CN106432170B - A kind of rhodamine B base RAFT reagents and preparation method and the method that fluorescent microsphere is prepared based on this reagent - Google Patents
A kind of rhodamine B base RAFT reagents and preparation method and the method that fluorescent microsphere is prepared based on this reagent Download PDFInfo
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- CN106432170B CN106432170B CN201610803894.7A CN201610803894A CN106432170B CN 106432170 B CN106432170 B CN 106432170B CN 201610803894 A CN201610803894 A CN 201610803894A CN 106432170 B CN106432170 B CN 106432170B
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Abstract
The invention discloses a kind of rhodamine B base RAFT reagents and preparation method thereof and the methods for preparing fluorescent microsphere based on this reagent.The structural formula of the rhodamine B base RAFT reagents is specific as follows：Using between the rhodamine B and trithiocarbonate RAFT reagents of hydroxyl modification esterification occurs for the present invention, can with simple and effective prepare the RAFT reagents of rhodamine B fluorescence labeling.Then, by the RAFT reagent one-step synthesis of this modification fluorescent microsphere of size uniformity, reaction condition is mild, and yield is higher, and the RAFT reagents of rhodamine B fluorescence labeling according to the present invention and the preparation method of fluorescent microsphere have good application prospect.
Description
Technical field
Fluorescent microsphere is prepared the present invention relates to a kind of rhodamine B base RAFT reagents and preparation method and based on this reagent
Method belongs to the technical field that well-controlled radical polymerization method prepares functional high molecule material.
Background technology
Invertible ideal (RAFT) is turned using two thio or trithiocarbonate compound as chain
Agent is moved, the design that can be simple and efficient simultaneously prepares specific structure and the controllable functional high molecule material of molecular weight distribution.It is glimmering
The polymer microsphere that cursor shows refers to that fluorescent material is contained in a kind of surface or inside, can under the light irradiation of certain wavelength
Send out the polymer microsphere of fluorescence.Due to functional fluorescent microsphere large specific surface area, adsorption is strong, and aggtegation is big, table
Face respond is strong and efficient luminous efficiency, fluorescent microsphere chemical analysis, biological medicine, medical diagnosis on disease, food engineering with
And the fields such as environmental science are widely used and study.The preparation of early stage fluorescent microsphere, mainly by fluorescent molecular with
High molecular non-bonding combines, however the binding force of this non-bonding is not secured enough.If standing time is long, microballoon absorption
Fluorescent molecular can slowly fall off, to make fluorescent microsphere lose fluorescent characteristic.In order to overcome this difficulty, people are not according to
Microsphere surface is modified with purposes chemical bonding mode, makes it with functional groups such as amino, carboxyl, sulfydryls, to enhance
The fastness that is combined between microballoon and fluorescent molecular.However, this method operating process is complicated, step is various, is unfavorable for big
Amount production.
At present for fluorescence polymer, the RAFT reagents of design synthesis fluorescence labeling, which have become, prepares fluorescent functional
Change the most common method of macromolecule.The fluorescence intensity of rhodamine fluorescent material is big, and fluorescence quantum yield is high, and is a kind of
The product of commercialization, it is at low cost, it is a kind of fluorescent dye that application prospect is boundless.By the fluorescent dyes rhodamine of commercialization
B is combined with RAFT reagents, prepares the RAFT reagents with fluorescence labeling, and can yet be regarded as a kind of easy, efficiently, economic synthesis side
Method.Using between the rhodamine B and trithiocarbonate RAFT reagents of hydroxyl modification esterification occurs for the present invention, can be easy
Efficiently prepare the RAFT reagents of rhodamine B fluorescence labeling.Then, equal by the RAFT reagent one-step synthesis of this modification size
One fluorescent microsphere, reaction condition is mild, and yield is higher, the RAFT reagents of rhodamine B fluorescence labeling according to the present invention with
And the preparation method of fluorescent microsphere has good application prospect.
Invention content
The purpose of the present invention is to provide a kind of the RAFT reagents and preparation method of easy, economic, efficient fluorescence labeling,
And it is one step of the chain-transferring agent method for preparing high molecular fluorescent microballoons based on this fluorescence RAFT reagents.
The present invention uses following technical scheme：
A kind of rhodamine B base RAFT reagents, the reagent have the following structure：
The preparation method of the upper rhodamine B base RAFT reagents, it includes the following steps：
(1) synthesis of hydroxyl modification rhodamine B：Weigh 0.5g-1g ethylene glycol, 0.5g-1g dicyclohexylcarbodiimides,
The 4-dimethylaminopyridine of 0.01g-0.05g is dissolved in 10mL-50mL dichloromethane, then dropwise by 1g-2g rhodamine Bs
It is added thereto, after being added dropwise, reacts 12 hours at ambient temperature, reaction product obtains sieve of hydroxyl modification through separating-purifying
Red bright B；The structural formula of the rhodamine B of the hydroxyl modification is as follows：
(2) synthesis of carboxyl RAFT reagents：
1) it takes potassium hydroxide 3g-4g, ethyl alcohol 3mL-5mL, water 10mL-20mL to be added in flask, stirs；2) curing is taken
Carbon 2g-6g is slowly added into above-mentioned solution, and ice bath reacts 2-5h；3) p-methyl benzene sulfonic chloride 6g-15g is taken to be added with alcohol solvent
It after heat of solution, is add to the above mixed solution, is stirred to react, extracted after reaction with dichloromethane, sodium bicarbonate saturation
Solution washs, and anhydrous sodium sulfate dries 12h, filtering, and rotary evaporation removes partial solvent, and n-hexane crosses column, dry head product；
4) it weighs 1.0-1.5 times of two isocyano group valeric acid of azo to be dissolved in 30-50ml ethyl acetate solvents, be mixed with step 3 products therefrom
Flow back 12h, uses n-hexane after reaction：Ethyl acetate=7:3 eluant, eluent matched post separation, eluent rotary evaporation
Afterwards, dry in vacuum drying chamber, it is carboxyl RAFT reagents i.e. 4- cyano -4- ethyl trithiocarbonic acids base penta to obtain oil product
Acid；
(3) preparation of rhodamine B base RAFT reagents：Weigh 0.5g-1g steps (1) preparation hydroxyl modification rhodamine B,
Carboxylic prepared by 0.5g-1g dicyclohexylcarbodiimides, the 4-dimethylaminopyridine of 0.01g-0.05g and 0.1g-0.5g steps (2)
Then 10mL dichloromethane is added in base RAFT reagents thereto, reaction 12 hours is stirred at room temperature, after reaction, separation
Purification obtains target product rhodamine B base RAFT reagents.
The specific process for separation and purification of reaction product is in the step (1)：Reaction product dilute hydrochloric acid and water are replaced
Washing can be obtained the rhodamine B of hydroxyl modification three times.
The specific method of reaction product separating-purifying is in the step (3)：Reaction product is filtered to remove by-product two
Cyclohexyl urea, then concentrated by rotary evaporation obtains crude product to filtrate again, finally uses silica gel chromatographic column separating-purifying crude product, and then vacuum is dry
It is dry；The silica gel chromatograph post separation eluant, eluent proportioning is ethyl acetate：Methanol=1:1.
A method of the rhodamine B base RAFT reagents prepared based on the above method prepare fluorescent microsphere, and specific steps are such as
Under：
Weigh 3g-5g acrylonitrile, 3mg-10mg initiator azo-bis-isobutyl cyanides, the RAFT examinations of 35mg-100mg rhodamine B bases
20mL-50mL dimethyl sulfoxide (DMSO)s are added in agent, and the deionized water of 5mL-10mL is then added, then deoxygenation half an hour is put in 70 DEG C
It is reacted 12 hours in oil bath pan, obtains red lotion, then precipitate in deionized water, be freeze-dried, obtained with fluorescence spy
The polyacrylonitrile fluorescent microsphere of property.
Compared with prior art, the present invention being prepared for the rhodamine B base of steady chemical structure using Covalent bonding together method
RAFT reagents, and using this RAFT reagent as chain-transferring agent, one-step synthesis method size uniformity and the macromolecule with fluorescent functional
Microballoon, reaction condition is mild, and step is simple, high income.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of hydroxyl modification rhodamine B prepared by the present invention；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of rhodamine B base RAFT reagents prepared by the present invention；
Fig. 3 is the TEM figures of high molecular fluorescent microballoons prepared by the present invention；
Fig. 4 is the excitation and emission spectra figure of high molecular fluorescent microballoons of the present invention；
Fig. 5 is rhodamine B base RAFT reagents fluorescent stability as a result, wherein (A) is that rhodamine B base RAFT reagent fluorescence is strong
Spend the situation of change with temperature；(B) it is situation of change of the rhodamine B base RAFT reagents fluorescence intensity with the time；
Fig. 6 is figure of changing of the high molecular fluorescent microballoons of the invention prepared with the time.
Specific implementation mode
Present disclosure is described in further detail with reference to specific embodiment.
Embodiment 1
The preparation of rhodamine B base RAFT reagents
It is as follows：
(1) synthesis of hydroxyl modification rhodamine B：Weigh 0.5g-1g ethylene glycol, 0.5g-1g dicyclohexylcarbodiimides,
The 4-dimethylaminopyridine of 0.01g-0.05g is dissolved in 10mL-50mL dichloromethane, then dropwise by 1g-2g rhodamine Bs
It is added thereto, after being added dropwise, reacts 12 hours at ambient temperature, reaction product obtains sieve of hydroxyl modification through separating-purifying
Red bright B；The structural formula of the rhodamine B of the hydroxyl modification is as follows：
(2) synthesis of carboxyl RAFT reagents：
1) it takes potassium hydroxide 3g-4g, ethyl alcohol 3mL-5mL, water 10mL-20mL to be added in flask, stirs；2) curing is taken
Carbon 2g-6g is slowly added into above-mentioned solution, and ice bath reacts 2-5h；3) p-methyl benzene sulfonic chloride 6g-15g is taken to be added with alcohol solvent
It after heat of solution, is add to the above mixed solution, is stirred to react, extracted after reaction with dichloromethane, sodium bicarbonate saturation
Solution washs, and anhydrous sodium sulfate dries 12h, filtering, and rotary evaporation removes partial solvent, and n-hexane crosses column, dry head product；
4) it weighs 1.0-1.5 times of two isocyano group valeric acid of azo to be dissolved in 30-50ml ethyl acetate solvents, be mixed with step 3 products therefrom
Flow back 12h, uses n-hexane after reaction：Ethyl acetate=7:3 eluant, eluent matched post separation, eluent rotary evaporation
Afterwards, dry in vacuum drying chamber, it is carboxyl RAFT reagents i.e. 4- cyano -4- ethyl trithiocarbonic acids base penta to obtain oil product
Acid；
(3) preparation of rhodamine B base RAFT reagents：Weigh 0.66g steps (1) preparation hydroxyl modification rhodamine B,
Carboxyl RAFT reagents prepared by 0.26g dicyclohexylcarbodiimides, the 4-dimethylaminopyridine of 0.016g and 0.22g steps (2),
Then 10mL dichloromethane is added thereto, reaction 12 hours is stirred at room temperature, after reaction, is filtered to remove by-product two
Cyclohexyl urea, filtrate concentrated by rotary evaporation again.Silica gel chromatographic column separating-purifying crude product is finally used, eluant, eluent proportioning used is acetic acid second
Ester：Methanol=1:1, finally vacuum drying obtains target product rhodamine B base RAFT reagents.The rhodamine B base RAFT reagents
Structural formula it is as follows：
Embodiment 2
The rhodamine B base RAFT reagent emulsion polymerizations prepared using embodiment 1 prepare fluorescent microsphere
It is as follows：
Weigh 5g acrylonitrile, 8mg initiator azo-bis-isobutyl cyanides, rhodamine B base RAFT examinations prepared by 35mg embodiments 1
20mL dimethyl sulfoxide (DMSO)s are added in agent, and the deionized water of 5mL is then added, then deoxygenation half an hour is put in 70 DEG C of oil bath pans anti-
It answers 12 hours, obtains red lotion, then precipitate in deionized water, be freeze-dried, obtain the polypropylene with fluorescent characteristic
Nitrile fluorescent microsphere, at 100nm-1 μm, TEM schemes as shown in figure 3, fluorescent emission spectrogram is shown in Fig. 4 the size of gained fluorescent microsphere.
Comparative example
In order to preferably compare, using carboxyl RAFT reagents as chain-transferring agent, 10mg Luo Dan are then added in the solution
Bright B fluorescent materials, during forming polymer microsphere by RAFT emulsion polymerizations, rhodamine B fluorescent molecular in physical absorption,
Make fluorescent characteristic on polymer microsphere band, to which the fluorescent microsphere of physical absorption be made.
Test case
The chemical stability based on rhodamine B base RAFT reagents prepared to the embodiment of the present invention 1 is tested.
Prepare rhodamine B base RAFT solution, solvent N, N '-dimethyl formamide (DMF), a concentration of 0.05mg/mL.It will
The DMF solution of the RAFT reagents of the fluorescence labeling of preparation is placed in oil bath pan, and tests the fluorescence intensity of solution under different temperatures.
As a result as shown in Fig. 5 (A), the results showed that, the fluorescence intensity of the RAFT reagents of the rhodamine B mark obtained by esterification is not
Can be affected by temperature, it is fine to the stability of temperature.In addition, again place the fluorescence RAFT reagent solutions of preparation 30 days,
Every 2 days, its fluorescent characteristic is tested, as a result as shown in Fig. 5 (B).The result shows that rhodamine B base prepared by the embodiment of the present invention 1
The fluorescence intensity of RAFT reagents will not weaken with the extension of time, illustrate the chemical stability of fluorescence RAFT reagents very
It is good.
The fluorescent stability for the high molecular fluorescent microballoons that the present invention is also prepared embodiment 2 is studied, as a result such as Fig. 6
It is shown.Compared with the fluorescent stability of fluorescent microsphere prepared by comparative example physical adsorption process, the present invention is prepared by embodiment 1
The polymer microsphere fluorescent stability that is obtained as chain-transferring agent emulsion polymerization of fluorescence RAFT reagents it is good, preparation method is easy to be high
Effect.
Claims (4)
1. a kind of method preparing fluorescent microsphere using rhodamine B base RAFT reagents, which is characterized in that it includes the following steps：
（1）The synthesis of hydroxyl modification rhodamine B：Weigh 0.5 g-, 1 g ethylene glycol, 0.5 g-, 1 g dicyclohexylcarbodiimides,
The 4-dimethylaminopyridine of 0.01 g-0.05 g is dissolved in 10 mL-50 mL dichloromethane, then by 1 g -2 g Luo Dan
Bright B is added dropwise wherein, after being added dropwise, reacts 12 hours at ambient temperature, reaction product obtains hydroxyl through separating-purifying
Modified rhodamine B；The structural formula of the rhodamine B of the hydroxyl modification is as follows：
；
（2）The synthesis of carboxyl RAFT reagents：1) 3 g -4 g of potassium hydroxide, ethyl alcohol 3 mL-5 mL, 10 mL-20 of water are taken
ML is added in flask, stirring；2) 2 g- of carbon disulfide, 6 g are taken to be slowly added into above-mentioned solution, ice bath reaction 2-5
h；3）It after taking 6 g-15g of p-methyl benzene sulfonic chloride to be dissolved by heating with alcohol solvent, is add to the above mixed solution, stirring is anti-
It answers, is extracted after reaction with dichloromethane, saturated solution of sodium bicarbonate washing, anhydrous sodium sulfate dries 12 h, filters, rotation
Evaporation removes partial solvent, and n-hexane crosses column, dry head product；4) it is molten that 1.0-1.5 times of two isocyano group valeric acids of azo are weighed
In 30-50ml ethyl acetate solvents, 12 h of reflux are mixed with step 3 products therefrom, use n-hexane after reaction：Acetic acid second
Ester=7:3 eluant, eluent matched post separation, and after eluent rotary evaporation, dry in vacuum drying chamber, obtaining oil product is
Carboxyl RAFT reagents, that is, 4- cyano -4- ethyl trithiocarbonic acid base valeric acids；
（3）The preparation of rhodamine B base RAFT reagents：Weigh 0.5 g-, 1 g steps（1）The hydroxyl modification rhodamine B of preparation, 0.5
0.5 g steps of 1 g dicyclohexylcarbodiimides of g-, the 4-dimethylaminopyridine of 0.01 g-0.05 g and 0.1 g-（2）It prepares
Carboxyl RAFT reagents, 10 mL dichloromethane are then added thereto, be stirred at room temperature reaction 12 hours, reaction terminates
Afterwards, separating-purifying obtains target product rhodamine B base RAFT reagents；The rhodamine B base RAFT reagents have the following structure：；
（4）The preparation of fluorescent microsphere：Weigh 3g-5g acrylonitrile, 3 mg-, 10 mg initiator azo-bis-isobutyl cyanides, 35 mg-100
Mg rhodamine B base RAFT reagents are added 20 mL-50 mL dimethyl sulfoxide (DMSO)s, the deionized water of 5 mL-10 mL are then added, removes
Then oxygen half an hour is put in 70 DEG C of oil bath pans and reacts 12 hours, obtains red lotion, then precipitate in deionized water, cold
It is lyophilized dry, obtains the polyacrylonitrile fluorescent microsphere with fluorescent characteristic.
2. the method according to claim 1 for preparing fluorescent microsphere using rhodamine B base RAFT reagents, which is characterized in that
The step（1）The middle specific process for separation and purification of reaction product is：Reaction product dilute hydrochloric acid and water are alternately washed three times
It can be obtained the rhodamine B of hydroxyl modification.
3. the method according to claim 1 for preparing fluorescent microsphere using rhodamine B base RAFT reagents, which is characterized in that
The step（3）The specific method of middle reaction product separating-purifying is：Reaction product is filtered to remove by-product of dicyclohexylurea,
Then concentrated by rotary evaporation obtains crude product to filtrate again, finally uses silica gel chromatographic column separating-purifying crude product, is then dried in vacuo.
4. the method according to claim 3 for preparing fluorescent microsphere using rhodamine B base RAFT reagents, which is characterized in that
The silica gel chromatograph post separation eluant, eluent proportioning is ethyl acetate：Methanol=1:1.
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