CN106432170A - Rhodamine B-based RAFT (reversible addition fragmentation chain transfer) reagent, preparation method and method for preparing fluorescent microspheres on basis of reagent - Google Patents
Rhodamine B-based RAFT (reversible addition fragmentation chain transfer) reagent, preparation method and method for preparing fluorescent microspheres on basis of reagent Download PDFInfo
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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Abstract
The invention discloses a rhodamine B-based RAFT (reversible addition fragmentation chain transfer) reagent, a preparation method of the reagent and a method for preparing fluorescent microspheres on the basis of the reagent. The structural formula of the rhodamine B-based RAFT reagent is specifically shown in the specification. Hydroxyl-modified rhodamine B and a trithiocarbonate RAFT agent are subjected to an esterification reaction, and the rhodamine B fluorescence marked RAFT reagent can be prepared simply and efficiently. Then the fluorescent microspheres with uniform size are synthesized from the modified RAFT reagent in one step, the reaction condition is mild, the yield is higher, and the rhodamine B fluorescence marked RAFT reagent and the method for preparing the fluorescent microspheres have bright application prospect.
Description
Technical field
The present invention relates to a kind of rhodamine B base RAFT reagent and preparation method and fluorescent microsphere is prepared 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 by the use of dithio or trithiocarbonate compound as chain
Move agent, simply can efficiently design and prepare ad hoc structure and the controlled functional high molecule material of molecular weight distribution.Glimmering
The polymer microsphere that light indicates refers to that fluorescent material is contained in a class surface or inside, under the light irradiation of certain wavelength, can
Send the polymer microsphere of fluorescence.Because feature fluorescent microsphere specific surface area is big, adsorption is strong, and aggregation is big, table
Face respond is strong and efficient luminous efficiency, fluorescent microsphere chemical analyses, biological medicine, medical diagnosis on disease, food engineering with
And the field such as environmental science is widely used and studies.The preparation of early stage fluorescent microsphere, mainly pass through fluorescence molecule with
High molecular non-bonding combines, but the adhesion of this non-bonding is not firm.If standing time is long, microsphere adsorbs
Fluorescence molecule can slowly come off, so that fluorescent microsphere loses fluorescent characteristic.In order to overcome this difficult, people are not according to
With purposes chemical bonding mode, microsphere surface is modified so as to be carried the functional groups such as amino, carboxyl, sulfydryl, thus strengthening
The fastness combining between microsphere and fluorescence molecule.However, this method operating process is complicated, step is various, and is unfavorable for big
Amount produces.
At present for fluorescence polymer, the RAFT reagent of design synthesis fluorescence labeling has become as prepares fluorescent functional
Change macromolecule most common method.The fluorescence intensity of rhodamine fluorescent material is big, and fluorescence quantum yield is high, and is a kind of
The product of commercialization, low cost, is a kind of boundless fluorescent dye of application prospect.Fluorescent dyes rhodamine by commercialization
B is combined with RAFT reagent, the RAFT reagent with fluorescence labeling for the preparation, and can yet be regarded as a kind of easy, efficient, economic synthesis side
Method.The present invention utilizes, between the rhodamine B of hydroxyl modification and trithiocarbonate RAFT reagent, esterification occurs, can be easy
Efficiently prepare the RAFT reagent of rhodamine B fluorescence labeling.Then, size is equal by this modified RAFT reagent one-step synthesis
One fluorescent microsphere, reaction condition is gentle, and yield is higher, the RAFT reagent of rhodamine B fluorescence labeling involved in the present invention with
And the preparation method of fluorescent microsphere has good application prospect.
Content of the invention
It is an object of the invention to provide a kind of easy, economic, efficient fluorescence labeling RAFT reagent and preparation method,
And its method that high molecular fluorescent microballoons are prepared for chain-transferring agent one step based on this fluorescence RAFT reagent.
The present invention employs the following technical solutions：
A kind of rhodamine B base RAFT reagent, this reagent has following structure：
The preparation method of upper described rhodamine B base RAFT reagent, it comprises the following steps：
(1) synthesis of hydroxyl modification rhodamine B：Weigh 0.5g-1g ethylene glycol, 0.5g-1g dicyclohexylcarbodiimide,
The DMAP of 0.01g-0.05g, is dissolved in 10mL-50mL dichloromethane, then by 1g-2g rhodamine B dropwise
It is added thereto, after completion of dropping, react 12 hours at ambient temperature, the separated purification of product obtains sieve of hydroxyl modification
Red bright B；The structural formula of the rhodamine B of described hydroxyl modification is as follows：
(2) synthesis of carboxyl RAFT reagent：
1) potassium hydroxide 3g-4g, ethanol 3mL-5mL are taken, water 10mL-20mL is added in flask, stirring；2) take curing
Carbon 2g-6g is slowly added in above-mentioned solution, and ice bath reacts 2 5h；3) take p-methyl benzene sulfonic chloride 6g-15g alcohol solvent plus
After heat of solution, it is added in above-mentioned mixed solution, stirring reaction, reaction is extracted with dichloromethane after terminating, sodium bicarbonate saturation
Solution washs, anhydrous sodium sulfate drying 12h, filters, and rotary evaporation removes partial solvent, and normal hexane crosses post, dry head product；
4) weigh 1.0-1.5 times of azo two isocyano group valeric acid to be dissolved in 30-50ml ethyl acetate solvent, mix with step 3 products therefrom
Backflow 12h, reaction uses normal hexane after terminating：Ethyl acetate=7:3 eluant proportioning crosses post separation, eluent rotary evaporation
Afterwards, it is dried in vacuum drying oven, obtain oil product to be carboxyl RAFT reagent is 4- cyano group -4- ethyl dihydrogen thiocarbonate. base penta
Acid；
(3) preparation of rhodamine B base RAFT reagent：Weigh hydroxyl modification rhodamine B prepared by 0.5g-1g step (1),
Carboxylic prepared by 0.5g-1g dicyclohexylcarbodiimide, the DMAP of 0.01g-0.05g and 0.1g-0.5g step (2)
Base RAFT reagent, is then added thereto to 10mL dichloromethane, and reaction 12 hour is stirred at room temperature, and after reaction terminates, separates
Purification obtains target product rhodamine B base RAFT reagent.
In described step (1), the specific process for separation and purification of product is：Product dilute hydrochloric acid and water are replaced
Washing can get the rhodamine B of hydroxyl modification for three times.
In described step (3), the concrete grammar of product separating-purifying is：Product is filtered to remove by-product two
Cyclohexyl urea, then filtrate concentrated by rotary evaporation obtains crude product again, finally use silica gel chromatographic column separating-purifying crude product, then vacuum do
Dry；Described silica gel chromatography post separation eluant proportioning is ethyl acetate：Methanol=1:1.
A kind of method preparing fluorescent microsphere based on the rhodamine B base RAFT reagent of said method preparation, concrete steps are such as
Under：
Weigh 3g-5g acrylonitrile, 3mg-10mg initiator azo-bis-isobutyl cyanide, 35mg-100mg rhodamine B base RAFT tries
Agent, adds 20mL-50mL dimethyl sulfoxide, is subsequently adding the deionized water of 5mL-10mL, deoxygenation half an hour, is then put in 70 DEG C
React 12 hours in oil bath pan, obtain red emulsion, then precipitate in deionized water, lyophilization, obtain special with fluorescence
The polyacrylonitrile fluorescent microsphere of property.
The present invention compared with prior art, is prepared for the rhodamine B base of steady chemical structure using Covalent bonding together method
RAFT reagent, and with this RAFT reagent as chain-transferring agent, one-step synthesis method size uniformity simultaneously has the macromolecule of fluorescent functional
Microsphere, reaction condition is gentle, and step is simple, high income.
Brief description
The nucleus magnetic hydrogen spectrum figure of the hydroxyl modification rhodamine B that Fig. 1 is prepared for the present invention；
The nucleus magnetic hydrogen spectrum figure of the rhodamine B base RAFT reagent that Fig. 2 is prepared for the present invention；
The TEM figure of the high molecular fluorescent microballoons that Fig. 3 is prepared for 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 reagent fluorescent stability result, and wherein (A) is that rhodamine B base RAFT reagent fluorescence is strong
Degree is with the situation of change of temperature；(B) it is rhodamine B base RAFT reagent fluorescence intensity situation of change over time；
Fig. 6 is the high molecular fluorescent microballoons situation of change figure over time of present invention preparation.
Specific embodiment
With reference to specific embodiment, present disclosure is described in further detail.
Embodiment 1
The preparation of rhodamine B base RAFT reagent
Comprise the following steps that：
(1) synthesis of hydroxyl modification rhodamine B：Weigh 0.5g-1g ethylene glycol, 0.5g-1g dicyclohexylcarbodiimide,
The DMAP of 0.01g-0.05g, is dissolved in 10mL-50mL dichloromethane, then by 1g-2g rhodamine B dropwise
It is added thereto, after completion of dropping, react 12 hours at ambient temperature, the separated purification of product obtains sieve of hydroxyl modification
Red bright B；The structural formula of the rhodamine B of described hydroxyl modification is as follows：
(2) synthesis of carboxyl RAFT reagent：
1) potassium hydroxide 3g-4g, ethanol 3mL-5mL are taken, water 10mL-20mL is added in flask, stirring；2) take curing
Carbon 2g-6g is slowly added in above-mentioned solution, and ice bath reacts 2 5h；3) take p-methyl benzene sulfonic chloride 6g-15g alcohol solvent plus
After heat of solution, it is added in above-mentioned mixed solution, stirring reaction, reaction is extracted with dichloromethane after terminating, sodium bicarbonate saturation
Solution washs, anhydrous sodium sulfate drying 12h, filters, and rotary evaporation removes partial solvent, and normal hexane crosses post, dry head product；
4) weigh 1.0-1.5 times of azo two isocyano group valeric acid to be dissolved in 30-50ml ethyl acetate solvent, mix with step 3 products therefrom
Backflow 12h, reaction uses normal hexane after terminating：Ethyl acetate=7:3 eluant proportioning crosses post separation, eluent rotary evaporation
Afterwards, it is dried in vacuum drying oven, obtain oil product to be carboxyl RAFT reagent is 4- cyano group -4- ethyl dihydrogen thiocarbonate. base penta
Acid；
(3) preparation of rhodamine B base RAFT reagent：Weigh hydroxyl modification rhodamine B prepared by 0.66g step (1),
Carboxyl RAFT reagent prepared by 0.26g dicyclohexylcarbodiimide, the DMAP of 0.016g and 0.22g step (2),
Then it is added thereto to 10mL dichloromethane, reaction 12 hours is stirred at room temperature, after reaction terminates, is filtered to remove by-product two
Cyclohexyl urea, filtrate concentrated by rotary evaporation again.Finally use silica gel chromatographic column separating-purifying crude product, eluant proportioning used is acetic acid second
Ester：Methanol=1:1, finally vacuum drying obtains target product rhodamine B base RAFT reagent.Described rhodamine B base RAFT reagent
Structural formula as follows：
Embodiment 2
Rhodamine B base RAFT reagent emulsion polymerization using embodiment 1 preparation prepares fluorescent microsphere
Comprise the following steps that：
Weigh 5g acrylonitrile, 8mg initiator azo-bis-isobutyl cyanide, the rhodamine B base RAFT examination of 35mg embodiment 1 preparation
Agent, adds 20mL dimethyl sulfoxide, is subsequently adding the deionized water of 5mL, deoxygenation half an hour, is then put in 70 DEG C of oil bath pans anti-
Answer 12 hours, obtain red emulsion, then precipitate in deionized water, lyophilization, obtain the polypropylene with fluorescent characteristic
Nitrile fluorescent microsphere, at 100nm-1 μm, its 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 contrast, it is used carboxyl RAFT reagent as chain-transferring agent, then adds 10mg Luo Dan in the solution
Bright B fluorescent material, during polymer microsphere is formed by RAFT emulsion polymerization, rhodamine B fluorescence molecule in physical absorption,
Make fluorescent characteristic on polymer microsphere band, thus the fluorescent microsphere of physical absorption is obtained.
Test case
To being tested based on the chemical stability of rhodamine B base RAFT reagent of the embodiment of the present invention 1 preparation.
Prepare rhodamine B base RAFT solution, solvent is N, N '-dimethyl Methanamide (DMF), concentration is 0.05mg/mL.Will
The DMF solution of the RAFT reagent of fluorescence labeling prepared is placed in oil bath pan, and tests the fluorescence intensity of solution under different temperatures.
Shown in result such as Fig. 5 (A), result shows, the fluorescence intensity of the RAFT reagent being indicated by the rhodamine B that esterification obtains is not
Can be affected by temperature, fine to the stability of temperature.In addition, the fluorescence RAFT reagent solution prepared is placed 30 days again,
Every 2 days, test its fluorescent characteristic, shown in result such as Fig. 5 (B).Result shows, the rhodamine B base of the embodiment of the present invention 1 preparation
The fluorescence intensity of RAFT reagent will not prolongation over time and weaken, the chemical stability of this fluorescence RAFT reagent is described very
Good.
The present invention is also studied to the fluorescent stability of the high molecular fluorescent microballoons of embodiment 2 preparation, result such as Fig. 6
Shown.Compared with the fluorescent stability of the fluorescent microsphere of comparative example physical adsorption process preparation, the present invention is prepared by embodiment 1
The polymer microsphere fluorescent stability that obtains as chain-transferring agent emulsion polymerization of fluorescence RAFT reagent good, preparation method is simple is high
Effect.
Claims (6)
1. a kind of rhodamine B base RAFT reagent is it is characterised in that this reagent has following structure：
2. a kind of preparation method of the rhodamine B base RAFT reagent described in claim 1 is it is characterised in that it includes following step
Suddenly：(1) synthesis of hydroxyl modification rhodamine B：Weigh 0.5g-1g ethylene glycol, 0.5g-1g dicyclohexylcarbodiimide, 0.01g-
The DMAP of 0.05g, is dissolved in 10mL-50mL dichloromethane, then 1g-2g rhodamine B is added dropwise over it
In, after completion of dropping, react 12 hours at ambient temperature, the separated purification of product obtains the rhodamine B of hydroxyl modification；
The structural formula of the rhodamine B of described hydroxyl modification is as follows：
(2) synthesis of carboxyl RAFT reagent：1) potassium hydroxide 3g-4g, ethanol 3mL-5mL are taken, water 10mL-20mL is added to flask
In, stirring；2) Carbon bisulfide 2g-6g is taken to be slowly added in above-mentioned solution, ice bath reacts 2 5h；3) take p-methyl benzene sulfonic chloride
With, after alcohol solvent heating for dissolving, being added in above-mentioned mixed solution, stirring reaction, reaction uses dichloromethane after terminating to 6g-15g
Extraction, saturated solution of sodium bicarbonate washs, anhydrous sodium sulfate drying 12h, filters, and rotary evaporation removes partial solvent, normal hexane
Cross post, dry head product；4) weigh 1.0-1.5 times of azo two isocyano group valeric acid to be dissolved in 30-50ml ethyl acetate solvent, with
Step 3 products therefrom mixing backflow 12h, reaction uses normal hexane after terminating：Ethyl acetate=7:3 eluant proportioning is crossed post and is divided
From after eluent rotary evaporation, dry in vacuum drying oven, obtain oil product to be carboxyl RAFT reagent is 4- cyano group -4-
Ethyl dihydrogen thiocarbonate. base valeric acid；
(3) preparation of rhodamine B base RAFT reagent：Weigh hydroxyl modification rhodamine B, 0.5g- prepared by 0.5g-1g step (1)
Carboxyl prepared by 1g dicyclohexylcarbodiimide, the DMAP of 0.01g-0.05g and 0.1g-0.5g step (2)
RAFT reagent, is then added thereto to 10mL dichloromethane, and reaction 12 hour is stirred at room temperature, and after reaction terminates, separates and carries
Pure obtain target product rhodamine B base RAFT reagent.
3. preparation method according to claim 2 it is characterised in that in described step (1) product specifically separate
Method of purification is：Product dilute hydrochloric acid and water are replaced the rhodamine B that washing can get hydroxyl modification for three times.
4. preparation method according to claim 2 is it is characterised in that product separating-purifying in described step (3)
Concrete grammar is：Product is filtered to remove by-product of dicyclohexylurea, then filtrate concentrated by rotary evaporation obtains crude product, finally again
With silica gel chromatographic column separating-purifying crude product, then it is vacuum dried.
5. preparation method according to claim 4 is it is characterised in that described silica gel chromatography post separation eluant proportioning is second
Acetoacetic ester：Methanol=1:1.
6. a kind of using the rhodamine B base RAFT reagent described in claim 1 prepare fluorescent microsphere method it is characterised in that
It is prepared by following methods：
Weigh 3g-5g acrylonitrile, 3mg-10mg initiator azo-bis-isobutyl cyanide, 35mg-100mg rhodamine B base RAFT reagent, plus
Enter 20mL-50mL dimethyl sulfoxide, be subsequently adding the deionized water of 5mL-10mL, deoxygenation half an hour, be then put in 70 DEG C of oil baths
React 12 hours in pot, obtain red emulsion, then precipitate in deionized water, lyophilization, obtain that there is fluorescent characteristic
Polyacrylonitrile fluorescent microsphere.
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| CN113884473A (en) * | 2021-08-16 | 2022-01-04 | 温州瓯衡检测咨询有限公司 | Preparation method of fluorescence detector for rapidly detecting carbon monoxide and ethylene |
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| CN113884473A (en) * | 2021-08-16 | 2022-01-04 | 温州瓯衡检测咨询有限公司 | Preparation method of fluorescence detector for rapidly detecting carbon monoxide and ethylene |
| CN113884473B (en) * | 2021-08-16 | 2024-04-30 | 温州瓯衡检测咨询有限公司 | Preparation method of fluorescent detector for rapidly detecting carbon monoxide and ethylene |
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