional polymer as claimed in claim 1 comprises step:

With the double bond containing 2-mercaptobenzothiazole derivatives monomer shown in N-vinyl imidazole monomer shown in the formula M5 and the formula M6 is raw material, causes two monomeric vinyl double bond generation copolyreaction by initiator, makes random copolymers;

3. the preparation method of functional polymer as claimed in claim 2 is characterized in that, described initiator is selected from Diisopropyl azodicarboxylate or benzoyl peroxide.

4. the preparation method of functional polymer as claimed in claim 2 is characterized in that, the consumption of described initiator is the 0.01%-5% of N-vinyl imidazole monomer and 2-mercaptobenzothiazole derivatives monomer gross weight.

5. the preparation method of functional polymer as claimed in claim 2 is characterized in that, described copolyreaction condition is: carry out free radicals copolymerization reaction under oxygen free condition in anhydrous solvent.

6. the preparation method of functional polymer as claimed in claim 5 is characterized in that, described anhydrous solvent is selected from 1,4-dioxane or tetrahydrofuran (THF).

7. the preparation method of functional polymer as claimed in claim 2 is characterized in that, described copolyreaction temperature is 60 ℃-90 ℃, and the copolyreaction time is 12 hours-24 hours.

8. the preparation method of functional polymer as claimed in claim 1 is characterized in that, the preparation method of the double bond containing 2-mercaptobenzothiazole derivatives monomer shown in the described formula M6 comprises step:

React under sodium hydride and tetrahydrofuran (THF) existence condition with the p-chloromethyl styrene shown in the formula M3 or to the 2-mercaptobenzothiazole shown in brooethyl vinylbenzene and the formula M4, make the double bond containing 2-mercaptobenzothiazole derivatives monomer shown in the formula M6;

Among the formula M3, X is selected from Cl or Br.

9. the preparation method of functional polymer as claimed in claim 7 is characterized in that, the preparation method of the double bond containing 2-mercaptobenzothiazole derivatives monomer shown in the described formula M6 comprises step:

(1) 2-mercaptobenzothiazole shown in the formula M4 is dissolved in the tetrahydrofuran (THF), behind the adding sodium hydride, reaction generates the tetrahydrofuran solution of 2-mercaptobenzothiazole sodium salt;

(2) be dissolved in the p-chloromethyl styrene shown in the formula M3 or to brooethyl vinylbenzene and form clear solution in the tetrahydrofuran (THF), mix with the tetrahydrofuran solution of above-mentioned 2-mercaptobenzothiazole sodium salt, 50 ℃-60 ℃ reactions 24 hours-48 hours, make the double bond containing 2-mercaptobenzothiazole derivatives monomer shown in the formula M6 through aftertreatment.

10. the application of functional polymer as claimed in claim 1 in identification underwater trace heavy metal ion, detection underwater trace heavy metal ion or preparation chemical sensor.

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