CN110294837A - A kind of amidoxim fluidized polymer, preparation method and application - Google Patents

A kind of amidoxim fluidized polymer, preparation method and application Download PDF

Info

Publication number
CN110294837A
CN110294837A CN201910604649.7A CN201910604649A CN110294837A CN 110294837 A CN110294837 A CN 110294837A CN 201910604649 A CN201910604649 A CN 201910604649A CN 110294837 A CN110294837 A CN 110294837A
Authority
CN
China
Prior art keywords
formula
polymer
preparation
amidoxim
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910604649.7A
Other languages
Chinese (zh)
Inventor
王宏青
张文峰
尹强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of South China
Original Assignee
University of South China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University of South China filed Critical University of South China
Priority to CN201910604649.7A priority Critical patent/CN110294837A/en
Publication of CN110294837A publication Critical patent/CN110294837A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Optics & Photonics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention provides a kind of preparation methods of amidoxim fluidized polymer, comprising: A) the alkyl fluorenes with formula (I) structure and connection boric acid pinacol ester are reacted under the effect of the catalyst, obtain the compound with formula (II) structure；B) will have formula (II) structure or the compound and 4 with formula (III) structure, 4'- dibromobenzo-phenone to react under the effect of the catalyst, and obtain first conjugated polymer with formula (IV) structure；C first conjugated polymer and malononitrile are reacted in a solvent), obtain second conjugated polymer with formula (V) structure；D second conjugated polymer and azanol are reacted in a solvent), obtain the amidoxim fluidized polymer with formula (VI) structure；Present invention also provides the applications of the amidoxim fluidized polymer.Polymer provided by the present application is a kind of fluorescent type polymer, and detection limit is low, water-soluble preferable, thus realization detection to trace uranyl ion source position in true environment and quickly.

Description

A kind of amidoxim fluidized polymer, preparation method and application
Technical field
The present invention relates to uranyl ion detection technique field more particularly to a kind of amidoxim fluidized polymers, preparation method With application.
Background technique
It is well known that uranium is a kind of radioactive element being widely distributed in the earth's crust and ocean.Uranium is in addition to being used for nuclear weapon Outside nuclear reactor, it is also widely used in manufacture steel alloy, catalyst, preservative and hardening agent and glass, ceramics, in enamel Colorant etc..But while people utilize uranium resource, also results in radioactive environmental pollution and the mankind and animal are produced Toxic effect is given birth to.Studies have shown that uranium element can damage the kidney and urinary system of people because of its radiotoxicity and chemical toxicity, very To induction lung cancer.It can't be ignored the uranium of very little concentration enters its toxicity of human body.Therefore, how uranium is detected rapidly and sensitively Ion suffers from important meaning to environment, life science.
Currently, the detection of uranium depends on the analysis method and synthesized micromolecule identification substance of instrument and equipment.However There is some disadvantages in these methods: if to need that the device is complicated expensive for instrument analysis, detection is time-consuming；Small molecule fluorescent passes Sensor then lacks enough optical stabilities and their photoluminescence efficiency is also relatively low.In addition, being reported before Liu seminar The detection limit of the uranyl ion sensor that DNA enzymatic of one, the road with specific recognition is made into, the sensor can achieve 45pM can reach 1,000,000 times or more to the selectivity of interfering ion.But since DNA enzymatic needs in vitro culture and extraction, behaviour It is cumbersome to make complexity, it is expensive, it is difficult to accomplish large-scale application.
Compared with these methods, fluorescent polymer can effectively amplify fluorescence signal and be realized by polymer backbone Energy transfer or energy resonance conversion.In addition to this, polymer is more easier to prepare and be modified.Till now, almost very It is rare to detect uranyl ion using fluorescent polymer.
Summary of the invention
Present invention solves the technical problem that be to provide a kind of preparation method of amidoxim fluidized polymer, this method preparation Amidoxim fluidized polymer can specific recognition uranyl ion, and have preferable sensitivity and anti-interference ability.
In view of this, this application provides a kind of preparation methods of amidoxim fluidized polymer, comprising the following steps:
A the alkyl fluorenes with formula (I) structure and connection boric acid pinacol ester are reacted under the effect of the catalyst), had There is the compound of formula (II) structure；
Or react the alkyl fluorenes with formula (I) structure and trimethylborate under the effect of the catalyst, it obtains with formula (III) compound of structure；
B) will have formula (II) structure or the compound with formula (III) structure with 4,4'- dibromobenzo-phenone in catalyst Under the action of react, obtain first conjugated polymer with formula (IV) structure；
C first conjugated polymer and malononitrile are reacted in a solvent), obtain having the second of formula (V) structure total Conjugated polymer；
D) second conjugated polymer and hydroxylamine hydrochloride are reacted in a solvent, obtain having formula (VI) structure together with amine Oximate polymer；
Wherein, X is halogen；
R is the alkyl of C1~C10.
Preferably, the R is amidoalkyl group, the C1 of the unsubstituted alkyl of C1~C8, the hydroxyalkyl of C1~C8, C1~C8 The quaternary ammonium alkyl of~C8 or the sulfonic alkyl of C1~C8.
Preferably, step A) in, in the compound for obtaining having formula (II) structure, the catalyst is palladium chloride, The molar ratio of the alkyl fluorenes and the connection boric acid pinacol ester is 1:2, and the temperature of the reaction is 95~110 DEG C.
Preferably, step A) in, in the compound for obtaining having formula (III) structure, the catalyst is magnesium chips and format The molar ratio of reagent, the alkyl fluorenes and the trimethylborate is 1:10.
Preferably, step B) in, the catalyst is tetra-triphenylphosphine palladium, and the catalyst is the compound and described The 1wt% of 4,4'- dibromobenzo-phenone gross mass；The molar ratio of the compound and the 4,4'- dibromobenzo-phenone is 1: 1, the reaction carries out in the mixed solution of wet chemical and toluene that volume ratio is 1:3, the wet chemical Concentration be 2mol/L；The temperature of the reaction is 90~100 DEG C.
Preferably, the molar ratio of first conjugated polymer and the malononitrile is 1:10, and the solvent is anhydrous two The volume ratio of the mixed liquor of chloromethanes, titanium tetrachloride and pyridine, the titanium tetrachloride and the pyridine is 1:2, the reaction Temperature is 0~60 DEG C.
Preferably, the molar ratio of second conjugated polymer and the hydroxylamine hydrochloride is 1:10, the temperature of the reaction It is 75~85 DEG C.
Present invention also provides one kind amidoxim fluidized polymer as shown in formula (VI),
Wherein, R is the alkyl of C1~C10.
Present invention also provides amidoxim fluidized polymer prepared by the preparation method or the amidoximization are poly- Close application of the object in identification uranyl ion.
It is finally by the dicyano on polymer this application provides a kind of preparation method of amidoxim fluidized polymer Vinyl and hydroxylamine hydrochloride react to obtain；The amidoxim fluidized polymer of the application preparation is a kind of fluorescent type polymer, the polymerization Amidoxime group in object has specificity and excellent recognition capability to uranyl ion, so that the amidoximization polymerization arrived Object has preferable sensitivity and anti-interference ability.
Detailed description of the invention
Fig. 1 is the infrared spectrum comparison diagram of the polymer P 0 of preparation of the embodiment of the present invention, P1 and P2；
Fig. 2 is the carbon spectrogram of the polymer P 0 of preparation of the embodiment of the present invention；
Fig. 3 is the carbon spectrogram of the polymer P 1 of preparation of the embodiment of the present invention；
Fig. 4 is the carbon spectrogram of the polymer P 2 of preparation of the embodiment of the present invention；
Fig. 5 is the fluorescence curve figure of uranyl ion under 2 various concentration of polymer P prepared by the embodiment of the present invention；
Fig. 6 is that the polymer P 2 of preparation of the embodiment of the present invention detects the selective histogram of different metal ions；
Fig. 7 is that the polymer P 2 of preparation of the embodiment of the present invention detects the competitive histogram of different metal ions.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention Limitation.
For being unable to trace detection or the cumbersome problem of detection method, the application in the method for detecting uranyl in the prior art A kind of preparation method of amidoxim fluidized polymer is provided, amidoxim fluidized polymer prepared by this method can be quenched due to uranyl ion Go out the fluorescence of the polymer, therefore the polymeric detection limits low, good water solubility, can be realized to trace uranyl in true environment from Sub in situ and quickly detection.Specifically, this application provides a kind of preparation method of amidoxim fluidized polymer, including following step It is rapid:
A the alkyl fluorenes with formula (I) structure and connection boric acid pinacol ester are reacted under the effect of the catalyst), had There is the compound of formula (II) structure；
Or react the alkyl fluorenes with formula (I) structure and trimethylborate under the effect of the catalyst, it obtains with formula (III) compound of structure；
B) will have formula (II) structure or the compound with formula (III) structure with 4,4'- dibromobenzo-phenone in catalyst Under the action of react, obtain first conjugated polymer with formula (IV) structure；
C first conjugated polymer and malononitrile are reacted in a solvent), obtain having the second of formula (V) structure total Conjugated polymer；
D) second conjugated polymer and hydroxylamine hydrochloride are reacted in a solvent, obtain having formula (VI) structure together with amine Oximate polymer；
Wherein, X is halogen；
R is the alkyl of C1~C10.
It is above-mentioned prepare amidoxim fluidized polymer during, will have first formula (I) structure alkyl fluorenes and connection boric acid Pinacol ester reacts under the effect of the catalyst, obtains the compound with formula (II)；In formula (I), R be chosen in particular from C1~ The alkyl of C10；More specifically, it can be selected from the acyl that R is the unsubstituted alkyl of C1~C8, the hydroxyalkyl of C1~C8, C1~C8 Amine alkyl, the quaternary ammonium alkyl of C1~C8 or the sulfonic alkyl of C1~C8, in a particular embodiment, the poly alkyl fluorene is specially 2, The bromo- 9,9- dioctyl fluorene of 7- bis-.During this, the catalyst is palladium chloride, the poly alkyl fluorene and boric acid frequency The molar ratio of that alcohol ester is 1:2, and the temperature of the reaction is 95~110 DEG C.It joined potassium acetate in the reaction, and organic It is carried out in solvent.The pure compound with formula (II) structure in order to obtain has also carried out a series of after having reacted Dedoping step, therefore, the poly alkyl fluorene is with bromo- 9, the 9- dioctyl fluorene of 2,7- bis-, the process specifically:
Under argon gas, by bromo- 9, the 9- dioctyl fluorene of 2,7- bis-, connection boric acid pinacol ester, drying potassium acetate and catalyst Palladium chloride is in anhydrous Isosorbide-5-Nitrae-dioxane mixing, and heating stirring is stayed overnight, reaction；
It is cooled to room temperature after reaction, is spin-dried for solvent, methylene chloride dissolution, washing, then have with anhydrous sodium sulfate drying Machine phase, filtering are spin-dried for, and crude product obtains white crystal, the column chromatography by column chromatography eluting, then with ethyl alcohol recrystallization The methylene chloride and petroleum ether for being 1:1 using volume ratio.
The reaction equation of above-mentioned reaction process specifically:
Then compound and 4,4'- dibromobenzo-phenone that the application will have formula (II) structure is under the effect of the catalyst Reaction, obtains first conjugated polymer with formula (IV) structure；During this, the catalyst used for tetra-triphenylphosphine palladium, The catalyst is the 1wt% of the compound and the 4,4'- dibromobenzo-phenone gross mass；The compound and described 4, The molar ratio of 4'- dibromobenzo-phenone is 1:1, and the reaction is in the wet chemical and toluene solution that volume ratio is 1:3 It is carried out in mixed solution, the concentration of the wet chemical is 2mol/L；The temperature of the reaction is 90~100 DEG C.In order to The first pure conjugated polymer is obtained, the application is purified after reacting, then the above process specifically:
Under an argon atmosphere, by 4,4'- dibromobenzo-phenone, with four triphen of compound and catalyst of formula (II) structure Base phosphine palladium is mixed in wet chemical and toluene solution, heating stirring, reaction；It is cooled to room temperature after reaction, uses dichloro Methane dilution, is washed with salt water and deionized water, and organic layer removes solvent after being dried, filtered with anhydrous sodium sulfate, then with most A small amount of methylene chloride dissolution, is deposited in anhydrous methanol, and the polymer that canescence has formula (IV) structure is obtained after vacuum drying. The above process specifically:
Above-mentioned first conjugated polymer in order to obtain, can also synthesize in the following manner:
To have the alkyl fluorenes and trimethylborate of formula (I) structure anti-under the action of catalyst magnesium chips and grignard reagent It answers, obtains the compound with formula (III) structure；
To have formula (II) structure or the compound with formula (III) structure with 4,4- dibromobenzo-phenone in catalyst The lower reaction of effect, obtains first conjugated polymer with formula (IV) structure；Specific reaction equation are as follows:
After obtaining the first conjugated polymer, then it is reacted in a solvent with malononitrile, obtain the second conjugated polymers Object；In the process, the molar ratio of first conjugated polymer and malononitrile is 1:10, and the reaction is 1:2 in volume ratio Titanium tetrachloride and pyridine mixed liquor in carry out, the temperature of the reaction is 0~60 DEG C, and the time of the reaction is for 24 hours.It is pure The preparation method of the second net conjugated polymer specifically:
Under an argon atmosphere, the first conjugated polymer and malononitrile are dissolved in anhydrous methylene chloride, the mixture that will be obtained After being cooled to required temperature, titanium tetrachloride and pyridine is added dropwise；Then cooling bath is removed, solution is heated to reflux；After reaction It is cooled to room temperature, dissolution is that the hydrochloric acid solution of 10wt% and sodium bicarbonate solution wash with concentration in methylene chloride, organic Layer is dry with anhydrous sodium sulfate；Solvent is removed after filtering, is then dissolved, is deposited in anhydrous methanol with minimum methylene chloride, The second conjugated polymer of yellow is obtained after vacuum drying.Above-mentioned preparation process specifically:
It is after obtaining the second conjugated polymer, then second conjugated polymer and hydroxylamine hydrochloride is anti-in a solvent It answers, obtains the amidoxim fluidized polymer with formula (VI) structure；In above process, second conjugated polymer and the salt The molar ratio of sour azanol is 1:10, and the temperature of the reaction is 75~85 DEG C, and the time of the reaction is 12h, and the solvent is N,N-Dimethylformamide.Obtain the process of pure amidoxim fluidized polymer specifically:
Second conjugated polymer and hydroxylamine hydrochloride solution are added in n,N-Dimethylformamide and heat reaction, is obtained Product is cooled to room temperature, and is then deposited in anhydrous methanol, and filtering obtains the solid powder of yellow after being placed in vacuum drying oven drying Last amidoxim fluidized polymer.Specific reaction equation are as follows:
Present invention also provides one kind amidoxim fluidized polymer as shown in formula (VI),
Wherein, R is the alkyl of C1~C10.
The present invention also provides application of the above-mentioned amidoxim fluidized polymer in identification uranyl ion.
Herein described amidoxim fluidized polymer can be in a variety of mixed metal solions, quick, trace detection Uranyl ion out；Such as: it can be simultaneously by UO2 2+、Cu2+、Co2+、Ni2+、Cd2+、Zn2+、Pb2+、Ba2+、Al3+、Cr3+、Fe3+、Zr4+、 Dy3+、La3+、Eu3+、Sm3+、Mg2+、Ca2+、Bi2+、Ag+、Mn2+、Na+And K+One of or it is a variety of be mixed in solution, due to The fluorescence of the polymer can be quenched in uranyl ion, therefore the polymer can quickly detect uranyl ion.
The present invention has synthesized a kind of polymer of uranyl ion specific recognition, the polymer alternative identify uranyl from Son, and there is preferable sensitivity and anti-interference ability；And the polymeric water-soluble synthesized is preferable, can be further used for reality The detection of water sample.
Preparation for a further understanding of the present invention, below with reference to embodiment to amidoxim fluidized polymer provided by the invention Method and its application are described in detail, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
Step 1: prepare compound 9,9- dioctyl fluorene -2,7- bis- (boric acid pinacol esters)
Under argon gas, by 5mmol 2, bromo- 9, the 9- dioctyl fluorene of 7- bis-, 10mmol connection boric acid pinacol ester, 1.47g drying Potassium acetate, 0.368g catalyst palladium chloride (Pd (dppf) Cl2) put into three-necked flask, the anhydrous Isosorbide-5-Nitrae-dioxy of 50ml is added Six rings make it dissolve and heating stirring is stayed overnight, and are cooled to room temperature after reaction, are spin-dried for solvent, and methylene chloride dissolution is washed, then With the dry organic phase of anhydrous sodium sulfate, filtering is spin-dried for, and crude product is by column chromatography eluting, then obtains white with ethyl alcohol recrystallization Crystal；
Step 2: preparing conjugated polymer P0
Under an argon atmosphere, by 1mmol 4,4'- dibromobenzo-phenone, 1mmol 9, the bis- (boric acid of 9- dioctyl fluorene -2,7- Pinacol ester) and 9.8mg catalyst tetra-triphenylphosphine palladium (Pd (PPh3)4) three-necked flask is put into, body is injected by syringe Than the wet chemical and toluene solution that are 1:3, heating stirring is cooled to room temperature product after reaction, dilute with methylene chloride It releases, is washed with salt water and deionized water, organic layer removes solvent after being dried, filtered with anhydrous sodium sulfate, then use methylene chloride Dissolution, is deposited in anhydrous methanol, canescence polymer P 0 is obtained after vacuum drying；
Step 3: preparing conjugated polymer P1
Under an argon atmosphere, 0.52mmol polymer P 0 and 5.2mmol malononitrile are dissolved in anhydrous methylene chloride；It will mixing After object is cooled to required temperature, the 0.6ml titanium tetrachloride and 1.2ml pyridine of volume ratio 1:2 is added dropwise；Then cooling bath is removed, it will Solution is heated to reflux, and is cooled to room temperature after reaction, and dissolution in methylene chloride, is washed with hydrochloric acid solution and sodium bicarbonate solution It washs；Organic layer removes solvent after being dried, filtered with anhydrous sodium sulfate, then dissolved with methylene chloride, is deposited in anhydrous methanol, Yellow polymer P1 is obtained after vacuum drying；
Step 4: preparation target conjugated polymer P2
0.25mmol P1 and 2.5mol hydroxylamine solution is added to heating reaction in n,N-Dimethylformamide (DMF), is obtained To product be cooled to room temperature, be then deposited in anhydrous methanol, filter, be placed in vacuum drying oven it is dry after obtain consolidating for yellow Body powder P2；
The infrared spectroscopy of polymer P 0, P1 and P2 are detected, testing result is as shown in Figure 1；Fig. 2 is manufactured in the present embodiment poly- Close the carbon spectrogram of object P0；Fig. 3 is the carbon spectrogram of polymer P 1 manufactured in the present embodiment；Fig. 4 is polymer manufactured in the present embodiment The carbon spectrogram of P2；
Step 5: preparation target conjugated polymer P2 standard solution
Above-mentioned conjugated polymer P2 is dissolved in n,N-dimethylacetamide (DMA), is configured to 1 × 10-4M standard is molten Liquid is kept in dark place at room temperature, and when use is diluted to required scale；
Step 6: conjugated polymer P2 standard solution and different metal ions fluorescence detection method
The conjugated polymer P2 standard solution that step 5 is configured to concentration to be measured is 1 × 10-5Other metals to be measured are added in M Solion (UO2 2+、Cu2+、Co2+、Ni2+、Cd2+、Zn2+、Pb2+、Ba2+、Al3+、Cr3+、Fe3+、Zr4+、Dy3+、La3+、Eu3+、Sm3 +、Mg2+、Ca2+、Bi2+、Ag+、Mn2+、Na+And K+One of), obtaining concentration to be measured is 1.5 × 10-5M mixed solution, will be to be measured Mixed solution concussion after, measure fluorescence spectrum；
Above-mentioned testing result is as shown in Fig. 5, Fig. 6 and Fig. 7, as shown in Figure 5, the mixed solution formed by P2 with uranyl from The concentration of son increases fluorescence intensity and constantly weakens；It will be appreciated from fig. 6 that selection of the mixed solution formed by P2 to its uranyl ion Property it is high；As shown in Figure 7, the mixed solution formed by P2 is to other ion strong interference immunities.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (9)

1. a kind of preparation method of amidoxim fluidized polymer, comprising the following steps:
A the alkyl fluorenes with formula (I) structure and connection boric acid pinacol ester are reacted under the effect of the catalyst), obtained with formula (II) compound of structure；
Or react the alkyl fluorenes with formula (I) structure and trimethylborate under the effect of the catalyst, it obtains with formula (III) The compound of structure；
B) will have formula (II) structure or with formula (III) structure compound and 4,4'- dibromobenzo-phenone catalyst work With lower reaction, first conjugated polymer with formula (IV) structure is obtained；
C first conjugated polymer and malononitrile are reacted in a solvent), obtain having second conjugation of formula (V) structure poly- Close object；
D second conjugated polymer and hydroxylamine hydrochloride are reacted in a solvent), obtain the amidoxim with formula (VI) structure Polymer；
Wherein, X is halogen；
R is the alkyl of C1~C10.
2. preparation method according to claim 1, which is characterized in that the R be the unsubstituted alkyl of C1~C8, C1~ The hydroxyalkyl of C8, the amidoalkyl group of C1~C8, the quaternary ammonium alkyl of C1~C8 or the sulfonic alkyl of C1~C8.
3. preparation method according to claim 1, which is characterized in that step A) in, obtaining that there is formula (II) structure In compound, the catalyst is palladium chloride, and the molar ratio of the alkyl fluorenes and the connection boric acid pinacol ester is 1:2, institute The temperature for stating reaction is 95~110 DEG C.
4. preparation method according to claim 1, which is characterized in that step A) in, obtaining that there is formula (III) structure In compound, the catalyst is magnesium chips and grignard reagent, and the molar ratio of the alkyl fluorenes and the trimethylborate is 1:10.
5. preparation method according to claim 1, which is characterized in that step B) in, the catalyst is four triphenylphosphines Palladium, the catalyst are the 1wt% of the compound and 4, the 4'- dibromobenzo-phenone gross mass；The compound and institute The molar ratio for stating 4,4'- dibromobenzo-phenone is 1:1, and the reaction is in the wet chemical and toluene that volume ratio is 1:3 It is carried out in mixed solution, the concentration of the wet chemical is 2mol/L；The temperature of the reaction is 90~100 DEG C.
6. preparation method according to claim 1, which is characterized in that first conjugated polymer and the malononitrile Molar ratio is 1:10, and the solvent is anhydrous methylene chloride, the mixed liquor of titanium tetrachloride and pyridine, the titanium tetrachloride and described The volume ratio of pyridine is 1:2, and the temperature of the reaction is 0~60 DEG C.
7. preparation method according to claim 1, which is characterized in that second conjugated polymer and the hydroxylamine hydrochloride Molar ratio be 1:10, the temperature of the reaction is 75~85 DEG C.
8. a kind of amidoxim fluidized polymer as shown in formula (VI),
Wherein, R is the alkyl of C1~C10.
9. amidoxim fluidized polymer or according to any one of claims 8 prepared by the described in any item preparation methods of claim 1~7 Application of the amidoxim fluidized polymer in identification uranyl ion.
CN201910604649.7A 2019-07-05 2019-07-05 A kind of amidoxim fluidized polymer, preparation method and application Pending CN110294837A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910604649.7A CN110294837A (en) 2019-07-05 2019-07-05 A kind of amidoxim fluidized polymer, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910604649.7A CN110294837A (en) 2019-07-05 2019-07-05 A kind of amidoxim fluidized polymer, preparation method and application

Publications (1)

Publication Number Publication Date
CN110294837A true CN110294837A (en) 2019-10-01

Family

ID=68030432

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910604649.7A Pending CN110294837A (en) 2019-07-05 2019-07-05 A kind of amidoxim fluidized polymer, preparation method and application

Country Status (1)

Country Link
CN (1) CN110294837A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110596082A (en) * 2019-10-17 2019-12-20 苏州大学 Probe for detecting trace uranyl ions and portable ECL detector based on probe
CN111303193A (en) * 2020-03-31 2020-06-19 南华大学 PADAP derivative, preparation method and application thereof
CN113340862A (en) * 2021-05-24 2021-09-03 中国工程物理研究院材料研究所 Fluorescent molecular sensor, preparation method thereof and detection method of trace uranyl ions in water

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004097921A (en) * 2002-09-09 2004-04-02 Japan Atom Energy Res Inst Synthetic method for amidoxime-type collecting material by graft polymerization
CN105860034A (en) * 2016-05-03 2016-08-17 桂林理工大学 Conjugated polymer electron donor material of polymer solar cell blended active layer and preparation method of conjugated polymer electron donor material
CN107138137A (en) * 2017-06-08 2017-09-08 四川大学 A kind of antibiotic property amidoxime group extraction of uranium from seawater adsorbent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004097921A (en) * 2002-09-09 2004-04-02 Japan Atom Energy Res Inst Synthetic method for amidoxime-type collecting material by graft polymerization
CN105860034A (en) * 2016-05-03 2016-08-17 桂林理工大学 Conjugated polymer electron donor material of polymer solar cell blended active layer and preparation method of conjugated polymer electron donor material
CN107138137A (en) * 2017-06-08 2017-09-08 四川大学 A kind of antibiotic property amidoxime group extraction of uranium from seawater adsorbent and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAMZA MF: "Uranium recovery from concentrated chloride solution produced from direct acid leaching of calcareous shale, Allouga ore materials, southwestern Sinai, Egypt", 《JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY》 *
WU XF: "Highly Selective and Sensitive Detection of Cyanide by a Reaction-Based Conjugated Polymer Chemosensor", 《MACROMOLECULES》 *
XU MY, ET AL: "Highly fluorescent conjugated microporous polymers for concurrent adsorption and detection of uranium", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110596082A (en) * 2019-10-17 2019-12-20 苏州大学 Probe for detecting trace uranyl ions and portable ECL detector based on probe
CN110596082B (en) * 2019-10-17 2020-07-24 苏州大学 Probe for detecting trace uranyl ions and portable EC L detector based on probe
WO2021072900A1 (en) * 2019-10-17 2021-04-22 苏州大学 Probe for detecting trace uranyl ions, and portable ecl detector based on same
CN111303193A (en) * 2020-03-31 2020-06-19 南华大学 PADAP derivative, preparation method and application thereof
CN111303193B (en) * 2020-03-31 2022-12-27 南华大学 PADAP derivative, preparation method and application thereof
CN113340862A (en) * 2021-05-24 2021-09-03 中国工程物理研究院材料研究所 Fluorescent molecular sensor, preparation method thereof and detection method of trace uranyl ions in water

Similar Documents

Publication Publication Date Title
CN110294837A (en) A kind of amidoxim fluidized polymer, preparation method and application
Ding et al. Reaction-based conjugated polymer fluorescent probe for mercury (II): good sensing performance with “turn-on” signal output
CN105385439B (en) Detect response type rhodamine fluorescence probe and its preparation and application of mercury ion
CN107132207B (en) It is a kind of for quickly detecting the fluorescent optical sensor and preparation method thereof of explosive, quickly detect explosive method
CN107286327B (en) It is a kind of for quickly detecting the fluorescent test paper and preparation method thereof of explosive, quickly detect explosive method
CN105924449A (en) Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions
CN110204693A (en) Macromolecule covalent organic framework polymer and preparation method and application based on triphenylamine derivative
CN104845612A (en) Polystyrene mercury ion fluorescence recognition materials and preparation method thereof
CN107573258B (en) A kind of fluorescence probe and preparation method and application detecting aluminium ion and zinc ion
CN110964042B (en) Preparation method and application of N, N-di (2-picolyl) amido BODIPY nickel ion fluorescent probe
CN103374100B (en) Preparation and application of europium base polymer with long fluorescence lifetime and capable of selective recognition of anion
CN103937487A (en) Phosphorescent fluorinion probe, preparation and applications thereof
CN110746423B (en) Synthesis of aryl imidazophenanthroline fluorescent dye and identification of metal ions
CN103408493B (en) Multi-arm naphthalimide fluorescent molecule and preparation method thereof
CN114230581B (en) Multidentate organic ligand, preparation method and application thereof, metal supramolecular polymer and preparation method thereof
Bao et al. Synthesis and fluorescence properties of Tb (III) complex with a novel aromatic carboxylic acid (L) as well as spectroscopic studies on the interaction between Tb (III) complex and bovine serum albumin
CN111454212A (en) Aromatic compound containing tetraphenylethylene structure and preparation method and application thereof
CN106397743A (en) Application of water-soluble fluorescent conjugated polymer to detection of nitroaromatic hydrocarbon
CN108218881A (en) Novel mercury ion fluorescence probe based on rhodamine B and preparation method and application
CN105294540A (en) Novel Schiff base compound taking triphenylamine as center and preparation of novel Schiff base compound
CN110627787B (en) Detectable aquatic Al3+、Fe3+、Ag+And Zn2+Julolidine fluorescent molecular sensor and preparation method thereof
CN114507213B (en) Fluorescent compound, fluorescent probe, fluorescent visual test paper, and preparation method and application thereof
CN104927834B (en) A kind of disubstituted polyacetylene fluorescent dye of carbazolyl-containing group and preparation method thereof
CN107098852A (en) The amine-modified pyrene derivatives fluorescence probe of two (2 picolines) and its synthetic method and application
CN108358952B (en) Compound for saxitoxin fluorescence detection and detection method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20191001