CN101885797A - Functional polymer and preparation method and application thereof - Google Patents
Functional polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a functional polymer. The functional polymer is a random copolymer consisting of N-vinylimidazole structural unit and 2-mercaptobenzothiazole derivative structural unit, and the weight-average molecular weight of the random copolymer is 6,000 to 15,000; and the molar percentage content of the N-vinylimidazole structural unit in the random copolymer is 20 to 45 percent, and the molar percentage content of the 2-mercaptobenzothiazole derivative structural unit is 55 to 80 percent. The invention also discloses a preparation method for the functional polymer and application. The polymer structure contains bonding points of an imidazole ring and S and N heteroatom groups easily coordinated with heavy metal ions, so the polymer prepared by the method and a film thereof can selectively adsorb and detect the heavy metal ions in the water.
Description
Technical field
The present invention relates to organic polymer sensing material and environmental monitoring field, be specifically related to a kind of functional polymer and preparation and application based on the QCM (Quartz Crystal Microbalance) technology, this functional polymer can be applicable to heavy metal ion identification in the water body, detects and preparation chemical sensor field.
Background technology
Over nearest more than 20 years, when the economic growth of extensive style causes the Chinese national economy high speed development also severe contamination physical environment.Heavy metal ion such as cadmium, cobalt, lead and cupric ion etc. that various environmental pollutant particularly produce in the industrial production enter water, edatope, not only pollute physical environment, and harm humans existence and healthy.So identification of trace heavy metal ionic and detection are significant for recovery, recycling and the early stage environmental pollution monitoring of metallic element in the water body.
The detection method of heavy metal ion mainly contains inductively coupled plasma mass spectrometry, atomic absorption spectrum and electrochemistry anodic stripping voltammetry etc. at present.Although these sensitivity height, high specificity exist sample pre-treatments complexity, defectives such as operation is consuming time, instrument is expensive and working cost is high, offline inspection, be difficult to adapt to the current detection requirements of one's work.Publication number be disclose in the Chinese patent application of CN 101021515A a kind of in water body the method for in-situ sampling, separation, enrichment and measure heavy metal ion, utilize osmosis that heavy metal ion is come out and macromolecular compound reacts from the film diffused inside, these macromolecular compounds mainly are Walocel MT 20.000PV, chitosan and sodium polyacrylate etc., its functional group can combine with heavy metal ion, but the performance that does not in fact have selective adsorption, detection step complexity expends time in; Because it is to utilize atomic absorption spectrometry to calculate concentration of heavy metal ion, can't detect in real time again.The application of a kind of fluorescent molecular probe in transition metal and heavy metal ion detect disclosed among the Chinese patent CN200610009925.8, design synthesized a kind of various solution particularly in the aqueous solution to Co
2+Selectivity fluorescence strengthens the fluorescent probe of identification, and this fluorescence molecule structure is comparatively complicated, and separation and purification need be carried out the column chromatography step, realizes that as sensing material industrial applications has certain difficulty, and still can't realize online in real time and easy rapid detection.Therefore, need seek a kind of more simple technology of qualitative, quantitative fast and identify the heavy metal ion that may exist in the water body.
Summary of the invention
The invention provides a kind of functional polymer and film thereof, can be used to detect the trace heavy metal ion.
A kind of 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%.
The preparation method of described functional polymer 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;
As preferably:
Described initiator can be selected radical type initiator commonly used in this area for use, in order to guarantee the better effect of building-up reactions, selects Diisopropyl azodicarboxylate or benzoyl peroxide for use.
The consumption of described initiator can be adjusted by experiment, is generally the 0.01%-5% of N-vinyl imidazole monomer and 2-mercaptobenzothiazole derivatives monomer gross weight, preferred 0.2%-3%.
Described copolyreaction condition is: carry out free radicals copolymerization reaction under oxygen free condition in anhydrous solvent.
Described oxygen free condition can realize by the method for this area routine, for example: reaction system is carried out vacuum-nitrogen replacement to remove oxygen wherein, perhaps directly will be reflected in the atmosphere of inert gases and carry out.Described rare gas element comprises the rare gas element of this area broad scope, a kind of as in nitrogen, the helium etc.
Described anhydrous solvent can be selected organic solvent commonly used in this area for use, as 1, and 4-dioxane or tetrahydrofuran (THF).Anhydrous solvent is to adopt general water-eliminating method as through hydrolith and sodium Metal 99.5 drying before use used solvent, and the minor amount of water of removing wherein obtains.
Described copolyreaction temperature is 60 ℃-90 ℃, and the copolyreaction time is 12 hours-24 hours.
After described copolyreaction is finished, reaction product can be carried out purification process, concrete purification process process comprises:
Reaction solution is cooled off, after centrifugation, remove the insoluble particle that suspends in the reaction solution, the light yellow clear liquid in upper strata precipitates in a large amount of acetone, get light-yellow precipitate through centrifugation again, precipitation is dried to constant weight, makes functional polymer: poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) random copolymers (P (MBTVBC-co-VIM)).
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.
Described p-chloromethyl styrene or to the brooethyl styrene monomer has two keys and can carry out polyreaction, and chloromethyl in the contraposition or brooethyl can be realized functionalization, can adopt the commercially available prod.
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.
Described last handling process comprises: reaction solution is precipitated in aqueous sodium hydroxide solution (be as mass concentration 3 ‰ aqueous sodium hydroxide solution) separate out, be dried to constant weight through suction filtration.
Described polymkeric substance has imidazole ring not only hydrophilic but also can bind metal ion, have again and have hydrophobic 2-mercaptobenzothiazole derivant structure unit, S wherein and N heteroatom group make it can the selective binding metal ion, thereby can be used for identification and detect the underwater trace heavy metal ion, also can be used for preparing chemical sensor.
Described heavy metal ion comprises Cd
2+, Pb
2+, Zn
2+, Cu
2+Deng in one or more, Cu especially
2+
In order to improve the sensitivity of detection, functional polymer is applied to the identification of trace heavy metal ionic, detection and chemical sensor field in the water body, all can realize in conjunction with the QCM (Quartz Crystal Microbalance) technology.For example: described functional polymer can be dissolved in organic solvent (as chloroform) and make functional polymer solution, the functional polymer drips of solution is added to the gold electrode surfaces of blank quartz wafer, after sol evenning machine is with the gold electrode surfaces spin-coating film of functional polymer solution at blank quartz wafer, dry, promptly make the quartz wafer of coating functions polymeric film.When the solution stream of metal ion functional polymer film through described quartz wafer surface, utilize the QCM (Quartz Crystal Microbalance) instrument to detect frequency resonance response, reflect that the GOLD FROM PLATING SOLUTION of metal ion belongs to ionic concentration.
The thickness of described functional polymer film can be regulated by the concentration of controlled function polymers soln, and the mass percentage concentration of functional polymer solution is that 0.065%-0.5% is more satisfactory, the preparation temperature be 10 ℃-20 ℃ more satisfactory.
Described functional polymer film is when being used for detecting the water concentration of heavy metal ion, and its thickness range is that 200nm-550nm is more satisfactory; In this thickness range, the functional polymer film is to heavy metal ion Cu in the water
2+The lowest detectable limit of concentration is 10ppm (mass percentage concentration 0.001%), and corresponding frequency response values is 9Hz.
The operational condition of described sol evenning machine is preferably 4000 rev/mins of low speed, changes 9s, 3000 rev/mins at a high speed, changes 30s.
Random copolymers of the present invention can characterize its molecular structure by means such as infrared and nuclear-magnetisms.
Principle of the present invention is: containing the unitary random copolymers of 2-mercaptobenzothiazole derivant structure shown in N-vinyl imidazole structural unit shown in the formula M1 and the formula M2 can be in conjunction with the imidazole ring of heavy metal ion and S, N heteroatom group (being referred to as functional groups) because of having on the side chain, be spun to the gold electrode surfaces of quartz wafer with the form of certain concentration solution, owing to contain the S atom on the random copolymers molecular chain, give birth to strong the interaction with golden hair and make film can be stably fixed on the gold electrode surfaces; When the quartz wafer of spin on polymers film contacts with heavy metal ion solution, functional groups on the film surface just can combine with heavy metal ion, the mass loading on quartz wafer surface is changed, and then cause the frequency response of wafer to change, thereby real-time and easily heavy metal ion is discerned and detected.
The present invention has following advantage:
1. comprise imidazole ring and S in the functional polymer structure of the present invention, the N heteroatom group is easy to heavy metal ion coordinate binding site for two kinds, thereby the polymkeric substance of the present invention preparation and film thereof can selective adsorptions and detect heavy metal ion, especially Cu in the water
2+
2. functional polymer film of the present invention presents vesicular structure, and pore diameter range is at 100nm-400nm, and average hole depth 10nm-20nm effectively increases specific surface area, can adsorb more multi-metal ion.
3. among the preparation method of the present invention, at first synthesized double bond containing 2-mercaptobenzothiazole derivative, again itself and the copolyreaction of N-vinyl imidazole have been obtained multipolymer, synthetic route is short and sweet.
4. QCM (Quartz Crystal Microbalance) technology of the present invention, be used to the heavy metal ion detection by quantitative owing to having the highly sensitive mass effect, scribble the detection sensitivity height of the quartz wafer of functional polymer film to heavy metal ion in the water, selectivity is better, and it is to Cu
2+Detectability can reach the concentration of 10ppm (mass percentage concentration 0.001%).
5. the preparation method of spin-coating film of the present invention, the technology simple controllable is applicable to suitability for industrialized production.
As seen, the preparation of the copolymer film of functional N-vinyl imidazole of the present invention and 2-mercaptobenzothiazole derivative and QCM (Quartz Crystal Microbalance) The Application of Technology prove a good selection.The prepared copolymer structure of the present invention is simple relatively, and synthetic route is short, and the method for modification by copolymerization can be given the performance of sensing material excellence, guarantee multipolymer can selective adsorption water in heavy metal ion; QCM (Quartz Crystal Microbalance) can produce response to the lip-deep small quality change of quartz wafer simultaneously, has high susceptibility, has realized real-time detection.
Description of drawings
Fig. 1 is the infrared spectrum of the poly-2-mercaptobenzothiazole derivative homopolymer (PMBTVBC) of preparation among the embodiment 1, poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) random copolymers (P (MBTVBC-co-VIM)) and polyvinyl imidazol homopolymer (PVIM);
Fig. 2 is that embodiment 2 is at absorption 40ppm Cu
2+Cu in the solution
2+The atomic force microscope surface topography map of front and back copolymer film;
Fig. 3 is the adsorption curve of copolymer film to different concns cupric ion in the water;
Fig. 4 is the selective adsorption of copolymer film to different heavy metal ion in the water.
Embodiment
Embodiment 1:
Getting the 6.0777g 2-mercaptobenzothiazole joins in the polymerization bottle, dissolve fully with the 15ml tetrahydrofuran (THF), in bottle, add the 1.5302g sodium hydride again, form a large amount of bubbles in the reaction process, treat at room temperature fully to react again after the bubble completely dissolve forming the 2-mercaptobenzothiazole sodium salt half an hour.With syringe with reaction flask at the middle and upper levels the sodium salt clear liquid take out, be added to 10.2ml subsequently and contain in the tetrahydrofuran solution of 5.20ml p-chloromethyl styrene and continue at 50 ℃ of reaction 24h.It is to precipitate in 3 ‰ aqueous sodium hydroxide solutions that reaction solution is added drop-wise to a large amount of mass concentrations, forms filter cake through suction filtration, is that 3 ‰ aqueous sodium hydroxide solutions clean the back separation with mass percentage concentration again, and vacuum-drying makes the 2-mercaptobenzothiazole derivative to constant weight.
The 2-mercaptobenzothiazole derivative of 1ml N-vinyl imidazole monomer and the above-mentioned preparation of 0.5073g is dissolved in the 15ml dioxane, stirring under the nitrogen atmosphere condition fully dissolves it, add the 19.4mg Diisopropyl azodicarboxylate again, fully stir, in isothermal reaction after 24 hours in 70 ℃ of oil baths under the nitrogen atmosphere condition, take out and naturally cool to room temperature.Be the slightly yellow solution of little muddiness after reaction is finished, in 3500 rev/mins speed, remove the insoluble particle that suspends in the reaction solution behind the centrifugal 10min; The light yellow clear liquid in upper strata precipitates in a large amount of acetone, in 3500 rev/mins speed, obtain light-yellow precipitate behind the centrifugal 10min equally, to be deposited in vacuum drying oven and be dried to constant weight for 60 ℃, make the 1.10g functional polymer: poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) random copolymers.The weight-average molecular weight of this random copolymers is 6200; The molar content of N-vinyl imidazole structural unit is 44.8% in this random copolymers, and the unitary molar content of 2-mercaptobenzothiazole derivant structure is 55.2%.
The infrared spectrum that has shown poly-2-mercaptobenzothiazole derivative homopolymer (PMBTVBC), poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) multipolymer (P (MBTVBC-co-VIM)), polyvinyl imidazol homopolymer (PVIM) among Fig. 1.
Take by weighing 51.9mg P (MBTVBC-co-VIM) multipolymer and be dissolved in fully in the 10ml chloroform and stirred one day, be made into massfraction and be 5.19 ‰ solution.Drips of solution is added to the gold electrode surfaces of the overhead white quartz wafer of sol evenning machine, 400 rev/mins of low speed is set, time 9s, 3000 rev/mins at a high speed, time 30s.Put vacuum drying oven and take out half an hour after wafer gold electrode surfaces spin-coating film, chloroform is volatilized totally fully, make the quartz wafer of area load copolymer film, the thickness of this copolymer film is 522.8nm.
The frequency resonance response of using the QCM (Quartz Crystal Microbalance) instrument to come the quartz wafer of blank testing wafer and area load copolymer film obtains the copolymer film load under pairing frequency change Δ F when the general frequency of quartz wafer resonates exponent number n=3
3, it is the clean difference of real-time frequency response value and bareline heart rate response value; Feed two to the sample pool that quartz wafer is housed with 100 μ L/min flow velocitys and steam water, obtain feeding Cu again behind the stable frequency response baseline
2+Concentration is 10ppm (mass percentage concentration 0.001%) Cu
2+The aqueous solution, cupric ion combines with the functional groups coordination of multipolymer film surface, adopts QCM (Quartz Crystal Microbalance) to detect the variation of resonant frequency of the quartz wafer in the adsorption process in real time, and the result shows the Cu in this copolymer film energy active adsorption water
2+The result as shown in Figure 3.
Embodiment 2:
The 2-mercaptobenzothiazole derivative of 0.5ml N-vinyl imidazole monomer and 1g embodiment 1 preparation is dissolved in the 15ml dioxane, stirring under the nitrogen atmosphere condition fully dissolves it, add the 10mg Diisopropyl azodicarboxylate again, fully stir, in isothermal reaction after 24 hours in 80 ℃ of oil baths under the nitrogen atmosphere condition, take out and naturally cool to room temperature.Be the slightly yellow solution of little muddiness after reaction is finished, behind 3500 rev/mins of centrifugal 10min, remove the insoluble particle that suspends in the reaction solution; The light yellow clear liquid in upper strata precipitates in a large amount of acetone, centrifugal 10min obtains light-yellow precipitate in 3500 rev/mins speed equally, to be deposited in vacuum drying oven and be dried to constant weight for 60 ℃, make the 0.85g functional polymer: poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) random copolymers.The weight-average molecular weight of this random copolymers is 11900; The molar content of N-vinyl imidazole structural unit is 24.9% in this random copolymers, and the unitary molar content of 2-mercaptobenzothiazole derivant structure is 75.1%.
Take by weighing the above-mentioned multipolymer of 25.0mg and be dissolved in fully in the 10ml chloroform and stirred 1 day, be made into massfraction and be 2.5 ‰ solution.Drips of solution is added to the gold electrode surfaces of the overhead white quartz wafer of sol evenning machine, 400 rev/mins of low speed is set, time 9s, 3000 rev/mins at a high speed, time 30s.Put vacuum drying oven and take out half an hour after wafer gold electrode surfaces spin-coating film, chloroform is volatilized totally fully, make the quartz wafer of area load copolymer film, the thickness of this copolymer film is 303.1nm.
The frequency response of using the QCM (Quartz Crystal Microbalance) instrument to come the quartz wafer of blank testing wafer and area load polymeric film obtains the frequency change Δ F of film load correspondence
3Feed two to the sample pool that quartz wafer is housed with 100 μ L/min flow velocitys and steam water, obtain feeding Cu again behind the stable frequency response baseline
2+Concentration is 40ppm (mass percentage concentration 0.004%) Cu
2+The aqueous solution, cupric ion combines with the functional groups coordination on polymeric film surface, and QCM (Quartz Crystal Microbalance) detects frequency change and the dissipate varied in the adsorption process in real time.Fig. 2 is at absorption 40ppm Cu
2+The shape appearance figure of the atomic force microscope of front and back copolymer film can see that the preceding film surface of absorption is a vesicular structure, and the variation of absorption back is little.
Embodiment 3:
The 2-mercaptobenzothiazole derivative of 0.5ml N-vinyl imidazole monomer and 0.5073g embodiment 1 preparation is dissolved in the 10ml dioxane, stirring under the nitrogen atmosphere condition fully dissolves it, add the 8mg Diisopropyl azodicarboxylate again, fully stir, in isothermal reaction after 24 hours in 80 ℃ of oil baths under the nitrogen atmosphere condition, take out and naturally cool to room temperature.Be the slightly yellow solution of little muddiness after reaction is finished, behind 3500 rev/mins of centrifugal 10min, remove the insoluble particle that suspends in the reaction solution; The light yellow clear liquid in upper strata precipitates in a large amount of acetone, same 3500 rev/mins of centrifugal 10min, obtain light-yellow precipitate, will be deposited in vacuum drying oven and be dried to constant weight for 60 ℃, make the 0.75g functional polymer: poly-(2-mercaptobenzothiazole derivative-co-N-vinyl imidazole) random copolymers.The weight-average molecular weight of this random copolymers is 15000; The molar content of N-vinyl imidazole structural unit is 35.1% in this random copolymers, and the unitary molar content of 2-mercaptobenzothiazole derivant structure is 64.9%.
Take by weighing the above-mentioned multipolymer of 35.0mg and be dissolved in fully in the 10ml chloroform and stirred 1 day, be made into massfraction and be 3.5 ‰ solution.Drips of solution is added to the gold electrode surfaces of the overhead white quartz wafer of sol evenning machine, 400 rev/mins of low speed is set, time 9s, 3000 rev/mins at a high speed, time 30s.Put vacuum drying oven and take out half an hour after wafer gold electrode surfaces spin-coating film, chloroform is volatilized totally fully, make the quartz wafer of area load copolymer film, the thickness of this copolymer film is 344.3nm.
The frequency response of using QCM (Quartz Crystal Microbalance) to come the quartz wafer of blank testing wafer and area load polymeric film obtains the normalized frequency changes delta F of film load correspondence
3Feed two to the sample pool that quartz wafer is housed with 100 μ L/min flow velocitys and steam water, obtain feeding Cu again behind the stable frequency response baseline
2+Concentration is 136.5ppm (mass percentage concentration 0.01365%) Cu
2+The aqueous solution, cupric ion combines with the functional groups coordination on polymeric film surface, and QCM (Quartz Crystal Microbalance) detects frequency change and the dissipate varied in the adsorption process in real time.Result such as Fig. 3.
Fig. 3 is the adsorption curve of copolymer film to different Cu ionic concn in the aqueous solution, be frequency response over time, can see under the higher copper ionic concn condition, the copolymer film surface can be in conjunction with more cupric ion, has higher frequency response values, steam water cleaning back curve with two and can not get back to initial point, illustrate that the lip-deep functional groups of copolymer film forms stable combining with cupric ion.
Embodiment 4:
Multipolymer synthetic with the multipolymer film preparation with above embodiment 1, the frequency response of using QCM (Quartz Crystal Microbalance) to come the quartz wafer of blank testing wafer and area load polymeric film obtains the normalized frequency changes delta F of copolymer film load correspondence
3Feed two to the sample pool that quartz wafer is housed with 100 μ L/min flow velocitys and steam water, obtain feeding Pb again behind the stable frequency response baseline
2+Concentration is 40ppm (mass percentage concentration 0.004%) Pb
2+The aqueous solution, Zn
2+Concentration is 40ppm (mass percentage concentration 0.004%) Zn
2+The aqueous solution, Cd
2+Concentration is 40ppm (mass percentage concentration 0.004%) Cd
2+The aqueous solution, Ni
2+Concentration is 40ppm (mass percentage concentration 0.004%) Ni
2+The aqueous solution, Co
2+Concentration is 40ppm (mass percentage concentration 0.004%) Co
2+The aqueous solution or Cu
2+Concentration is 40ppm (mass percentage concentration 0.004%) Cu
2+The aqueous solution, QCM (Quartz Crystal Microbalance) detect frequency change and the dissipate varied in the adsorption process in real time.Result such as Fig. 4.
Fig. 4 is in the different heavy metal ion aqueous solution of 40ppm (mass percentage concentration 0.004%) for the copolymer film in the same thickness scope in concentration, to the selective adsorption result of different sorts heavy metal ion.Can see under the same ionic concn condition that the copolymer film surface can have higher frequency response values in conjunction with more cupric ion, be Co secondly
2+And Cd
2+, then be pb
2+And Ni
2+, the Zn of absorption response value minimum
2+Imidazole ring on the copolymer molecule chain and S, N heteroatom group have effectively captured heavy metal ion, nuclear power such as the S on the molecular chain, N form coordinate bond with a pair of lone-pair electron and metal ion unoccupied orbital, constitute the rock steady structure similar, have good ligand complex ability to the small molecules inner complex.Other heavy metal ion demonstrate Cu relatively
2+Stronger ligand complex performance, adsorption effect is obvious.
The above only is several embodiments of the present invention; should be understood that; for the person of ordinary skill of the art, can also make many modification and improvement, all do not exceed the described modification of claim or improvement all should be considered as 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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