CN109053955A - A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone - Google Patents
A kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone Download PDFInfo
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- CN109053955A CN109053955A CN201810947172.8A CN201810947172A CN109053955A CN 109053955 A CN109053955 A CN 109053955A CN 201810947172 A CN201810947172 A CN 201810947172A CN 109053955 A CN109053955 A CN 109053955A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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Abstract
Simultaneous temperature-responsive fluorescent polymer of the water solubility that the present invention relates to a kind of based on sulfone and preparation method thereof, belong to polymeric material field, specifically implement according to the following steps: (1) 4,4 '-dihydroxydiphenylsulisomers, triethylamine and methacrylic chloride reaction prepare polymerizable fluorescent monomer；(2) polymerizable fluorescent monomer, acrylamide (AM), n-isopropyl acrylamide (NIPAM) obtain water-soluble and temperature-responsive fluorescent polymer by Raolical polymerizable.Since sulfuryl, the oxygen atom of hydroxyl and two phenyl ring constitute 4,4 '-dihydroxydiphenylsulisomer systems of height conjugation, the fluorescence property of polymer ensure that；The water soluble group of polyamino makes polymer have good dissolubility in water phase, while NIPAM is a kind of monomer of temperature sensitivity, can effectively control the lower critical solution temperature of polymer and have temperature-responsive.
Description
Technical field
The present invention relates to polymeric material field, specifically a kind of water solubility and the polymerization of temperature-responsive fluorescence based on sulfone
Object and preparation method thereof.
Background technique
Detection technique of fluorescence is because of the hot spot of sensitivity and extremely wide responding range as research field with height
One of project.And in practical applications, small molecule fluorescent compound occur it is such as easy to fall off, with base-material intermiscibility is bad, instrument
In place of the deficiencies of device stability is poor, it is subject to certain restrictions its application range.Fluorescent polymer is small molecule fluorescent base
Group is introduced into polymer in the form that chemical bond combines, and has many advantages, such as stable content, is evenly distributed and is not easily to fall off.By
The material made of most polymer and polymer is all not soluble in water, to greatly limit it in fluorescence
The application of detection field.Water-soluble polymer then realizes the purpose for carrying out fluorescence detection in aqueous solution, largely opens up
Its wide application range.
Stimulating responsive polymer refers to that physically or chemically variation that itself can be subtle to external environment is made accordingly
Reaction.Wherein by MOLECULE DESIGN, stimulating responsive component is introduced into different polymer, realizes the sound to external world's variation
It answers, has caused the highest attention of functional polymer research and application study person.Temperature is one of the most common type environmental factor, because
This water-soluble and temperature-responsive fluorescent polymer will have wide in various fields such as material, life science, medicine and chemistry
Application prospect.
Summary of the invention
Simultaneous temperature-responsive fluorescent polymer of the water solubility that it is an object of the present invention to provide a kind of based on sulfone and preparation method thereof.
The polymer has many advantages, such as good water-soluble and temperature-fluorescence response.
The present invention is to realize that goal of the invention uses following specific technical solution:
1) the polymerizable fluorescent monomer based on sulfone is synthesized；
2) water solubility and temperature-responsive fluorescent polymer of the synthesis based on sulfone；
3) in a preferred embodiment of the invention, the step 1) is by 4,4 '-dihydroxydiphenylsulisomers, acid binding agent
Three is placed in container with solvent, and stirring and dissolving is simultaneously sufficiently mixed；Under the conditions of ice-water bath, excessive methacrylic chloride is dissolved in
It is slowly dropped in above-mentioned mixed liquor after a small amount of solvent, is stirred at room temperature to stopping and reacts；It filters and removes insoluble matter, filtrate is through rotating
A large amount of deionized waters are added after evaporation of solvent, are stored at room temperature 24~26h, filter to obtain crude product；Dehydrated alcohol recrystallization, does
It is dry to obtain white polymerizable fluorescent monomer.
Preferably, the solvent in the step 1) is tetrahydrofuran, 4,4 '-dihydroxydiphenylsulisomers and solvents tetrahydrofurane
Mass volume ratio (g/mL) is 1:15~20；Acid binding agent is triethylamine.
Preferably, being to make sulfone hydroxyl fully reacting, 4,4 '-dihydroxydiphenylsulisomers and methacryl in the step 1)
The ratio between molal quantity of chlorine is 1:3~4；Reaction time is 12~14h.
Preferably, 4,4 '-dihydroxydiphenylsulisomers and acid binding agent molar ratio are 1:3~4 in the step 1).
4) in a preferred embodiment of the invention, the step 2) are as follows: n-isopropyl acrylamide (NIPAM) is used
Mixed solvent toluene/n-hexane (volume ratio: uses after 1/4) recrystallizing；Polymerisable fluorescent monomer, NIPAM, acrylamide
(AM) it is placed in container with solvent, magnetic agitation dissolution；The initiator azodiisobutyronitrile for being dissolved in a small amount of solvent in advance is added
(AIBN) it and is uniformly mixed.First lead to N2About 15~20min deoxygenation continues N2It protects and agitating and heating carries out polymerization reaction；Reaction knot
It is cooled to room temperature after beam, the precipitation purification in the precipitating reagent of 50~60 times of volumes, the product of precipitating is dissolved in a small amount of tetrahydro furan
It mutters and is precipitated in ether again, which is repeated 2 times to remove unreacted monomer, dry that white solid fluorescence polymerize
Object.
Preferably, water solubility and temperature-responsive fluorescent polymer of the synthesis based on sulfone, feature in the step 2)
Be: experimental water is homemade deionized water；Initiator A IBN accounts for about monomer gross mass 1%；Reaction temperature is 65 DEG C；Instead
Between seasonable for 22~for 24 hours, precipitating reagent is ether.
Preferably, water solubility and temperature-responsive fluorescent polymer, feature of the step 2) synthesis based on sulfone exist
In: solvent is tetrahydrofuran, is (mmol/mL) 1:0.8~1 addition by the molal volume ratio of (NIPAM+AM) and tetrahydrofuran；
(NIPAM+AM) and molar ratio 100:0.5~1 of polymerizable fluorescent monomer.
Preferably, water solubility and temperature-responsive fluorescent polymer, feature of the step 2) synthesis based on sulfone exist
In: the molar ratio of polymerized monomer NIPAM and AM are 1:1~4.
Beneficial effect
Compared with prior art, the present invention its advantages are embodied in:
1) methacrylic chloride and 4 are used, 4 '-dihydroxydiphenylsulisomer reactions prepare polymerisable fluorescent monomer, react item
Part is mild, and yield is high, and purification is simple.
2) use NIPAM, AM as high molecular polymerization monomer, it is from a wealth of sources, it is cheap and easy to get, it can save into well
This, reduces the difficulty of large-scale production.
3) polymer prepared has both water-soluble and fluorescence-temperature-responsive, and a series of differences can be obtained by changing reaction condition
The low Critical Solution temperature of polymer can be changed by adjusting ratio of the NIPAM in polymerized monomer in the fluorescent polymer of molecular weight
It spends (LCST), the method is simple, easy.
Specific embodiment
Explanation is further explained to the present invention below by way of specific embodiment.
Embodiment one
10mmol 4,4 '-dihydroxydiphenylsulisomer, 5mL triethylamine, 30mL tetrahydrofuran (THF) are added to round-bottomed flask
In, stirring and dissolving.Under the conditions of ice-water bath, 30mmol methacrylic chloride is dissolved in after 5mL tetrahydrofuran and is slowly added dropwise to flask
It is interior, continue to stir 12h at room temperature.It is filtered to remove precipitating, filtrate removes solvent through rotary evaporation, and 100mL is added into reaction flask
Water is placed at room temperature for for 24 hours, refilters, dry.White solid is recrystallized with dehydrated alcohol, obtains polymerizable fluorescent monomer.
Take the polymerizable fluorescent monomer of 15mmol NIPAM, 35mmol AM and 0.1g in three-necked flask respectively, then plus
The AIBN for entering 45mL tetrahydrofuran solvent, while weighing 0.04g is dissolved in 5mL tetrahydrofuran, is then mixed with monomer mixed solution
Uniformly.Reaction solution is heated to 65 DEG C and insulation reaction for 24 hours under nitrogen protection, is cooled to room temperature by logical nitrogen 15min deoxygenation
Afterwards, product precipitates 3 times in ether, dry.
Embodiment two
The fluorometric investigation of fluorescent polymer and polymerizable fluorescent monomer:
Fig. 3 be in embodiment two polymerizable fluorescent monomer and fluorescent polymer in the fluorescence spectra of ethanol water.Figure
In the polymer it is similar to the wavelength where the maximum absorption band of polymerizable fluorescent monomer, can deduce by sulfone singulation and and it is other
Monomer is copolymerized and has not been changed its fluorescence property.
Fluorescence-temperature-responsive of polymer:
The fluorescence spectrum of fluorescent polymer aqueous solution (about 1mg/mL) in different temperatures is tested, by figure four it is found that in wave
At long 292nm, fluorescence intensity reaches maximum, and does not change with the change of temperature, and in the temperature range of test, general trend is
Temperature increases, and the fluorescence intensity of polymer weakens.
Detailed description of the invention
Fig. 1 is the infrared spectrum of polymerizable fluorescent monomer；
Fig. 2 is the infrared spectrum of fluorescent polymer；
Fig. 3 is the fluorescence spectra of polymerizable fluorescent monomer and fluorescent polymer；
Fig. 4 is the fluorescence spectra of polymer different temperatures.
Claims (2)
1. a kind of water solubility and temperature-responsive fluorescent polymer and preparation method thereof based on sulfone, which is characterized in that structural formula
It is as follows:
2. a kind of water solubility and temperature-responsive fluorescent polymer and its preparation side based on sulfone according to claim 1
Method, which is characterized in that following specific steps are implemented:
(1) preparation of polymerizable fluorescent monomer
4,4 '-dihydroxydiphenylsulisomers, acid binding agent and solvent three are placed in container, and stirring and dissolving is simultaneously sufficiently mixed；Ice-water bath item
Under part, the excess methyl acryloyl chloride for being dissolved in a small amount of solvent is slowly dropped in above-mentioned mixed liquor, is stirred at room temperature anti-to stopping
It answers；It filters and removes insoluble matter, filtrate rotary evaporation is added a large amount of deionized waters after removing solvent, is stored at room temperature, filters slightly to produce
Object；Crude product is recrystallized with dehydrated alcohol, is filtered, dry that white polymerizable fluorescent monomer, structural formula are as follows:
(2) n-isopropyl acrylamide (NIPAM) toluene/n-hexane mixed solvent recrystallization, for use；
(3) water-soluble and temperature-responsive fluorescent polymer synthesis
Polymerizable fluorescent monomer, NIPAM, acrylamide (AM) and solvents tetrahydrofurane are placed in container, and magnetic agitation is to complete
Dissolution；Account for about monomer gross mass 1% initiator azodiisobutyronitrile (AIBN) be dissolved in a small amount of tetrahydrofuran after mixed with monomer
Liquid is uniformly mixed；First lead to N2About 15~20min deoxygenation, then N265 DEG C of insulation reactions 22~for 24 hours are heated with stirring under protection；It is cooling
To room temperature, precipitating removes unreacted monomer in ether, and the product of precipitating is dissolved in a small amount of tetrahydrofuran and again in second
It is precipitated 2 times in ether, it is dry.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113861099A (en) * | 2021-09-30 | 2021-12-31 | 香港中文大学（深圳） | Free radical initiator, luminescent free radical polymer and preparation method thereof |
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| WO2015129901A1 (en) * | 2014-02-27 | 2015-09-03 | 株式会社セルシード | Amino acid derivative fluorescent polymer and fluorescent probe employing same |
| CN107151324A (en) * | 2017-05-22 | 2017-09-12 | 西南科技大学 | Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof |
| CN108164712A (en) * | 2018-01-06 | 2018-06-15 | 福州大学 | A kind of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere and preparation method thereof |
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| WO2015129901A1 (en) * | 2014-02-27 | 2015-09-03 | 株式会社セルシード | Amino acid derivative fluorescent polymer and fluorescent probe employing same |
| CN107151324A (en) * | 2017-05-22 | 2017-09-12 | 西南科技大学 | Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof |
| CN108164712A (en) * | 2018-01-06 | 2018-06-15 | 福州大学 | A kind of Synthesis, Characterization of Polyphosphazenes fluorescent microsphere and preparation method thereof |
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| CN113861099A (en) * | 2021-09-30 | 2021-12-31 | 香港中文大学（深圳） | Free radical initiator, luminescent free radical polymer and preparation method thereof |
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