CN107628966B - Preparation method of three-arm chain transfer agent with photoresponse - Google Patents
Preparation method of three-arm chain transfer agent with photoresponse Download PDFInfo
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Abstract
The invention discloses a preparation method of a three-arm chain transfer agent with photoresponse, wherein the structural formula of the three-arm chain transfer agent is as follows:Wherein R is O or NH; the invention provides a preparation method of a three-arm chain transfer agent with photoresponse, and a polymer with a crosslinking point taking the molecule as a center can be generated by reaction due to the existence of an active group on the para position of an azo double bond of the three-arm chain transfer agent.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method of a three-arm chain transfer agent with photoresponse.
Background
Azobenzene is a photoresponsive group that can isomerize from trans to cis under ultraviolet light. An azobenzene group is a photoisomerization group containing a conjugated large pi bond, the cis-trans configuration of which corresponds to different types of electronic transition states. Wherein the trans configuration is stable and strongly absorbed in the ultraviolet region by pi-pi*Generation of an electronic transition; while the absorption of the cis configuration is in the visible range, from n- π*The transition occurs. Under the ultraviolet irradiation, azobenzene is isomerized into cis configuration, n electron obtains enough energy, n-pi*The electron transition becomes the main absorption, the corresponding pi-pi*The electronic transition is weakened, and the absorption in a visible light region is enhanced and the absorption in an ultraviolet light region is reduced in a spectrum; the cis configuration is an unstable form, can be recovered to a trans configuration through thermal relaxation, and the absorption in an ultraviolet region is enhanced, and the configuration transformation is shown in figure 1. After the azobenzene group is isomerized, the UV-Vis spectrum is changed, and the fluorescence emission of benzene is caused. The single or multiple azobenzene groups are generally prepared by diazotisation and azo couplingIn (1). The polyazobenzene molecule is generally prepared by multi-step reaction (see: xudongmei, li wei, CN102336745A, a pentaazobenzene and its synthesis method). The existing three-arm azobenzene derivative has complicated preparation process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a three-arm chain transfer agent with photoresponse.
The technical scheme of the invention is as follows:
A preparation method of a three-arm chain transfer agent with photoresponse is disclosed, wherein the structural formula of the three-arm chain transfer agent is as follows:
Wherein R is O or NH;
The method comprises the following steps:
(1) Reacting 1, 3, 5-tris (4-aminophenyl) benzene with sodium nitrite and hydrochloric acid aqueous solution at the temperature of-20-5 ℃ for 0.5-24 h to generate light yellow diazonium salt solution;
(2) Dissolving a mono-substituted benzene compound in a first solvent to form a mono-substituted benzene compound solution, and placing the solution in an ice bath;
(3) gradually dropwise adding the mono-substituted benzene compound solution obtained in the step (2) into the diazonium salt solution obtained in the step (1), reacting for 2-12 hours at the temperature of-20-5 ℃, and turning the solution into wine red, which indicates that azo coupling reaction occurs to generate the three-arm azobenzene with three functionality.
(4) Adjusting the material obtained in the step (3) to be neutral by using a sodium bicarbonate solution with the mass concentration of 10%, precipitating, filtering, and washing for a plurality of times to obtain a product;
(5) And (3) reacting the product obtained in the step (4) with 2-bromoisobutyryl bromide under the conditions of an acid-binding agent and a second solvent, and purifying by using column chromatography with ethyl acetate and n-hexane as eluent to obtain the three-arm chain transfer agent with photoresponse.
in a preferred embodiment of the present invention, the concentration of hydrochloric acid in the aqueous hydrochloric acid solution in the step (1) is 10 to 25 wt%.
further preferably, the ratio of the 1, 3, 5-tri (4-aminophenyl) benzene to the hydrochloric acid is 1 g: 5-20 mL.
in a preferred embodiment of the present invention, the mono-substituted benzene compound is phenol or aniline.
In a preferred embodiment of the present invention, the first solvent in the step (2) is a mixed solvent of water and ethanol, wherein the volume ratio of water to ethanol is 1: 0-0.7.
further preferably, the mass ratio of the mono-substituted benzene compound to the first solvent is 1: 8-20.
In a preferred embodiment of the present invention, the second solvent in the step (4) is dichloromethane, tetrahydrofuran or chloroform.
in a preferred embodiment of the present invention, the acid-binding agent in the step (4) is triethylamine.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of a three-arm chain transfer agent with photoresponse, and the polymer with a crosslinking point taking the molecule as the center can be generated by reaction due to the existence of active groups on the azo double bond contraposition;
(2) the three-arm chain transfer agent prepared by the invention has the advantages that the molecule is changed from trans-isomer to cis-isomer under ultraviolet light due to the existence of azobenzene, and slowly changed from cis-structure to trans-isomer under white light or dark conditions, so that the polymer in the molecular reaction center has sensitivity to ultraviolet light.
(3) The three-arm polymer prepared by the invention has better rigidity and conjugation effect due to the existence of large benzene rings.
drawings
FIG. 1 shows the principle of configuration transformation of an azobenzene group.
FIG. 2 is a reaction scheme of example 1 of the present invention.
FIG. 3 is a reaction scheme of example 2 of the present invention.
FIG. 4 is a nuclear magnetic hydrogen spectrum of a three-armed azobenzene product of example 1 of the present invention, wherein the abscissa is Chemical shift (ppm); the solvent is d-DMSO.
FIG. 5 is a nuclear magnetic carbon spectrum of a three-arm azobenzene product of example 2 of the present invention, wherein the abscissa is Chemical shift (ppm); the solvent is d-DMSO.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
The reaction principle is shown in figure 2, and the specific reaction steps are as follows:
(1) 0.875g of 1, 3, 5-tris (4-aminophenyl) benzene was added to 6ml of HCl and 6ml of H2reacting in O at 0-5 deg.C to obtain NaNO20.5175g were gradually added dropwise to the reaction and reacted for half an hour to give a pale yellow solution of the diazonium salt.
(2) then 0.795g of phenol is dissolved in 8ml of mixed solution of water and ethanol (the volume ratio of the water to the ethanol is 1: 0.5) to form a mono-substituted phenol compound solution, and the solution is subjected to ice bath to 0-5 ℃.
(3) And (3) dropwise adding the mono-substituted benzene compound solution obtained in the step (2) into the diazonium salt solution obtained in the step (1), and reacting for 2 hours at 0-5 ℃ to change the solution from light yellow to wine red.
(4) adjusting the reacted solution to be neutral by using a sodium bicarbonate solution with the mass concentration of 10%, precipitating, filtering, washing for multiple times, and freeze-drying to obtain the three-arm azobenzene product shown in the figure 4.
(5) Under the condition of acid-binding agent triethylamine and dichloromethane, reacting the three-arm azobenzene product obtained by reaction with 2-bromoisobutyryl bromide to generate a monomer with three terminal groups both having bromine, and performing column chromatography separation by using ethyl acetate and n-hexane as eluent at the volume ratio of 1: 10 to obtain the final product, namely the three-arm chain transfer agent with photoresponse. The final product mass can serve as a crosslinking point for the ATRP reaction.
Example 2
The reaction principle is shown in fig. 3, and the specific reaction steps are as follows:
(1) 0.875g of 1, 3, 5-tris (4-aminophenyl) benzene was added to 6ml of HCl and 6ml of H2Reacting in O at 0-5 deg.C to obtain NaNO20.5175g were gradually added dropwise to the reaction and reacted for half an hour to give a pale yellow solution of the diazonium salt.
(2) Dissolving 0.686g of aniline in 7ml of mixed solution of water and ethanol (the volume ratio of water to ethanol is 1: 0.4) to form a mono-substituted benzene compound solution, and carrying out ice bath to 0-5 ℃.
(3) And (3) dropwise adding the mono-substituted benzene compound solution obtained in the step (2) into the diazonium salt solution obtained in the step (1), and reacting at 0-5 ℃ for 2 hours until the solution gradually turns red, which indicates that azobenzene is generated.
(4) Adjusting the pH value of the solution to be neutral by using a sodium bicarbonate solution with the mass concentration of 10%, generating a precipitate, filtering, and freeze-drying to obtain the three-arm azobenzene product shown in figure 5.
(5) Under the condition of acid-binding agent triethylamine and chloroform, reacting the three-arm azobenzene product obtained by reaction with 2-bromoisobutyryl bromide to generate a monomer with three terminal groups having bromine, and performing column chromatography separation by using ethyl acetate and n-hexane in a volume ratio of 1: 12 as eluent to obtain a final product, namely the three-arm chain transfer agent with photoresponse. The final product can be used as a crosslinking point of ATRP reaction or nucleophilic reaction
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (7)
1. a preparation method of a three-arm chain transfer agent with photoresponse is disclosed, wherein the structural formula of the three-arm chain transfer agent is as follows:
Wherein R is O or NH;
The method comprises the following steps:
(1) Reacting 1, 3, 5-tris (4-aminophenyl) benzene with sodium nitrite and hydrochloric acid aqueous solution at the temperature of-20-5 ℃ for 0.5-24 h to generate light yellow diazonium salt solution;
(2) Dissolving a mono-substituted benzene compound in a first solvent to form a mono-substituted benzene compound solution, and placing the solution in an ice bath, wherein the mono-substituted benzene compound is phenol or aniline;
(3) Gradually dropwise adding the mono-substituted benzene compound solution obtained in the step (2) into the diazonium salt solution obtained in the step (1), reacting for 2-12 hours at the temperature of-20-5 ℃, wherein the solution turns into wine red, which indicates that azo coupling reaction occurs to generate three-arm azobenzene with three functionality;
(4) Adjusting the material obtained in the step (3) to be neutral by using a sodium bicarbonate solution with the mass concentration of 10%, precipitating, filtering, and washing for a plurality of times to obtain a product;
(5) And (3) reacting the product obtained in the step (4) with 2-bromoisobutyryl bromide under the conditions of an acid-binding agent and a second solvent, and then purifying by using column chromatography with a mixed solvent of ethyl acetate and n-hexane as an eluent to obtain the three-arm chain transfer agent with photoresponse.
2. the method of claim 1, wherein: the concentration of hydrochloric acid in the hydrochloric acid aqueous solution in the step (1) is 10-25 wt%.
3. The method of claim 2, wherein: the ratio of the 1, 3, 5-tri (4-aminophenyl) benzene to the hydrochloric acid aqueous solution is 1 g: 5-20 mL.
4. the method of claim 1, wherein: the first solvent in the step (2) is a mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 1: 0-0.7.
5. the method of claim 4, wherein: the mass ratio of the mono-substituted benzene compound to the first solvent is 1: 8-20.
6. the method of claim 1, wherein: the second solvent in the step (5) is dichloromethane, tetrahydrofuran or chloroform.
7. The method of claim 1, wherein: and (3) the acid-binding agent in the step (5) is triethylamine.
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