CN108929243B - Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof - Google Patents

Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof Download PDF

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CN108929243B
CN108929243B CN201810971723.4A CN201810971723A CN108929243B CN 108929243 B CN108929243 B CN 108929243B CN 201810971723 A CN201810971723 A CN 201810971723A CN 108929243 B CN108929243 B CN 108929243B
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CN108929243A (en
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周宏伟
苏凯欣
王大明
孙宁伟
陈春海
赵晓刚
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Jilin University
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Abstract

The invention provides a diamine monomer containing an asymmetric fluorophore structure and having a structure shown in formula I, and polyamide or polyimide prepared by using the diamine monomer as a monomer can improve the solubility and the film-forming property of a polymer while keeping the thermal stability of the polymer, and endow the polymer with excellent electrochromic and electrically-controlled fluorescence properties. Specifically, in the diamine monomer containing the asymmetric fluorophore structure, the derivative of triarylamine provides an electroactive site; the introduction of the fluorophore can enhance the fluorescence intensity of the polymer and improve the contrast of a fluorescence switch; the asymmetric structure can effectively weaken the accumulation effect of the polymer, enhance the solubility and solid fluorescence and accelerate the response speed. According to the description of the embodiment, the electrochromism and the electrically controlled fluorescence performance of the polyamide or the polyimide prepared by the diamine monomer containing the asymmetric fluorophore structure are obviously improved.

Description

Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrochromism and electric control fluorescence, in particular to a diamine monomer containing an asymmetric fluorophore structure, and a preparation method and application thereof.
Background
Electrochromism refers to a phenomenon in which optical properties (reflectivity, transmittance, absorption, and the like) of a material undergo a stable and reversible color change under the action of an applied electric field, and is visually represented as a reversible change in color and transparency. In 1969, s.k.deb reported the first tungsten trioxide electrochromic material. After that, researchers successively discovered the electrochromic properties of small organic molecules and conducting polymers. Electrically controlled fluorescence refers to reversible regulation of the fluorescence intensity or color of a material under electrical stimulation. Among them, triphenylamine derivatives have attracted much attention because of their colorless behavior and low driving voltage. The cation free radical can effectively quench fluorescence while causing color change.
Polyamides and polyimides have attracted the attention of many researchers by virtue of excellent thermal properties, mechanical properties and excellent corrosion resistance. However, their strong intermolecular interactions result in poor solubility. Triphenylamine with a propeller structure is introduced into polyamide and polyimide, so that the solubility of the triphenylamine is improved, and the electrochromic and electrically-controlled fluorescence properties of the triphenylamine are endowed.
However, triphenylamine is weak in fluorescence, and in addition, close packing of polyamide and polyimide significantly quenches solid state fluorescence, resulting in a decrease in ion doping speed. In order to meet commercial requirements, it is of great significance to prepare diamine monomers with novel structures and prepare electrochromic and electrically controlled fluorescent materials with easy processing and high performance from the diamine monomers.
Disclosure of Invention
The invention aims to provide a diamine monomer containing an asymmetric fluorophore structure for preparing polyamide or polyimide with excellent electrochromic and electrically-controlled fluorescence properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a diamine monomer containing an asymmetric fluorophore structure, which has a structure shown in a formula I:
Figure BDA0001776367190000021
in the formula I, R1Is composed of
Figure BDA0001776367190000022
R2Is composed of
Figure BDA0001776367190000023
Preferably, the diamine monomer containing an asymmetric fluorophore structure comprises N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene, N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene or N-1-aminoanthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene.
The invention also provides a preparation method of the diamine monomer containing the asymmetric fluorophore structure, which comprises the following steps:
4-fluoronitrobenzene and R2-NH2Mixing triethylamine and dimethyl sulfoxide to perform nucleophilic substitution reaction I to obtain a compound with a structure shown in a formula II;
the compound with the structure shown in the formula II, copper powder, potassium carbonate, 18-crown-6 and R1Mixing the-X and o-dichlorobenzene to perform Ullmann reaction to obtain a compound with a structure shown in a formula III; the R is1X in X is Cl, Br or I;
mixing the compound with the structure shown in the formula III, Pd/C, hydrazine hydrate and dioxane to perform a reduction reaction I to obtain a compound with the structure shown in the formula IV;
mixing a compound with a structure shown in a formula IV, triethylamine, N-dimethylformamide and 3, 5-dinitrobenzoyl chloride to perform nucleophilic substitution reaction II to obtain a compound with a structure shown in a formula V;
mixing a compound with a structure shown in a formula V, Pd/C, hydrazine hydrate and dioxane to perform a reduction reaction II to obtain a compound with a structure shown in a formula I;
Figure BDA0001776367190000031
preferably, the temperature of the nucleophilic substitution reaction I is 80-100 ℃, and the time of the nucleophilic substitution reaction I is 30-45 h.
Preferably, the temperature of the Ullmann reaction is 140-180 ℃, and the time of the Ullmann reaction is 12-20 h.
Preferably, the temperature of the reduction reaction I is 70-90 ℃, and the time of the reduction reaction I is 1-24 hours.
Preferably, the temperature of the nucleophilic substitution reaction II is 135-145 ℃, and the time of the nucleophilic substitution reaction II is 3-8 h.
Preferably, the temperature of the reduction reaction II is 75-95 ℃, and the time of the reduction reaction II is 3-30 h.
The invention also provides application of the diamine monomer containing the asymmetric fluorophore structure in electrochromic and electrically controlled fluorescent materials, wherein the electrochromic and electrically controlled fluorescent materials are polyamide or polyimide.
Preferably, the preparation method of the polyamide comprises the following steps:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound with a structure shown in a formula a, and carrying out polymerization reaction to obtain polyamide;
Figure BDA0001776367190000032
in the formula a, Ar is
Figure BDA0001776367190000033
The preparation method of the polyimide comprises the following steps:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound having a structure shown in a formula b, and carrying out polymerization reaction to obtain polyimide;
Figure BDA0001776367190000034
in the formula b, Ar' is
Figure BDA0001776367190000041
The invention provides a diamine monomer containing an asymmetric fluorophore structure and having a structure shown in formula I, and polyamide or polyimide prepared by using the diamine monomer as a monomer can improve the solubility and the film-forming property of a polymer while keeping the thermal stability of the polymer, and endow the polymer with excellent electrochromic and electrically-controlled fluorescence properties. Specifically, in the diamine monomer containing the asymmetric fluorophore structure, the derivative of triarylamine provides an electroactive site; the introduction of the fluorophore can enhance the fluorescence intensity of the polymer and improve the contrast of a fluorescence switch; the asymmetric structure can effectively weaken the accumulation effect of the polymer, enhance the solubility and solid fluorescence and accelerate the response speed. According to the description of the embodiment, the electrochromism and the electrically controlled fluorescence performance of the polyamide or the polyimide prepared by the diamine monomer containing the asymmetric fluorophore structure are obviously improved.
Drawings
FIG. 1 is a nuclear magnetic spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 1;
FIG. 2 is an IR spectrum of a polyimide of the type N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 together with cyclohexane tetracarboxylic dianhydride;
FIG. 3 is a TGA graph of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and a polyimide of the cyclohexane tetracarboxylic dianhydride type;
FIG. 4 is a cyclic voltammogram of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and a polyimide of the cyclohexane tetracarboxylic dianhydride type;
FIG. 5 is an electrochromic spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and a polyimide of the cyclohexane tetracarboxylic dianhydride type;
FIG. 6 is an electrochromic response time spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and a cyclohexane tetracarboxylic dianhydride-type polyimide;
FIG. 7 shows an electrically controlled fluorescence spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and a polyimide of cyclohexane tetracarboxylic dianhydride type.
Detailed Description
The invention provides a diamine monomer containing an asymmetric fluorophore structure, which has a structure shown in a formula I:
Figure BDA0001776367190000051
in the formula I, R1Is composed of
Figure BDA0001776367190000052
R2Is composed of
Figure BDA0001776367190000053
In the present invention, the diamine monomer containing an asymmetric fluorophore structure includes N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene, N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene, or N-1-aminoanthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene.
The invention also provides a preparation method of the diamine monomer containing the asymmetric fluorophore structure, which comprises the following steps:
4-fluoronitrobenzene and R2-NH2Mixing triethylamine and dimethyl sulfoxide to perform nucleophilic substitution reaction I to obtain a compound with a structure shown in a formula II;
mixing a compound with a structure shown in formula II, copper powder, potassium carbonate, 18-crown-6 and R1Mixing the-X and the o-dichlorobenzene to perform Ullmann reaction to obtain a compound with a structure shown in a formula III;
mixing a compound with a structure shown in a formula III, Pd/C, hydrazine hydrate and dioxane, and carrying out a reduction reaction I to obtain a compound with a structure shown in a formula IV;
mixing a compound with a structure shown in a formula IV, triethylamine, N-dimethylformamide and 3, 5-dinitrobenzoyl chloride to perform nucleophilic substitution reaction II to obtain a compound with a structure shown in a formula V;
mixing a compound with a structure shown in a formula V, Pd/C, hydrazine hydrate and dioxane to perform a reduction reaction II to obtain a compound with a structure shown in a formula I;
Figure BDA0001776367190000061
in the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The invention uses 4-fluoronitrobenzene and R2-NH2Mixing triethylamine and dimethyl sulfoxide to perform nucleophilic substitution reaction I to obtain a compound with a structure shown in a formula II. In the invention, the 4-fluoronitrobenzene and R2-NH2And triethylamine are preferably present in a molar ratio of 1: (1.3-1.5): (1.3 to 1.5), more preferably 1: (1.35-1.45): (1.35-1.45). In the invention, the volume ratio of the amount of the 4-fluoronitrobenzene substance to the dimethyl sulfoxide is preferably (0.9-0.94) mol:1L, more preferably (0.91 to 0.93) mol:1L of the compound.
In the invention, the 4-fluoronitrobenzene and R2-NH2The total solid content of the reaction system obtained by mixing triethylamine and dimethyl sulfoxide is preferably 15-28%, more preferably 16-27%, and most preferably 18-26%.
In the invention, the 4-fluoronitrobenzene and R2-NH2And triethylamine is used as a reactant, and dimethyl sulfoxide is used as a reaction solvent.
The order of addition of the above-mentioned raw materials is not particularly limited in the present invention, and the addition can be carried out by the order of addition well known to those skilled in the artMixing; in the invention, firstly, 4-fluoronitrobenzene and R are mixed2-NH2And triethylamine were mixed, and then dimethyl sulfoxide was added to the resulting mixture.
In the present invention, the mixing is preferably carried out in a protective atmosphere, and the present invention does not limit the kind of the protective gas for providing the protective atmosphere in any way, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
The mixing method and the mixing conditions are not particularly limited in the present invention, and the mixing may be performed by a mixing method and mixing conditions known to those skilled in the art.
In the invention, the temperature of the nucleophilic substitution reaction I is preferably 80-100 ℃, more preferably 85-95 ℃, and most preferably 88-92 ℃; the time of the nucleophilic substitution reaction I is preferably 30-45 h, more preferably 35-42 h, and most preferably 38-40 h.
In the present invention, the nucleophilic substitution reaction i is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the present invention, the nucleophilic substitution reaction i is preferably performed under stirring conditions; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
The device for the nucleophilic substitution reaction I is not limited in any way, and the reaction can be carried out by adopting a device which is well known by the technical personnel in the field and can realize the reaction; in the present invention, a three-neck flask equipped with mechanical stirring can be specifically selected.
After the nucleophilic substitution reaction i is completed, the present invention preferably subjects the resulting product system to a post-treatment, which preferably comprises the steps of:
and mixing the product system with an ice-water mixture, carrying out suction filtration on the obtained material, and recrystallizing the obtained filter cake to obtain the compound with the structure shown in the formula II.
The mixing method and conditions are not limited in any way, and the mixing method and conditions known to those skilled in the art can be used.
The invention does not have any special limitation on the suction filtration, and the aim of solid-liquid separation can be achieved by adopting suction filtration conditions well known to those skilled in the art.
In the present invention, the agent for recrystallization is preferably ethanol and/or N, N-dimethylformamide; when the recrystallization reagent is ethanol and N, N-dimethylformamide, the volume ratio of the two substances is preferably (0.5-2): 1, more preferably (0.8 to 1.2): 1.
after the compound with the structure shown in the formula II is obtained, the invention uses the compound with the structure shown in the formula II, copper powder, potassium carbonate, 18-crown-6 and R1Mixing the-X and o-dichlorobenzene to perform Ullmann reaction to obtain a compound with a structure shown in a formula III; the R is1X in X is Cl, Br or I.
In the present invention, the compound having the structure represented by the formula II, copper powder, potassium carbonate, 18-crown-6 and R1The molar ratio of-X is preferably (1.1-1.5): (3-6): (3-6): (0.5-1): 1, more preferably (1.2 to 1.4): (4-5.5): (4-5.5): (0.6-0.8): 1.
in the present invention, the volume ratio of the amount of the compound having the structure represented by formula ii to o-dichlorobenzene is preferably (0.1 to 0.7) mol:1L, more preferably (0.2 to 0.6) mol:1L of the compound.
In the invention, the compound with the structure shown in the formula II, copper powder, potassium carbonate, 18-crown-6 and R1The total solid content of the reaction system obtained after mixing-X and o-dichlorobenzene is preferably 15-30%, more preferably 18-25%, and most preferably 20-23%.
In the invention, the copper powder is used as a catalyst, potassium carbonate is used as a cocatalyst, 18-crown-6 is used as a phase transfer catalyst, and o-dichlorobenzene is used as a solvent.
The order of mixing is not particularly limited, and the mixing may be performed in any order. In the present invention, it can be specifically selected to firstA compound having a structure represented by formula II, copper powder, potassium carbonate, 18-crown-6 and R1-X and then o-dichlorobenzene is added to the resulting mixture.
In the present invention, the mixing is preferably carried out in a protective atmosphere, and the present invention does not limit the kind of the protective gas for providing the protective atmosphere in any way, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
The mixing method and the mixing conditions are not particularly limited in the present invention, and the mixing may be performed by a mixing method and mixing conditions known to those skilled in the art.
In the invention, the temperature of the Ullmann reaction is preferably 140-180 ℃, more preferably 150-170 ℃, and most preferably 155-165 ℃; the time of the Ullmann reaction is preferably 12-20 h, and more preferably 14-18 h.
In the present invention, the ullmann reaction is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the present invention, the ullmann reaction is preferably carried out under stirring conditions; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
The device for the Ullmann reaction is not limited in any way, and the device which can realize the Ullmann reaction and is well known to the technical personnel in the field can be used for carrying out the reaction; in the present invention, a three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser can be specifically selected.
After the Ullmann reaction is finished, the invention preferably carries out post-treatment on the obtained product system, wherein the post-treatment comprises the following steps:
and carrying out suction filtration on the product system, carrying out reduced pressure distillation on the obtained filtrate, and recrystallizing the obtained residue to obtain the compound with the structure shown in the formula III.
The invention does not have any special limitation on the suction filtration, and the aim of solid-liquid separation can be achieved by adopting suction filtration conditions well known to those skilled in the art.
The reduced pressure distillation is not particularly limited in the present invention, and the o-dichlorobenzene may be removed by reduced pressure distillation known to those skilled in the art.
In the present invention, the agent for recrystallization is preferably a mixture of ethanol and N, N-dimethylacetamide; in the present invention, the volume ratio of ethanol to N, N-dimethylacetamide is preferably 1: (1-3), more preferably 1: (1.5-2.5).
After the compound with the structure shown in the formula III is obtained, the compound with the structure shown in the formula III, Pd/C, hydrazine hydrate and dioxane are mixed to carry out reduction reaction I, and the compound with the structure shown in the formula IV is obtained. In the present invention, the hydrazine hydrate is preferably an aqueous solution of hydrazine hydrate; the mass fraction of hydrazine hydrate in the hydrazine hydrate aqueous solution is preferably 70-90%, more preferably 75-85%, and most preferably 78-92%.
In the present invention, the mass ratio of Pd to C in the Pd/C is preferably (0.05-0.2): 1, more preferably (0.08-0.15): 1, most preferably (0.1 to 0.12): 1.
in the present invention, the mass ratio of the compound having the structure represented by the formula iii to Pd/C is preferably 1: (0.3 to 0.4), more preferably 1: (0.32 to 0.38), most preferably 1: (0.34-0.36).
In the present invention, the molar ratio of the compound having the structure represented by formula iii to hydrazine hydrate is preferably 1: (5-20), more preferably 1: (8-16), most preferably 1: (12-14).
In the present invention, the volume ratio of the amount of the substance of the compound having the structure represented by the formula III to dioxane is preferably (0.1 to 0.3) mol:1L, more preferably (0.15 to 0.25) mol:1L, most preferably (0.18 to 0.22) mol:1L of the compound.
In the invention, the total solid content of the reaction system obtained by mixing the compound with the structure shown in the formula III, Pd/C, hydrazine hydrate and dioxane is preferably 10-20%, more preferably 12-18%, and most preferably 14-16%.
In the invention, Pd/C is used as a catalyst, hydrazine hydrate is used as a reducing agent, and dioxane is used as a solvent.
In the present invention, the order of mixing is preferably to mix the compound having the structure shown in formula iii, Pd/C and dioxane, and then to drop hydrazine hydrate into the obtained mixture, and the dropping of hydrazine hydrate is performed by using a dropping manner and a dropping rate well known to those skilled in the art without any particular limitation in the present invention.
In the present invention, the mixing is preferably performed under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and stirring may be performed under stirring conditions known to those skilled in the art.
The mixing manner and mixing conditions are not particularly limited in the present invention, and mixing may be performed by using a mixing manner and mixing conditions known to those skilled in the art.
In the invention, the temperature of the reduction reaction I is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 78-82 ℃; in the present invention, the reduction reaction i is preferably carried out under reflux. In the invention, the time of the reduction reaction I is preferably 1-24 h, more preferably 5-20 h, and most preferably 10-15 h.
In the present invention, the reduction reaction i is preferably carried out under stirring; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
The device for the reduction reaction I is not limited in any way, and the reaction can be carried out by adopting a device which is well known by the technical personnel in the field and can realize the reaction; in the present invention, a three-necked flask equipped with a magnetic stirrer and a condenser can be specifically selected.
After the reduction reaction i is completed, the present invention preferably performs a post-treatment of the resulting product system, said post-treatment comprising the steps of:
and filtering the product system, and carrying out reduced pressure concentration and cooling precipitation on the obtained filtrate to obtain the compound with the structure shown in the formula IV.
The present invention does not have any particular limitation on the filtration, and Pd/C can be removed by using filtration conditions well known to those skilled in the art. In the present invention, the filtration is preferably carried out while it is hot after the reduction reaction I is completed.
In the present invention, the concentration under reduced pressure is performed so that the ratio of the volume of the concentrated filtrate to the original volume is preferably less than 1, more preferably less than 0.8, and most preferably less than 0.4; the concentration under reduced pressure in the present invention is not particularly limited, and may be a concentration under reduced pressure known to those skilled in the art.
In the present invention, the cooling precipitation is preferably performed in a protective atmosphere, and the present invention does not limit the kind of the protective gas providing the protective atmosphere at all, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
After the compound with the structure shown in the formula IV is obtained, the compound with the structure shown in the formula IV, triethylamine, N-dimethylformamide and 3, 5-dinitrobenzoyl chloride are mixed to carry out nucleophilic substitution reaction II, and the compound with the structure shown in the formula V is obtained. In the present invention, the molar ratio of the compound having the structure represented by formula iv, triethylamine and 3, 5-dinitrobenzoyl chloride is preferably 1: (1-1.7): (1 to 1.7), more preferably 1: (1.2-1.3): (1.2-1.3).
In the invention, the volume ratio of the amount of the compound having the structure shown in formula IV to N, N-dimethylformamide is preferably (0.4-0.7) mol:1L, more preferably (0.45 to 0.65) mol:1L, most preferably (0.5-0.6) mol:1L of the compound.
In the invention, the total solid content of the reaction system obtained by mixing the compound having the structure shown in the formula IV, triethylamine, N-dimethylformamide and 3, 5-dinitrobenzoyl chloride is preferably 15-30%, more preferably 20-28%, and most preferably 22-26%.
In the invention, the compound with the structure shown in the formula IV and 3, 5-dinitrobenzoyl chloride are used as reactants, the N, N-dimethylformamide is used as a solvent, and the triethylamine is used as a catalyst.
In the present invention, the mixing sequence is preferably that the compound having the structure represented by formula IV, triethylamine and N, N-dimethylformamide are mixed, and then 3, 5-dinitrobenzoyl chloride is added dropwise to the obtained mixture. In the present invention, the volume ratio of the amount of the triethylamine to the N, N-dimethylformamide is preferably (0.6 to 1.0) mol: 1mL, more preferably (0.7 to 0.9) mol:1L, most preferably (0.75-0.85) mol:1L of the compound. The concentration of the N, N-dimethylformamide solution of the 3, 5-dinitrobenzoyl chloride in the invention is preferably (1-3.5) mol/L, more preferably (1.5-3) mol/L, and most preferably (2-2.5) mol/L. The addition temperature of the solution of 3, 5-dinitrobenzoyl chloride in N, N-dimethylformamide in the present invention is preferably room temperature. The N, N-dimethylformamide solution of the 3, 5-dinitrobenzoyl chloride is preferably added dropwise; in the invention, the dripping time is preferably 0.5-3 h, more preferably 1-2.5 h, and most preferably 1.5-2 h.
After the dropwise addition is finished, the obtained system is subjected to temperature rise reaction; the reaction temperature is preferably 130-150 ℃, and more preferably 135-145 ℃; in the present invention, the reaction is preferably carried out under reflux. The reaction time is preferably 12-20 h, more preferably 14-18 h, and most preferably 15-16 h.
In the present invention, the nucleophilic substitution reaction II is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
The device for the nucleophilic substitution reaction II is not limited in any way, and the reaction can be carried out by adopting a device which is well known by the technical personnel in the field and can realize the reaction; in the present invention, a three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser can be specifically selected.
After the nucleophilic substitution reaction II is completed, the present invention preferably performs a post-treatment of the resulting product system, said post-treatment comprising the steps of:
and mixing the product system with ethanol, carrying out suction filtration on the obtained material, and recrystallizing the obtained filter cake to obtain the compound with the structure shown in the formula V.
The mixing method and conditions are not limited in any way, and the mixing method and conditions known to those skilled in the art can be used. The amount of ethanol used in the present invention is not particularly limited, and may be an amount well known to those skilled in the art.
The invention does not have any special limitation on the suction filtration, and the aim of solid-liquid separation can be achieved by adopting suction filtration conditions well known to those skilled in the art.
In the present invention, the agent for recrystallization is preferably ethanol and N, N-dimethylacetamide; in the present invention, the volume ratio of ethanol to N, N-dimethylformamide is preferably 1: (2-4), more preferably 1: (2.2 to 3.8), most preferably 1: (2.8 to 3.2)
After the compound with the structure shown in the formula V is obtained, the compound with the structure shown in the formula V, Pd/C, hydrazine hydrate and dioxane are mixed to carry out reduction reaction II, and the compound with the structure shown in the formula I is obtained. In the present invention, the mass ratio of Pd to C in the Pd/C is preferably (0.05-0.2): 1, more preferably (0.5-0.15): 1, most preferably (0.8 to 0.12): 1.
in the present invention, the mass ratio of the compound having the structure represented by formula v to Pd/C is preferably 1: (0.1 to 0.4), more preferably 1: (0.2 to 0.3), most preferably 1: (0.24-0.26).
In the present invention, the molar ratio of the compound having the structure represented by formula v to hydrazine hydrate is preferably 1: (15-40), more preferably 1: (20-30), and most preferably 1: (23-27).
In the present invention, the volume ratio of the amount of the substance of the compound having the structure represented by formula V to dioxane is preferably (0.1 to 0.2) mol:1L, more preferably (0.12 to 0.18) mol:1L, most preferably (0.14-0.16) mol:1L of the compound.
In the invention, the total solid content of the reaction system obtained by mixing the compound with the structure shown in the formula V, Pd/C, hydrazine hydrate and dioxane is preferably 10-20%, more preferably 12-18%, and most preferably 14-16%.
In the invention, Pd/C is used as a catalyst, hydrazine hydrate is used as a reducing agent, and dioxane is used as a solvent.
In the present invention, the mixing sequence is preferably that the compound having the structure represented by formula V, Pd/C and dioxane are mixed first, and then hydrazine hydrate is added dropwise to the resulting mixture.
In the present invention, the mixing is preferably performed under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and stirring may be performed under stirring conditions known to those skilled in the art.
The mixing manner and mixing conditions are not particularly limited in the present invention, and mixing may be performed by using a mixing manner and mixing conditions known to those skilled in the art.
In the invention, the temperature of the reduction reaction II is preferably 75-95 ℃, more preferably 80-90 ℃, and most preferably 83-86 ℃; in the present invention, the reduction reaction II is preferably carried out under reflux. In the invention, the time of the reduction reaction II is preferably 3-30 h, more preferably 10-20 h, and most preferably 12-15 h.
In the present invention, the reduction reaction ii is preferably carried out under stirring; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
The device for the reduction reaction II is not limited in any way, and the reaction can be carried out by adopting a device which is well known by the technical personnel in the field and can realize the reaction; in the present invention, a three-necked flask equipped with a magnetic stirrer and a condenser can be specifically selected.
After the reduction reaction II is completed, the invention preferably carries out post-treatment on the obtained product system, wherein the post-treatment comprises the following steps:
and filtering the product system, concentrating the obtained filtrate under reduced pressure, and cooling to precipitate the compound with the structure shown in the formula I.
The present invention does not have any particular limitation on the filtration, and Pd/C can be removed by using filtration conditions well known to those skilled in the art. In the present invention, the filtration is preferably a hot filtration after the completion of the reduction reaction II.
In the present invention, the concentration under reduced pressure is preferably such that the ratio of the volume of the filtrate after concentration to the original volume is preferably less than 1, more preferably less than 0.8, and most preferably less than 0.4; the concentration under reduced pressure in the present invention is not particularly limited, and may be a concentration under reduced pressure known to those skilled in the art.
In the present invention, the cooling precipitation is preferably performed in a protective atmosphere, and the present invention does not have any particular limitation on the type of protective gas used for providing the protective atmosphere, and protective gases well known to those skilled in the art, such as nitrogen; the specific process of cooling precipitation is not limited in any way, and the cooling precipitation process known to those skilled in the art can be adopted.
The invention also provides application of the diamine monomer containing the asymmetric fluorophore structure in electrochromic and electrically controlled fluorescent materials, wherein the electrochromic and electrically controlled fluorescent materials are polyamide or polyimide.
In the present invention, the polyamide has a structure represented by formula c:
Figure BDA0001776367190000141
in the formula c, Ar is
Figure BDA0001776367190000142
n is an integer of 30 to 100.
The polyimide has a structure shown in a formula d:
Figure BDA0001776367190000143
in the formula d, Ar' is
Figure BDA0001776367190000144
m is an integer of 30 to 100.
In the present invention, the method for producing the polyamide preferably comprises the steps of:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound with a structure shown in a formula a, and carrying out polymerization reaction to obtain polyamide;
Figure BDA0001776367190000145
in the formula a, Ar is
Figure BDA0001776367190000146
In the present invention, the molar ratio of the diamine monomer containing an asymmetric fluorophore structure to the compound having the structure represented by formula a is preferably 1: 1.
in the invention, the polymerization reaction temperature is preferably 110-130 ℃, more preferably 115-125 ℃, and most preferably 118-122 ℃; the time of the polymerization reaction is preferably 3 to 6 hours, more preferably 3.5 to 6 hours, and most preferably 4 to 5 hours.
In the present invention, the polymerization reaction is preferably carried out in the presence of a catalyst; in the present invention, the catalyst is preferably calcium chloride; in the invention, the ratio of the mass of the catalyst to the total mass of the diamine monomer containing the asymmetric fluorophore structure is preferably (0.15-0.35): 1, more preferably (0.18 to 0.3): 1.
in the present invention, the polymerization reaction is preferably carried out in the presence of a condensing agent; in the present invention, the condensing agent is preferably triphenyl phosphite and pyridine; in the invention, the volume ratio of triphenyl phosphite to pyridine is preferably (1.8-2.2): 1, more preferably (1.9 to 2.1): 1. in the present invention, the ratio of the volume of triphenyl phosphite to the amount of the diamine monomer containing an asymmetric fluorophore structure is preferably 1L: (0.8 to 1.2) mol, more preferably 1L: (0.9-1.1) mol.
In the present invention, the polymerization reaction is preferably carried out in the presence of an organic solvent; in the present invention, the organic solvent is preferably N-methylpyrrolidone; in the present invention, the ratio of the amount of the substance containing the diamine monomer having an asymmetric fluorophore structure to the volume of the solvent is preferably 1 mol: (2-3) L, more preferably 1 mol: (2.2-2.8) L, most preferably 1 mol: (2.4-2.6) L.
In the present invention, the total solid content of the reaction system of the polymerization reaction is preferably 15% to 30%, more preferably 18% to 28%, and most preferably 22% to 26%.
In the present invention, the polymerization reaction is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the present invention, the polymerization reaction is preferably carried out under stirring conditions; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
After the polymerization reaction is completed, the present invention preferably performs a post-treatment on the obtained product system, wherein the post-treatment comprises the following steps:
and mixing the product system with ethanol, washing and drying to obtain the polyamide.
The present invention does not have any particular limitation in the mixing, and the mixing may be carried out under mixing conditions well known to those skilled in the art; in the present invention, the purpose of mixing the product system with ethanol is to precipitate out the polyamide.
In the present invention, the washing liquid for washing is preferably ethanol and water; the invention does not have any special limitation on the washing times, and the obtained polyamide is washed cleanly.
The drying method of the present invention is not particularly limited, and drying may be carried out under drying conditions known to those skilled in the art.
In the present invention, the preparation method of the polyimide preferably includes the steps of:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound having a structure shown in a formula b, and carrying out polymerization reaction to obtain polyimide;
Figure BDA0001776367190000161
in the formula b, Ar' is
Figure BDA0001776367190000162
In the present invention, the molar ratio of the diamine monomer containing an asymmetric fluorophore structure to the compound having the structure represented by formula b is preferably 1: 1.
in the invention, the polymerization reaction temperature is preferably 160-180 ℃, more preferably 165-175 ℃, and most preferably 168-172 ℃; the time of the polymerization reaction is preferably 8-20 h, more preferably 10-18 h, and most preferably 13-16 h.
In the present invention, the polymerization reaction is preferably carried out in the presence of isoquinoline. In the invention, the molar ratio of the volume of the isoquinoline to the diamine monomer containing the asymmetric fluorophore structure is preferably (0.03-0.09) L: 1mol, more preferably (0.04 to 0.08) L:1 mol. In the invention, the addition time of the isoquinoline is preferably 12-20 h, more preferably 14-18 h, and most preferably 15-16 h after the diamine monomer containing the asymmetric fluorophore structure reacts with the compound having the structure shown in the formula b at room temperature.
In the invention, the reaction of the diamine monomer containing the asymmetric fluorophore structure and the compound with the structure shown in the formula b at room temperature is polycondensation reaction; the isoquinoline reacts with diamine monomer containing asymmetric fluorophore structure and dianhydride at room temperature for 12-20 h, and then is dehydrated.
In the present invention, the polymerization reaction is preferably carried out in the presence of an organic solvent; in the present invention, the solvent is preferably N-methylpyrrolidone; in the present invention, the volume ratio of the amount of the diamine monomer containing an asymmetric fluorophore structure to the solvent is preferably (0.4 to 0.6) mol:1L, more preferably (0.45 to 0.55) mol:1L, and most preferably (0.48 to 0.52) mol: 1L.
In the present invention, the total solid content of the reaction system of the polymerization reaction is preferably 25% to 40%, more preferably 28% to 35%, and most preferably 30% to 32%.
In the present invention, the polymerization reaction is preferably carried out in a protective atmosphere, and the kind of the protective gas for providing the protective atmosphere is not particularly limited, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the present invention, the polymerization reaction is preferably carried out under stirring conditions; the stirring is not particularly limited in the present invention, and the stirring may be carried out under stirring conditions known to those skilled in the art.
After the polymerization reaction is completed, the present invention preferably performs a post-treatment on the obtained product system, wherein the post-treatment comprises the following steps:
and mixing the product system with ethanol, washing and drying to obtain the polyimide.
The present invention does not have any particular limitation in the mixing, and the mixing may be carried out under mixing conditions well known to those skilled in the art; in the present invention, the purpose of mixing the product system with ethanol is to precipitate polyimide.
In the present invention, the washing liquid is preferably ethanol; the washing method is not limited in any way, and the washing method known to those skilled in the art is adopted for washing, and in the invention, the washing can be specifically reflux washing; the invention does not have any special limitation on the washing times, and the obtained polyimide is washed cleanly.
The drying method of the present invention is not particularly limited, and drying may be carried out under drying conditions known to those skilled in the art.
The diamine monomer containing an asymmetric fluorophore structure and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
The preparation method of the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene has the following structural formula:
Figure BDA0001776367190000171
a500 mL three-necked flask equipped with a mechanical stirrer was charged with 35.3g (250mmol) of 4-fluoronitrobenzene, 40.0g (325mmol) of p-anisidine, and 32.9g (325mmol) of triethylamine under nitrogen, followed by 273mL of dimethyl sulfoxide, and reacted at 85 ℃ for 38 hours. Discharging the mixture in an ice-water mixture at room temperature, performing suction filtration, and recrystallizing a filter cake by using ethanol and N, N-dimethylformamide (V: V ═ 1:1), thereby obtaining 45g of orange-red acicular crystal 4-nitro-4' -methoxydiphenylamine with the yield of 74%;
in a 250mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 10.0g (35.6mmol) of 1-bromopyrene, 9.2g (37.4mmol) of 4-methoxy-4' -nitrodiphenylamine, 9.0g (142.2mmol) of copper powder, 19.6g (142.2mmol) of potassium carbonate and 4.7g (17.8mmol) of 18-crown-6 were added under nitrogen, and then 220mL of o-dichlorobenzene was added and reacted at 160 ℃ for 18 hours; carrying out suction filtration while the product is hot, distilling off o-dichlorobenzene under reduced pressure, and recrystallizing the obtained crude product with ethanol and N, N-dimethylacetamide (V: V ═ 1:2) to obtain 9.6g of 4-nitrophenyl-4' -methoxyphenyl-1-aminopyrene with the yield of 60%;
7.0g (15.6mmol) of 4-nitrophenyl-4 '-methoxyphenyl-1-aminopyrene, 70mL of dioxane and 2.4g of Pd with the mass fraction of 10% in a 250mL three-necked flask provided with a magnetic stirrer and a condenser tube are added, and after heating to reflux, the mixture is slowly added dropwise, wherein the molar ratio of the mixture to the 4-nitrophenyl-4' -methoxyphenyl-1-aminopyrene is 10: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 18 hours under the reflux state; filtering the reaction solution while the reaction solution is hot to remove Pd/C, concentrating the filtrate under reduced pressure to 1/3 of the original volume, and cooling and separating out the solution in the nitrogen atmosphere to obtain 6.2g of 4-aminophenyl-4' -methoxyphenyl-1-aminopyrene with the yield of 89%;
a250 mL three-necked flask equipped with a magnetic stirrer, a thermometer, and a condenser was charged with 5.8g (14.0mmol) of 4-aminophenyl-4' -methoxyphenyl-1-aminopyrene and 1.6g (15.4mmol) of triethylamine and 20mL of N, N-dimethylformamide under stirring and nitrogen protection. Then, 3.5g (15.4mmol) of 3, 5-dinitrobenzoyl chloride was dissolved in 10mL of N, N-dimethylformamide, and then it was slowly dropped into a three-necked flask with a rubber-tipped dropper. Stirring at normal temperature for 3h, and heating to 140 ℃ for reaction for 16 h; discharging the mixture into ethanol at room temperature, performing suction filtration, and recrystallizing the filter cake with ethanol and N, N-dimethylacetamide to obtain 7.3g of N-4-methoxyphenyl-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminopyrene with a yield of 85%;
5.2g (8.6mmol) of N-4-methoxyphenyl-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminopyrene, 50mL of dioxane and 2.0g of Pd/C with the mass fraction of 10 percent are added into a 250mL three-necked flask provided with a magnetic stirrer and a condenser tube, and after the mixture is heated to reflux, the mixture is slowly dripped into the flask according to the mol ratio of 20: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 25 hours in a reflux state; filtering the reaction solution while the reaction solution is hot to remove Pd/C, concentrating the filtrate under reduced pressure to 2/5 of the original volume, and cooling and separating out the solution under the nitrogen atmosphere to obtain 4.0g of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene with the yield of 84%;
FIG. 1 shows a hydrogen nuclear magnetic spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene, and it can be seen that chemical shift assignment of H atoms is clear and can correspond to each other one by one, and the structure of the obtained N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene is shown.
Example 2
Preparation of N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene, which has the following structural formula:
Figure BDA0001776367190000191
35.3g (250mmol) of 4-fluoronitrobenzene, 46.5g (325mmol) of 1-naphthylamine and 32.9g (325mmol) of triethylamine were placed in a 500mL three-necked flask equipped with mechanical stirring under nitrogen, 273mL of dimethyl sulfoxide was then added and the reaction was carried out at 85 ℃ for 38 hours. Discharging the mixture in an ice-water mixture at room temperature, performing suction filtration, and recrystallizing a filter cake by using ethanol and N, N-dimethylformamide (V: V ═ 1:1), thereby obtaining 50.1g of orange-red acicular crystal 4-nitrophenyl-1' -naphthylamine with the yield of 76%;
a250 mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 8.30g (35.0mmol) of 1-bromo-2-methoxynaphthalene, 9.9g (37.4mmol) of 4-nitrophenyl-1' -naphthylamine, 9.0g (142.2mmol) of copper powder, 19.6g (142.2mmol) of potassium carbonate, 4.7g (17.8mmol) of 18-crown-6 under nitrogen, and then 220mL of o-dichlorobenzene was added thereto, followed by reaction at 160 ℃ for 18 hours; vacuum-filtering while hot, distilling off o-dichlorobenzene under reduced pressure, recrystallizing the obtained crude product with ethanol and N, N-dimethylacetamide (V: V ═ 1:2) to obtain 11.5g of 4-nitrophenyl-1' -methoxynaphthyl-1-aminonaphthalene with a yield of 78%;
a250 mL three-necked flask equipped with a magnetic stirrer and a condenser was charged with 8.4g (20.0mmol) of 4-nitrophenyl-1' -methoxynaphthyl-1-aminonaphthalene, 70mL of dioxane, and 3.0g of Pd/C with a mass fraction of 10%, heated to reflux, and slowly dropped at a molar ratio of 10: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 18 hours under the reflux state; the reaction solution was filtered while hot to remove Pd/C, the filtrate was concentrated under reduced pressure to 1/3 of the original volume, and cooled and precipitated in a nitrogen atmosphere to obtain 6.9g of 4-aminophenyl-1' -methoxynaphthyl-1-aminonaphthalene with a yield of 88%;
a250 mL three-necked flask equipped with a magnetic stirrer, a thermometer, and a condenser was charged with 6.0g (15.4mmol) of 4-aminophenyl-1' -methoxynaphthyl-1-aminonaphthalene and 1.6g (15.4mmol) of triethylamine and 20mL of N, N-dimethylformamide under stirring and nitrogen protection. Then, 3.5g (15.4mmol) of 3, 5-dinitrobenzoyl chloride was dissolved in 10mL of N, N-dimethylformamide, and then it was slowly dropped into a three-necked flask with a rubber-tipped dropper. Stirring at normal temperature for 3h, and heating to 140 ℃ for reaction for 16 h; discharging the mixture into ethanol at room temperature, performing suction filtration, and recrystallizing a filter cake by using ethanol and N, N-dimethylacetamide to obtain 7.5g of N-1-methoxynaphthyl-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminonaphthalene with the yield of 83%;
6.0g (10.3mmol) of N-1-methoxynaphthyl-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminonaphthalene, 50mL of dioxane and 2.0g of 10% Pd/C are added into a 250mL three-necked flask provided with a magnetic stirrer and a condenser tube, heated to reflux, and slowly added dropwise with the N-1-methoxynaphthyl-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminonaphthalene in a molar ratio of 20: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 25 hours in a reflux state; the reaction solution was filtered while it was hot to remove Pd/C, and the filtrate was concentrated under reduced pressure to 2/5 of the original volume and cooled and precipitated in a nitrogen atmosphere to give 4.2g of N-1-methoxynaphthyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene in a yield of 79%.
Example 3
The preparation method of the N-1-amino anthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene has the following structural formula:
Figure BDA0001776367190000201
in a 500mL three-necked flask equipped with a mechanical stirrer, 35.3g (250mmol) of 4-fluoronitrobenzene, 62.7g (325mmol) of 1-aminoanthracene, and 32.9g (325mmol) of triethylamine were placed under nitrogen, followed by 273mL of dimethyl sulfoxide and reacted at 85 ℃ for 38 hours. Discharging the mixture into an ice-water mixture at room temperature, performing suction filtration, and recrystallizing a filter cake by using ethanol and N, N-dimethylformamide (V: V ═ 1:1), so as to obtain 50.1g of orange-red acicular crystal 4-nitro-1' -anthrylamine with the yield of 76%;
in a 250mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 10.0g (35.6mmol) of 4-bromopyrene, 11.7g (37.4mmol) of 4-nitro-1' -anthracylamine, 9.0g (142.2mmol) of copper powder, 19.6g (142.2mmol) of potassium carbonate and 4.7g (17.8mmol) of 18-crown-6 were added under nitrogen, and then 220mL of o-dichlorobenzene was added and reacted at 160 ℃ for 18 hours; carrying out suction filtration while the solution is hot, distilling off o-dichlorobenzene under reduced pressure, and recrystallizing the obtained crude product with ethanol and N, N-dimethylacetamide (V: V ═ 1:2) to obtain 12.5g of 4-nitrophenyl-1' -anthrylamine-4-aminopyrene with a yield of 68%;
12.0g (23.4mmol) of 4-nitrophenyl-1 '-anthracylamine-4-aminopyrene, 70mL of dioxane and 2.5g of Pd with the mass fraction of 10% in a 250mL three-necked flask provided with a magnetic stirrer and a condenser tube are added, the mixture is heated to reflux, and then slowly and dropwise added, wherein the molar ratio of the mixture to the 4-nitrophenyl-1' -anthracylamine-4-aminopyrene is 10: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 18 hours under the reflux state; filtering the reaction solution while the reaction solution is hot to remove Pd/C, concentrating the filtrate under reduced pressure to 1/3 of the original volume, and cooling and separating out the solution in a nitrogen atmosphere to obtain 9.8g of 4-aminophenyl-1' -anthrylamine-4-aminopyrene with the yield of 86%;
a250 mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser was charged with 9.0g (18.6mmol) of 4-aminophenyl-1' -anthracenamine-4-aminopyrene, 3.2g (30.8mmol) of triethylamine and 20mL of N, N-dimethylformamide under stirring and nitrogen protection. Then, 7.0g (30.8mmol) of 3, 5-dinitrobenzoyl chloride was dissolved in 10mL of N, N-dimethylformamide, and then it was slowly dropped into a three-necked flask with a rubber-tipped dropper. Stirring at normal temperature for 3h, and heating to 140 ℃ for reaction for 16 h; discharging the mixture into ethanol at room temperature, performing suction filtration, and recrystallizing the filter cake with ethanol and N, N-dimethylacetamide to obtain 10.9g of N-1-aminoanthracene-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminopyrene with a yield of 85%;
10g (10.3mmol) of N-1-amino anthracene-N-4- (3, 5-dinitrobenzamido) phenyl-1-aminopyrene, 50mL of dioxane and 2.0g of Pd/C with the mass fraction of 10% are dropwise added into a 250mL three-necked flask provided with a magnetic stirrer and a condenser tube, and after the mixture is heated to reflux, the mixture is slowly added into the flask in a molar ratio of 20: 1, hydrazine hydrate with the mass fraction of 85 percent, and continuously reacting for 25 hours in a reflux state; the reaction solution was filtered while hot to remove Pd/C, the filtrate was concentrated under reduced pressure to 2/5 of the original volume, and cooled and precipitated in a nitrogen atmosphere to obtain 4.0g of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene with a yield of 84%.
Example 4
Polymerizing N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene with terephthalic acid to prepare polyamide:
in a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 0.5502g (1mmol) of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzene obtained in example 1 was charged under nitrogenCarboxamido) phenyl-1-aminopyrene, 0.1661g (1mmol) of terephthalic acid, 0.15g of CaCl21.0mL of triphenyl phosphite, 0.5mL of pyridine, and 2.5mL of N-methylpyrrolidone, and reacted at 120 ℃ for 3 hours. Discharging the materials to be in a yellow fiber shape in ethanol, heating the materials to reflux and wash for 30min by using ethanol, water and ethanol in sequence, and drying the materials at 120 ℃ to finally obtain 0.6731g of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and terephthalic acid polyamide, wherein the mark is 9 a.
Example 5
Preparation of polyimide by polymerizing N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride
0.5502g (1mmol) of N-1-aminobenzene-N-4-methoxyphenyl-N' -benzene-3, 5-diaminobenzamide obtained in example 1, 0.2181g (1mmol) of cyclohexanetetracarboxylic dianhydride, and 2.0mL of N-methylpyrrolidone were charged into a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer, and a condenser under nitrogen, reacted at room temperature for 12 hours, and then 0.05mL of isoquinoline was charged and reacted at 180 ℃ for 12 hours. Discharging the materials to be in a yellow fibrous shape in ethanol, heating the materials to reflux and wash the materials twice by using the ethanol for 30min respectively, and drying the materials to finally obtain the polyimide of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type. Labeled 9b and had a mass of 0.7134 g.
FIG. 2 is an infrared spectrum of the polyimide of the type N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexanetetracarboxylic dianhydride at 3343cm-1Is the absorption peak of the stretching vibration of N-H, 1790cm-1Asymmetric stretching vibration absorption peak of C ═ O, 1725cm-1Symmetric stretching vibration absorption peak of C ═ O, 1346cm-1The stretching vibration absorption peak of C-N proves that the obtained polymer is polyimide of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type;
FIG. 3 is a TGA graph of the polyimide of the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type, from which it can be seen that the temperature of 5% weight loss is 453 ℃ and the temperature of 10% weight loss is 473 ℃ in a nitrogen atmosphere, which indicates good thermal stability;
FIG. 4 is a cyclic voltammogram of a polyimide of the type N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexanetetracarboxylic dianhydride, which shows that the redox process of the polyimide is reversible and has high stability;
the spectroelectrochemical properties of the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type polyimide prepared in example 5 were tested by the following specific method:
dissolving the polyimide in N, N-dimethylacetamide, wherein the concentration of the polyimide solution is 3mg/mL, dripping the polyimide solution on an ITO glass plate, drying at 90-120 ℃ to serve as a working electrode, taking a platinum wire as a counter electrode, taking Ag/AgCl as a reference electrode, and taking a 0.1M acetonitrile solution of tetrabutylammonium perchlorate (TBAP) as an electrolyte to construct a three-electrode system. Applying an increasing voltage through the electrochemical workstation, and monitoring the change of the absorption spectrum of the electrochemical workstation by using an ultraviolet-visible spectrometer;
FIG. 5 is an electrochromic diagram of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type polyimide, when the applied voltage is increased from 0V to 1.1V, the color of the film changes from yellow to purple;
the electrochromic conversion performance of the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and cyclohexane tetracarboxylic dianhydride type polyimide was tested by the following specific method:
based on the three-electrode system, square wave voltage is applied through an electrochemical workstation, and an ultraviolet spectrometer is used for monitoring the change of an absorption spectrum at the maximum absorption peak in the process.
FIG. 6 is an electrochromic response time spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type polyimide, from which it can be seen that the square wave voltage is 0-1.1V, the ultraviolet spectrum monitors the change of the absorption spectrum at 785nm, and when the duration time is 20s, the coloring/fading time is 4.37/1.61s, which shows that the asymmetric structure can weaken the stacking effect of the polymer and is beneficial to the embedding and extraction of electrolyte ions;
the electrically controlled fluorescence properties of the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene prepared in example 5 and cyclohexane tetracarboxylic dianhydride type polyimide were tested by the following specific method:
based on the three-electrode system, the change in fluorescence intensity was monitored by a fluorescence spectrometer during the application of increasing voltage through the electrochemical workstation.
FIG. 7 is a graph of an electrically controlled fluorescence spectrum of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride type polyimide, from which it can be seen that when an applied voltage is increased from 0V to 1.1V, the fluorescence intensity at 518nm is gradually reduced, the yellow fluorescence of the film is quenched, and when a voltage is applied in the reverse direction, the yellow fluorescence of the film is recovered, thus proving that the polyimide has reversible electrically controlled fluorescence behavior; at 518nm, the fluorescence contrast ratio is 106, which shows that the loose asymmetric structure can reduce the solid fluorescence quenching degree caused by stacking and enhance the fluorescence on-off contrast ratio.
Example 6
Preparation of polyamide by copolymerization of N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene, terephthalic acid and 1, 4-cyclohexanedicarboxylic acid
In a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 0.5502g (1mmol) of N-1-aminobenzene-N-4-methoxyphenyl-N' -benzene-3, 5-diaminobenzamide obtained in example 1, 0.0831g (0.5mmol) of terephthalic acid, 0.0861(0.5mmol) of 1, 4-cyclohexanedicarboxylic acid, 0.15g of CaCl were charged under nitrogen21.0mL of triphenyl phosphite, 0.5mL of pyridine, and 2.5mL of N-methylpyrrolidone, and reacted at 120 ℃ for 3 hours. Discharging the materials to be in a yellow fiber shape in ethanol, heating the materials to reflux and wash for 30min by using ethanol, water and ethanol in sequence, and drying the materials at 120 ℃ to finally obtain the N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene, terephthalic acid and 1, 4-cyclohexane dicarboxylic acid type copolyamide. MarkingWas 9c and had a mass of 0.6129 g.
Example 7
Preparation of polyamide by polymerization of N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene and terephthalic acid
In a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 0.5246g (1mmol) of N-1-aminobenzene-N-4-methoxyphenyl-N' -benzene-3, 5-diaminobenzamide obtained in example 2, 0.1661g (1mmol) of terephthalic acid, 0.15g of CaCl were charged under nitrogen21.0mL of triphenyl phosphite, 0.5mL of pyridine, and 2.5mL of N-methylpyrrolidone, and reacted at 120 ℃ for 3 hours. Discharging the materials to be in yellow fiber shape in ethanol, heating the materials to reflux and wash for 30min by using ethanol, water and ethanol in sequence, and drying the materials at 120 ℃ to finally obtain N-1- (2-methoxy naphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene and terephthalic acid type polyamide. Labeled 10a, and having a mass of 0.5981 g.
Example 8
Preparation of polyimide by polymerizing N-1- (2-methoxy naphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene with cyclohexane tetracarboxylic dianhydride
In a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer and a condenser, 0.5246g (1mmol) of N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene prepared in example 2, 0.2181g (1mmol) of cyclohexanetetracarboxylic dianhydride and 2.0mL of N-methylpyrrolidone were charged under nitrogen, reacted at room temperature for 12 hours, and then 0.05mL of isoquinoline was charged and reacted at 180 ℃ for 12 hours. Discharging the materials to be in yellow fiber shape in ethanol, heating the materials to reflux and washing the materials twice by using the ethanol for 30min respectively, and drying the materials to finally obtain the polyimide of N-1- (2-methoxy naphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene and cyclohexane tetracarboxylic dianhydride type. Labeled 10b, and had a mass of 0.7113 g.
Example 9
Preparation of polyamide by polymerization of N-1-aminoanthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and terephthalic acid
50mL of a flask equipped with a magnetic stirrer, a thermometer and a condenser were charged with nitrogen gasA three-necked flask was charged with 0.6787g (1mmol) of N-1-aminoanthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene obtained in example 4, 0.1661g (1mmol) of terephthalic acid, and 0.15g of CaCl21.0mL of triphenyl phosphite, 0.5mL of pyridine, and 2.5mL of N-methylpyrrolidone, and reacted at 120 ℃ for 3 hours. Discharging the materials to be in yellow fiber shape in ethanol, heating the materials to reflux and wash for 30min by using ethanol, water and ethanol in sequence, and drying the materials at 120 ℃ to finally obtain the N-1-amino anthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-amino pyrene and terephthalic acid type polyamide. Labeled 11a, and having a mass of 0.7018 g.
Example 10
Preparation of polyimide by polymerizing N-1-amino anthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene and cyclohexane tetracarboxylic dianhydride
0.6787g (1mmol) of N-1-aminoanthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene obtained in example 4, 0.2181g (1mmol) of cyclohexanetetracarboxylic dianhydride, and 2.0mL of N-methylpyrrolidone were charged into a 50mL three-necked flask equipped with a magnetic stirrer, a thermometer, and a condenser under nitrogen, reacted at room temperature for 12 hours, then 0.05mL of isoquinoline was charged, and reacted at 180 ℃ for 12 hours. Discharging the materials to be in yellow fiber shape in ethanol, heating the materials with the ethanol to reflux and wash the materials twice, each time for 30min, and drying the materials to finally obtain the polyimide of N-1-amino anthracene-N-4- (3, 5-diaminobenzamido) phenyl-1-amino pyrene and cyclohexane tetracarboxylic dianhydride type. Labeled 11b, and had a mass of 0.7623 g.
Example 11
The polyamide or polyimide obtained in example 4 to 10 was treated with N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), Tetrahydrofuran (THF) and chloroform (CHCl)3) The solubility of (1) was tested, and the test results are shown in table 1:
table 1: solubility of polyamides and polyimides prepared in examples 4-10 in 6 common solvents
Figure BDA0001776367190000261
Note: the concentration of the solution used for determining the solubility was 10 mg/mL;
++: soluble at room temperature; +: heating to dissolve; + -: is partially soluble; -: heating for insolubilization.
From the above examples, it can be seen that the polyamide or polyimide prepared from the diamine monomer containing the asymmetric fluorophore structure provided by the present invention has stable electrical activity, better solubility, higher fluorescence contrast, and faster fluorescence and color change electrical response speed.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A diamine monomer containing an asymmetric fluorophore structure, having the structure shown in formula I:
Figure FDA0002232026220000011
in the formula I, R1Is composed of
Figure FDA0002232026220000012
R2Is composed of
Figure FDA0002232026220000013
2. The asymmetric fluorophore structure-containing diamine monomer of claim 1, wherein the asymmetric fluorophore structure-containing diamine monomer is N-4-methoxyphenyl-N-4- (3, 5-diaminobenzamido) phenyl-1-aminopyrene or N-1- (2-methoxynaphthyl) -N-4- (3, 5-diaminobenzamido) phenyl-1-aminonaphthalene.
3. A method of preparing a diamine monomer containing an asymmetric fluorophore structure as claimed in claim 1 or 2, comprising the steps of:
4-fluoronitrobenzene and R2-NH2Mixing triethylamine and dimethyl sulfoxide to perform nucleophilic substitution reaction I to obtain a compound with a structure shown in a formula II;
the compound with the structure shown in the formula II, copper powder, potassium carbonate, 18-crown-6 and R1Mixing the-X and o-dichlorobenzene to perform Ullmann reaction to obtain a compound with a structure shown in a formula III; the R is1X in X is Cl, Br or I;
mixing the compound with the structure shown in the formula III, Pd/C, hydrazine hydrate and dioxane to perform a reduction reaction I to obtain a compound with the structure shown in the formula IV;
mixing a compound with a structure shown in a formula IV, triethylamine, N-dimethylformamide and 3, 5-dinitrobenzoyl chloride to perform nucleophilic substitution reaction II to obtain a compound with a structure shown in a formula V;
mixing a compound with a structure shown in a formula V, Pd/C, hydrazine hydrate and dioxane to perform a reduction reaction II to obtain a compound with a structure shown in a formula I;
Figure FDA0002232026220000021
4. the preparation method according to claim 3, wherein the temperature of the nucleophilic substitution reaction I is 80-100 ℃, and the time of the nucleophilic substitution reaction I is 30-45 h.
5. The preparation method according to claim 3, wherein the Ullmann reaction temperature is 140-180 ℃ and the Ullmann reaction time is 12-20 h.
6. The method according to claim 3, wherein the temperature of the reduction reaction I is 70 to 90 ℃ and the time of the reduction reaction I is 1 to 24 hours.
7. The preparation method according to claim 3, wherein the temperature of the nucleophilic substitution reaction II is 135-145 ℃, and the time of the nucleophilic substitution reaction II is 3-8 h.
8. The method according to claim 3, wherein the temperature of the reduction reaction II is 75 to 95 ℃ and the time of the reduction reaction II is 3 to 30 hours.
9. Use of a diamine monomer containing an asymmetric fluorophore structure according to claim 1 or 2 in an electrochromic and electrically controllable fluorescent material, which is a polyamide or polyimide.
10. Use according to claim 9, characterized in that the polyamide is prepared by a process comprising the following steps:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound with a structure shown in a formula a, and carrying out polymerization reaction to obtain polyamide;
Figure FDA0002232026220000022
in the formula a, Ar is
Figure FDA0002232026220000023
The preparation method of the polyimide comprises the following steps:
mixing the diamine monomer containing the asymmetric fluorophore structure with a compound having a structure shown in a formula b, and carrying out polymerization reaction to obtain polyimide;
Figure FDA0002232026220000024
in the formula b, Ar' is
Figure FDA0002232026220000031
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