CN108929243A - A kind of diamine monomer and its preparation method and application containing asymmetric fluorophore structure - Google Patents

A kind of diamine monomer and its preparation method and application containing asymmetric fluorophore structure Download PDF

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CN108929243A
CN108929243A CN201810971723.4A CN201810971723A CN108929243A CN 108929243 A CN108929243 A CN 108929243A CN 201810971723 A CN201810971723 A CN 201810971723A CN 108929243 A CN108929243 A CN 108929243A
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CN108929243B (en
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陈春海
苏凯欣
王大明
孙宁伟
周宏伟
赵晓刚
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Jilin University
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    • C07C237/28—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton
    • C07C237/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The present invention provides a kind of diamine monomers containing asymmetric fluorophore structure with structure shown in formula I, the polyamide or polyimides being prepared using it as monomer can be while keeping polymer thermostable, its dissolubility and film forming are improved, and assigns the excellent electrochromism of polymer and automatically controlled fluorescence property.Specifically, the derivative of triaryl amine provides electroactive site in the diamine monomer containing asymmetric fluorophore structure；The introducing of fluorogen can enhance the fluorescence intensity of polymer, improve fluorescent switch contrast；Dissymmetrical structure can effectively weaken the sedimentation of polymer, enhance dissolubility and solid state fluorescence, accelerate response speed.Record according to the embodiment, the electrochromism of the polyamide or polyimides provided by the invention by the diamine monomer preparation containing asymmetric fluorophore structure and automatically controlled fluorescence property significantly improve.

Description

A kind of diamine monomer and its preparation method and application containing asymmetric fluorophore structure
Technical field
The present invention relates to electrochromism and automatically controlled fluorescent technique fields more particularly to a kind of containing asymmetric fluorophore structure Diamine monomer and its preparation method and application.
Background technique
Electrochromism refers to the optical properties (reflectivity, transmitance, absorptivity etc.) of material under the action of extra electric field Color change there is a phenomenon where stablizing, reversible shows as the reversible change of color and transparency in appearance.1969, S.K.Deb reports the first tungstic acid electrochromic material.Hereafter researcher has found small organic molecule successively again and leads The electrochromic property of electric polymer.Automatically controlled fluorescence refers to that reversible tune occurs under electro photoluminescence for the fluorescence intensity of material or color Control.Wherein, triphen amine derivant receives more concerns because wherein condition is colourless, driving voltage is low.Its cation is certainly It can effective quenching fluorescence while leading to discoloration by base.
Polyamide and polyimides rely on outstanding hot property, mechanical performance and outstanding corrosion resistance, have attracted crowd The attention of more researchers.However its stronger molecule inter-chain action results in poor dissolubility.By the triphen of propeller arrangement Amine is introduced into polyamide and polyimides, and in improvement, its is deliquescent while assigning its electrochromism and automatically controlled fluorescence property.
However, the fluorescence of triphenylamine is weaker, it is glimmering solid-state to be significantly quenched in the closs packing of polyamide and polyimides in addition Light also results in the reduction of ion doping speed.In order to meet business demand, new structural diamine monomer is prepared and by it It prepares and has great importance with easy processing and high performance electrochromism and automatically controlled fluorescent material.
Summary of the invention
The purpose of the present invention is to provide a kind of polyamide prepared with excellent electrochromism and automatically controlled fluorescence property Or the diamine monomer containing asymmetric fluorophore structure of polyimides.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of diamine monomers containing asymmetric fluorophore structure, have structure shown in formula I:
In formula I, R1For
R2For
Preferably, the diamine monomer containing asymmetric fluorophore structure includes N-4- methoxyphenyl-N-4- (3,5- bis- Aminobenzoyl amido) phenyl -1- amino pyrene, N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) benzene Base -1- amino naphthalenes or N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene.
The present invention also provides the preparation methods of the diamine monomer containing asymmetric fluorophore structure, including following step It is rapid:
By 4- fluoronitrobenzene, R2-NH2, triethylamine and dimethyl sulfoxide mixing, occur nucleophilic substitution I, had There is the compound of structure shown in formula II；
By compound, copper powder, potassium carbonate, the 18- crown ether -6, R with structure shown in formula II1- X and o-dichlorohenzene are mixed It closes, ullmann reaction occurs, obtains the compound with structure shown in formula III；The R1X is Cl, Br or I in-X；
The compound with structure shown in formula III, Pd/C, hydrazine hydrate and dioxane are mixed, reduction reaction occurs I, obtain the compound with structure shown in formula IV；
By compound, triethylamine, N,N-dimethylformamide and 3,5- dinitrobenzene first with structure shown in formula IV Acyl chlorides mixing, occurs nucleophilic substitution II, obtains the compound with structure shown in formula V；
Compound, Pd/C, hydrazine hydrate and dioxane with structure shown in formula V are mixed, reduction reaction II occurs, Obtain the compound with structure shown in formula I；
Preferably, the temperature of the nucleophilic substitution I is 80~100 DEG C, and the time of the nucleophilic substitution I is 30 ~45h.
Preferably, the temperature of the ullmann reaction is 140~180 DEG C, time of the ullmann reaction is 12~ 20h。
Preferably, the temperature of the reduction reaction I is 70~90 DEG C, time of the reduction reaction I is 1~for 24 hours.
Preferably, the temperature of the nucleophilic substitution II is 135~145 DEG C, the time of the nucleophilic substitution II For 3~8h.
Preferably, the temperature of the reduction reaction II is 75~95 DEG C, and the time of the reduction reaction II is 3~30h.
The present invention also provides the diamine monomers containing asymmetric fluorophore structure in electrochromism and automatically controlled fluorescence Application in material, the electrochromism and automatically controlled fluorescent material are polyamide or polyimides.
Preferably, the polyamide preparation method the following steps are included:
The diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula a are mixed, occurred Polymerization reaction obtains polyamide；
Ar is in the formula a
The preparation method of the polyimides the following steps are included:
The diamine monomer containing asymmetric fluorophore structure is mixed with the compound with structure shown in formula b, is occurred Polymerization reaction obtains polyimides；
Ar' is in the formula b
The present invention provides a kind of diamine monomers containing asymmetric fluorophore structure with structure shown in formula I, are with it The polyamide or polyimides that monomer is prepared can while keeping polymer thermostable, improve its dissolubility and at Film property, and assign the excellent electrochromism of polymer and automatically controlled fluorescence property.Specifically, described containing asymmetric fluorophore structure In diamine monomer, the derivative of triaryl amine provides electroactive site；The introducing of fluorogen can enhance the fluorescence intensity of polymer, Improve fluorescent switch contrast；Dissymmetrical structure can effectively weaken the sedimentation of polymer, enhance dissolubility and solid state fluorescence, Accelerate response speed.Record according to the embodiment, it is provided by the invention to be prepared by the diamine monomer containing asymmetric fluorophore structure Polyamide or polyimides electrochromism and automatically controlled fluorescence property significantly improve.
Detailed description of the invention
Fig. 1 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 1 is prepared The hydrogen nuclear magnetic spectrogram of 1- amino pyrene；
Fig. 2 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The infrared spectrum of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides；
Fig. 3 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The TGA of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides schemes；
Fig. 4 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The cyclic voltammetry curve figure of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides；
Fig. 5 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The electrochromism spectrogram of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides；
Fig. 6 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The electrochromism response time spectrogram of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides；
Fig. 7 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl-that embodiment 5 is prepared The automatically controlled fluorogram of 1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides.
Specific embodiment
The present invention provides a kind of diamine monomers containing asymmetric fluorophore structure, have structure shown in formula I:
In formula I, R1For
R2For
In the present invention, the diamine monomer containing asymmetric fluorophore structure include N-4- methoxyphenyl-N-4- (3, 5- diaminobenzene formamido) phenyl -1- amino pyrene, N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamide Base) phenyl -1- amino naphthalenes or N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene.
The present invention also provides the preparation methods of the diamine monomer containing asymmetric fluorophore structure, including following step It is rapid:
By 4- fluoronitrobenzene, R2-NH2, triethylamine and dimethyl sulfoxide mixing, occur nucleophilic substitution I, had There is the compound of structure shown in formula II；
By compound, copper powder, potassium carbonate, 18- crown ether -6, R with structure shown in formula II1- X, o-dichlorohenzene mixing, hair Raw ullmann reaction, obtains the compound with structure shown in formula III；
Compound, Pd/C, hydrazine hydrate and dioxane with structure shown in formula III are mixed, reduction reaction I occurs, obtains To the compound with structure shown in formula IV；
By compound, triethylamine, N,N-dimethylformamide and 3,5- dinitrobenzene first with structure shown in formula IV Acyl chlorides mixing, occurs nucleophilic substitution II, obtains the compound with structure shown in formula V；
Compound, Pd/C, hydrazine hydrate and dioxane with structure shown in formula V are mixed, reduction reaction II occurs, Obtain the compound with structure shown in formula I；
In the present invention, if without specified otherwise, commercial product that all raw materials are well known to the skilled person.
The present invention is by 4- fluoronitrobenzene, R2-NH2, triethylamine and dimethyl sulfoxide mixing, occur nucleophilic substitution I, Obtain the compound with structure shown in formula II.In the present invention, the 4- fluoronitrobenzene, R2-NH2With mole of triethylamine Than being preferably 1:(1.3~1.5): (1.3~1.5), more preferably 1:(1.35~1.45): (1.35~1.45).In the present invention In, the amount of the substance of the 4- fluoronitrobenzene and the volume ratio of dimethyl sulfoxide are preferably (0.9~0.94) mol:1L, more preferably For (0.91~0.93) mol:1L.
In the present invention, the 4- fluoronitrobenzene, R2-NH2, obtained reaction after triethylamine and dimethyl sulfoxide mixing The total solid content of system is preferably 15%~28%, and more preferably 16%~27%, most preferably 18%~26%.
In the present invention, the 4- fluoronitrobenzene, R2-NH2It is reactant with triethylamine, the dimethyl sulfoxide is anti- Answer solvent.
The present invention does not have any special restriction to the addition sequence of above-mentioned raw materials, and it is known that those skilled in the art can be used Addition sequence mixed；In the present invention, specially first by 4- fluoronitrobenzene, R2-NH2It mixes with triethylamine, then exists Dimethyl sulfoxide is added in obtained mixture.
In the present invention, the mixing carries out preferably in protective atmosphere, guarantor of the present invention to the offer protective atmosphere Shield gaseous species do not have any special restriction, specific such as nitrogen using protective gas well known to those skilled in the art.
The present invention does not have any special restriction to the hybrid mode and mixing condition, using those skilled in the art institute Well known hybrid mode and mixing condition are mixed.
In the present invention, the temperature of the nucleophilic substitution I is preferably 80~100 DEG C, and more preferably 85~95 DEG C, most Preferably 88~92 DEG C；The time of the nucleophilic substitution I is preferably 30~45h, more preferably 35~42h, most preferably 38~40h.
In the present invention, the nucleophilic substitution I carries out preferably in protective atmosphere, and the present invention is to the offer protection The protective gas type of atmosphere does not have any special restriction, using protective gas well known to those skilled in the art, tool Body such as nitrogen.In the present invention, the nucleophilic substitution I preferably carries out under stirring conditions；The present invention is to the stirring There is no any special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the device of the nucleophilic substitution I, using those skilled in the art The well known device that can be realized above-mentioned reaction is reacted；In the present invention, it can be selected specifically to stir equipped with machinery The three-neck flask mixed.
After the completion of nucleophilic substitution I, the present invention preferably post-processes obtained product system, and the post-processing is excellent Choosing the following steps are included:
The product system is mixed with mixture of ice and water, resulting material is filtered, gained filter cake is tied again Crystalline substance obtains the compound with structure shown in formula II.
The present invention does not have any special restriction to the hybrid mode and condition, and use is well known to those skilled in the art Hybrid mode and condition mixing.
The present invention filters no any special restriction to described, real using suction filtration condition well known to those skilled in the art The purpose being now separated by solid-liquid separation.
In the present invention, the reagent of the recrystallization is preferably ethyl alcohol and/or n,N-Dimethylformamide；When the heavy knot When brilliant reagent is ethyl alcohol and n,N-Dimethylformamide, the present invention is preferably (0.5 to the dosage volume ratio of described two substances ~2): 1, more preferably (0.8~1.2): 1.
After obtaining the compound with structure shown in formula II, the present invention by with structure shown in formula II compound, copper powder, Potassium carbonate, 18- crown ether -6, R1- X and o-dichlorohenzene mixing, occur ullmann reaction, obtain the chemical combination with structure shown in formula III Object；The R1X is Cl, Br or I in-X.
In the present invention, compound, copper powder, potassium carbonate, 18- crown ether -6 and the R with structure shown in formula II1- X's Molar ratio is preferably (1.1~1.5): (3~6): (3~6): (0.5~1): 1, more preferably (1.2~1.4): (4~5.5): (4~5.5): (0.6~0.8): 1.
In the present invention, the amount of the substance of the compound with structure shown in formula II and the volume ratio of o-dichlorohenzene are excellent It is selected as (0.1~0.7) mol:1L, more preferably (0.2~0.6) mol:1L.
In the present invention, compound, copper powder, potassium carbonate, the 18- crown ether -6, R with structure shown in formula II1- X with The total solid content of the reaction system obtained after o-dichlorohenzene mixing is preferably 15%~30%, and more preferably 18%~25%, most Preferably 20%~23%.
In the present invention, the copper powder is catalyst, and potassium carbonate is co-catalyst, and 18- crown ether -6 is phase transfer catalyst, O-dichlorohenzene is solvent.
The present invention does not have any special restriction to the mixed sequence, can be mixed in any order.In this hair In bright, it can be selected specifically to compound, copper powder, potassium carbonate, 18- crown ether -6 and R with structure shown in formula II first1- X is mixed It closes, o-dichlorohenzene then is added in obtained mixture.
In the present invention, the mixing carries out preferably in protective atmosphere, guarantor of the present invention to the offer protective atmosphere Shield gaseous species do not have any special restriction, specific such as nitrogen using protective gas well known to those skilled in the art.
The present invention does not have any special restriction to the hybrid mode and mixing condition, using those skilled in the art institute Well known hybrid mode and mixing condition are mixed.
In the present invention, the temperature of the ullmann reaction is preferably 140~180 DEG C, and more preferably 150~170 DEG C, most Preferably 155~165 DEG C；The time of the ullmann reaction is preferably 12~20h, more preferably 14~18h.
In the present invention, the ullmann reaction carries out preferably in protective atmosphere, and the present invention is to the offer protection gas The protective gas type of atmosphere does not have any special restriction, using protective gas well known to those skilled in the art, specifically Such as nitrogen.In the present invention, the ullmann reaction preferably carries out under stirring conditions；The present invention is to the stirring without appointing What special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the device of the ullmann reaction, using known to those skilled in the art The device that can be realized above-mentioned reaction reacted；In the present invention, can be selected specifically to equipped with magnetic stir bar, The three-neck flask of thermometer and condenser pipe.
After the completion of ullmann reaction, the present invention preferably post-processes obtained product system, and the post-processing includes Following steps:
The product system is filtered, gained filtrate is evaporated under reduced pressure, obtained residue is tied again Crystalline substance obtains the compound with structure shown in formula III.
The present invention filters no any special restriction to described, real using suction filtration condition well known to those skilled in the art The purpose being now separated by solid-liquid separation.
The present invention steams the no any special restriction of vacuum distillation using decompression well known to those skilled in the art It evaporates except o-dichlorohenzene.
In the present invention, the reagent of the recrystallization is preferably the mixture of ethyl alcohol and n,N-dimethylacetamide；At this In invention, the volume ratio of the ethyl alcohol and n,N-dimethylacetamide is preferably 1:(1~3), more preferably 1:(1.5~2.5).
After obtaining the compound with structure shown in formula III, the present invention by with structure shown in formula III compound, Pd/C, Hydrazine hydrate and dioxane mixing, occur reduction reaction I, obtain the compound with structure shown in formula IV.In the present invention, institute State the aqueous solution that hydrazine hydrate is preferably hydrazine hydrate；In the hydrazine hydrate aqueous solution mass fraction of hydrazine hydrate be preferably 70%~ 90%, more preferably 75%~85%, most preferably 78%~92%.
In the present invention, the mass ratio of the Pd in the Pd/C and C is preferably (0.05~0.2): 1, more preferably (0.08 ~0.15): 1, most preferably (0.1~0.12): 1.
In the present invention, it is described have the compound of structure and the mass ratio of Pd/C shown in formula III be preferably 1:(0.3~ 0.4), more preferably 1:(0.32~0.38), most preferably 1:(0.34~0.36).
In the present invention, it is described have the compound of structure and the molar ratio of hydrazine hydrate shown in formula III be preferably 1:(5~ 20), more preferably 1:(8~16), most preferably 1:(12~14).
In the present invention, the amount of the substance of the compound with structure shown in formula III and the volume ratio of dioxane are excellent It is selected as (0.1~0.3) mol:1L, more preferably (0.15~0.25) mol:1L, most preferably (0.18~0.22) mol:1L.
In the present invention, compound, Pd/C, hydrazine hydrate and the dioxane with structure shown in formula III is mixed to get The total solid content of reaction system be preferably 10%~20%, more preferably 12%~18%, most preferably 14%~16%.
In the present invention, the Pd/C is catalyst, and hydrazine hydrate is reducing agent, and dioxane is solvent.
In the present invention, the mixed sequence is preferably first by compound, Pd/C and two with structure shown in formula III The mixing of six ring of oxygen, is then added dropwise hydrazine hydrate, the present invention is not any to the dropwise addition of the hydrazine hydrate in obtained mixture again Special restriction is added dropwise using dropwise addition mode well known to those skilled in the art and drop rate.
In the present invention, the mixing preferably carries out under stirring conditions, and the present invention does not have the condition of the stirring Any special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the hybrid mode and mixing condition, ripe using those skilled in the art The hybrid mode and mixing condition known are mixed.
In the present invention, the temperature of the reduction reaction I is preferably 70~90 DEG C, and more preferably 75~85 DEG C, most preferably It is 78~82 DEG C；In the present invention, the reduction reaction I preferably carries out under conditions of reflux.In the present invention, the reduction The time of reaction I is preferably 1~for 24 hours, more preferably 5~20h, most preferably 10~15h.
In the present invention, the reduction reaction I preferably carries out under stirring conditions；The present invention is to the stirring without appointing What special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the device of the reduction reaction I, using known to those skilled in the art The device that can be realized above-mentioned reaction reacted；In the present invention, it can be selected specifically to that magnetic stir bar is housed With the three-neck flask of condenser pipe.
After the completion of reduction reaction I, the present invention preferably post-processes obtained product system, it is described post-processing include with Lower step:
The product system is filtered, gained filtrate is concentrated under reduced pressure, cools down precipitation, is obtained with IV institute of formula Show the compound of structure.
The present invention goes the no any special restriction of filtering using filter condition well known to those skilled in the art Except Pd/C.In the present invention, the filtering is preferably filtered after the completion of reduction reaction I while hot.
It is in the present invention, described to be concentrated under reduced pressure to make the ratio of filtrate volume and original volume after concentration be preferably less than 1, More preferably less than 0.8, most preferably less than 0.4；No any special restriction is concentrated under reduced pressure to described in the present invention, using this It is concentrated under reduced pressure known to the technical staff of field.
In the present invention, cooling be precipitated carries out preferably in protective atmosphere, and the present invention is to the offer protective atmosphere Protective gas type there is no any special restriction, using protective gas well known to those skilled in the art, specifically such as Nitrogen.
After obtaining the compound with structure shown in formula IV, the present invention is by the compound with structure shown in formula IV, three second Base amine, n,N-Dimethylformamide and 3, the mixing of 5- dinitrobenzoyl chloride, occur nucleophilic substitution II, obtain with formula V The compound of shown structure.In the present invention, compound, the triethylamine and 3 with structure shown in formula IV, 5- dinitro The molar ratio of chlorobenzoyl chloride is preferably 1:(1~1.7): (1~1.7), more preferably 1:(1.2~1.3): (1.2~1.3).
In the present invention, the amount and n,N-Dimethylformamide of the substance of the compound with structure shown in formula IV Volume ratio is preferably (0.4~0.7) mol:1L, more preferably (0.45~0.65) mol:1L, most preferably (0.5~0.6) Mol:1L.
In the present invention, compound, the triethylamine, n,N-Dimethylformamide and 3 with structure shown in formula IV, The total solid content of the reaction system obtained after the mixing of 5- dinitrobenzoyl chloride is preferably 15%~30%, more preferably 20%~ 28%, most preferably 22%~26%.
In the present invention, the compound and 3 with structure shown in formula IV, 5- dinitrobenzoyl chloride are reactant, The n,N-Dimethylformamide is solvent, and the triethylamine is catalyst.
In the present invention, the order by merging be preferably first by with structure shown in formula IV compound, triethylamine and N,N-Dimethylformamide mixing, then 3,5- dinitrobenzoyl chloride is added dropwise in obtained mixture.In the present invention, described The amount of the substance of triethylamine and the volume ratio of n,N-Dimethylformamide are preferably (0.6~1.0) mol:1mL, more preferably (0.7~0.9) mol:1L, most preferably (0.75~0.85) mol:1L.The DNBC 3,5 dinitrobenzoylchloride in the present invention N,N-Dimethylformamide solution concentration be preferably (1~3.5) mol/L, more preferably (1.5~3) mol/L, most preferably For (2~2.5) mol/L.The addition of the N,N-dimethylformamide solution of the DNBC 3,5 dinitrobenzoylchloride in the present invention Temperature is preferably room temperature.The addition side of the N,N-dimethylformamide solution of the DNBC 3,5 dinitrobenzoylchloride in the present invention Formula is preferably added dropwise；In the present invention, the time of the dropwise addition is preferably 0.5~3h, more preferably 1~2.5h, most preferably 1.5~2h.
After completion of dropwise addition, system temperature reaction that the present invention will obtain；The temperature of the reaction is preferably 130~150 DEG C, More preferably 135~145 DEG C；In the present invention, the reaction preferably carries out under conditions of reflux.The time of the reaction is excellent It is selected as 12~20h, more preferably 14~18h, most preferably 15~16h.
In the present invention, the nucleophilic substitution II carries out preferably in protective atmosphere, and the present invention is to the offer guarantor The protective gas type of shield atmosphere does not have any special restriction, using protective gas well known to those skilled in the art, Specific such as nitrogen.
The present invention does not have any special restriction to the device of the nucleophilic substitution II, using those skilled in the art The well known device that can be realized above-mentioned reaction is reacted；In the present invention, it can be selected specifically to stir equipped with magnetic force Mix the three-neck flask of son, thermometer and condenser pipe.
After the completion of nucleophilic substitution II, the present invention preferably post-processes obtained product system, the post-processing The following steps are included:
The product system is mixed with ethyl alcohol, resulting material is filtered, obtained filter cake is recrystallized, is obtained To the compound with structure shown in formula V.
The present invention does not have any special restriction to the hybrid mode and condition, and use is well known to those skilled in the art Hybrid mode and condition mixing.The present invention does not have any special restriction to the dosage of the ethyl alcohol, using this field skill Dosage known to art personnel.
The present invention filters no any special restriction to described, real using suction filtration condition well known to those skilled in the art The purpose being now separated by solid-liquid separation.
In the present invention, the reagent of the recrystallization is preferably ethyl alcohol and n,N-dimethylacetamide；In the present invention, institute The volume ratio for stating ethyl alcohol and n,N-Dimethylformamide is preferably 1:(2~4), more preferably 1:(2.2~3.8), most preferably 1:(2.8~3.2)
After obtaining the compound with structure shown in formula V, the present invention by with structure shown in formula V compound, Pd/C, Hydrazine hydrate and dioxane mixing, occur reduction reaction II, obtain the compound with structure shown in formula I.In the present invention, institute The mass ratio for stating the Pd and C in Pd/C is preferably (0.05~0.2): 1, more preferably (0.5~0.15): 1, most preferably (0.8 ~0.12): 1.
In the present invention, it is described have the compound of structure and the mass ratio of Pd/C shown in formula V be preferably 1:(0.1~ 0.4), more preferably 1:(0.2~0.3), most preferably 1:(0.24~0.26).
In the present invention, it is described have the compound of structure and the molar ratio of hydrazine hydrate shown in formula V be preferably 1:(15~ 40), more preferably 1:(20~30), most preferably 1:(23~27).
In the present invention, the amount of the substance of the compound with structure shown in formula V and the volume ratio of dioxane are excellent It is selected as (0.1~0.2) mol:1L, more preferably (0.12~0.18) mol:1L, most preferably (0.14~0.16) mol:1L.
In the present invention, compound, Pd/C, hydrazine hydrate and the dioxane with structure shown in formula V is mixed to get The total solid content of reaction system be preferably 10%~20%, more preferably 12%~18%, most preferably 14%~16%.
In the present invention, the Pd/C is catalyst, and hydrazine hydrate is reducing agent, and dioxane is solvent.
In the present invention, the order by merging is preferably the compound, Pd/C and dioxy that will first have structure shown in formula V The mixing of six rings, is then added dropwise hydrazine hydrate in obtained mixture again.
In the present invention, the mixing preferably carries out under stirring conditions, and the present invention does not have the condition of the stirring Any special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the hybrid mode and mixing condition, ripe using those skilled in the art The hybrid mode and mixing condition known are mixed.
In the present invention, the temperature of the reduction reaction II is preferably 75~95 DEG C, and more preferably 80~90 DEG C, most preferably It is 83~86 DEG C；In the present invention, the reduction reaction II preferably carries out under conditions of reflux.In the present invention, described to go back The time of original reaction II is preferably 3~30h, more preferably 10~20h, most preferably 12~15h.
In the present invention, the reduction reaction II preferably carries out under stirring conditions；The present invention does not have the stirring Any special restriction, is stirred using stirring condition well known to those skilled in the art.
The present invention does not have any special restriction to the device of the reduction reaction II, using known to those skilled in the art The device that can be realized above-mentioned reaction reacted；In the present invention, it can be selected specifically to that magnetic stir bar is housed With the three-neck flask of condenser pipe.
After the completion of reduction reaction II, the present invention preferably post-processes obtained product system, and the post-processing includes Following steps:
The product system is filtered, gained filtrate is concentrated under reduced pressure, cooling be precipitated obtains with shown in formula I The compound of structure.
The present invention goes the no any special restriction of filtering using filter condition well known to those skilled in the art Except Pd/C.In the present invention, the filtering is preferably filtered after the completion of the reduction reaction II while hot.
In the present invention, the reduced pressure is preferably preferably less than the ratio of filtrate volume and original volume after concentration 1, more preferably less than 0.8, most preferably less than 0.4；No any special restriction is concentrated under reduced pressure to described in the present invention, uses Reduced pressure well known to those skilled in the art.
In the present invention, cooling be precipitated carries out preferably in protective atmosphere, and the present invention is to the offer protective atmosphere Protective gas type there is no any special restriction, using protective gas well known to those skilled in the art, specifically such as Nitrogen；The present invention does not have any special restriction to the cooling detailed process being precipitated, using known to those skilled in the art Cooling precipitation process.
The present invention also provides the diamine monomers containing asymmetric fluorophore structure in electrochromism and automatically controlled phosphor Application in material, the electrochromism and automatically controlled fluorescent material are polyamide or polyimides.
In the present invention, the polyamide has structure shown in formula c:
Ar is in the formula c
N is the integer between 30~100.
The polyimides has structure shown in formula d:
Ar' is in the formula d
M is the integer between 30~100.
In the present invention, the preparation method of the polyamide preferably includes following steps:
The diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula a are mixed, occurred Polymerization reaction obtains polyamide；
Ar is in the formula a
In the present invention, the diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula a Molar ratio be preferably 1:1.
In the present invention, the temperature of the polymerization reaction is preferably 110~130 DEG C, more preferably 115~125 DEG C, optimal It is selected as 118~122 DEG C；The time of the polymerization reaction is preferably 3~6h, more preferably 3.5~6h, most preferably 4~5h.
In the present invention, the polymerization reaction preferably existing for the catalyst under the conditions of carry out；In the present invention, described to urge Agent is preferably calcium chloride；In the present invention, the quality of the catalyst with containing asymmetric fluorophore structure diamine monomer with Total mass ratio be preferably (0.15~0.35): 1, more preferably (0.18~0.3): 1.
In the present invention, the polymerization reaction preferably existing for the condensing agent under the conditions of carry out；In the present invention, the contracting Mixture is preferably triphenyl phosphite and pyridine；In the present invention, the volume ratio of the triphenyl phosphite and pyridine is preferably (1.8~2.2): 1, more preferably (1.9~2.1): 1.In the present invention, the volume of the triphenyl phosphite with containing asymmetry The mass ratio of the material of the diamine monomer of fluorophore structure is preferably 1L:(0.8~1.2) mol, more preferably 1L:(0.9~1.1) mol。
In the present invention, the polymerization reaction preferably existing for the organic solvent under the conditions of carry out；In the present invention, described Organic solvent is preferably N-Methyl pyrrolidone；In the present invention, the object of the diamine monomer containing asymmetric fluorophore structure The amount of matter and the volume ratio of solvent are preferably 1mol:(2~3) L, more preferably 1mol:(2.2~2.8) L, most preferably 1mol: (2.4~2.6) L.
In the present invention, the total solid content of the reaction system of the polymerization reaction is preferably 15%~30%, more preferably 18%~28%, most preferably 22%~26%.
In the present invention, the polymerization reaction carries out preferably in protective atmosphere, and the present invention is to the offer protective atmosphere Protective gas type there is no any special restriction, using protective gas well known to those skilled in the art, specifically such as Nitrogen.In the present invention, the polymerization reaction preferably carries out under stirring conditions；The present invention is to the no any spy of stirring Different restriction is stirred using stirring condition well known to those skilled in the art.
After the completion of polymerization reaction, the present invention preferably post-processes obtained product system, it is described post-processing include with Lower step:
The product system is mixed with ethyl alcohol, is washed, is dry, obtains polyamide.
The present invention is mixed using mixing condition well known to those skilled in the art to the no any special restriction of mixing Conjunction；It in the present invention, is in order to which polyamide is precipitated by the purpose that the product system is mixed with ethyl alcohol.
In the present invention, the cleaning solution of the washing is preferably second alcohol and water；The present invention does not have the number of the washing Any special restriction, the polyamide washes clean that will be obtained.
The present invention any special restriction no to the drying, using drying condition well known to those skilled in the art into Row is dry.
In the present invention, the preparation method of the polyimides preferably includes following steps:
The diamine monomer containing asymmetric fluorophore structure is mixed with the compound with structure shown in formula b, is occurred Polymerization reaction obtains polyimides；
Ar' is in the formula b
In the present invention, the diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula b Molar ratio be preferably 1:1.
In the present invention, the temperature of the polymerization reaction is preferably 160~180 DEG C, more preferably 165~175 DEG C, optimal It is selected as 168~172 DEG C；The time of the polymerization reaction is preferably 8~20h, more preferably 10~18h, most preferably 13~ 16h。
In the present invention, the polymerization reaction preferably existing for the isoquinolin under the conditions of carry out.In the present invention, described different The volume of quinoline and the molar ratio of the diamine monomer containing asymmetric fluorophore structure are preferably (0.03~0.09) L:1mol, more excellent It is selected as (0.04~0.08) L:1mol.In the present invention, the addition time of the isoquinolin is preferably containing asymmetric fluorescence unity After the diamine monomer of structure reacts 12~20h at room temperature with the compound with structure shown in formula b, more preferably 14~18h is optimal It is selected as 15~16h.
In the present invention, the diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula b Reaction at room temperature is polycondensation reaction；Isoquinolin reacts 12 with dianhydride in the diamine monomer containing asymmetric fluorophore structure at room temperature The effect being added after~20h is dehydration.
In the present invention, the polymerization reaction preferably existing for the organic solvent under the conditions of carry out；In the present invention, described Solvent is preferably N-Methyl pyrrolidone；In the present invention, the substance of the diamine monomer containing asymmetric fluorophore structure Volume ratio preferably (0.4~0.6) mol:1L, more preferably (0.45~0.55) mol:1L of amount and solvent, most preferably (0.48~0.52) mol:1L.
In the present invention, the total solid content of the reaction system of the polymerization reaction is preferably 25%~40%, more preferably 28%~35%, most preferably 30%~32%.
In the present invention, the polymerization reaction carries out preferably in protective atmosphere, and the present invention is to the offer protective atmosphere Protective gas type there is no any special restriction, using protective gas well known to those skilled in the art, specifically such as Nitrogen.In the present invention, the polymerization reaction preferably carries out under stirring conditions；The present invention is to the no any spy of stirring Different restriction is stirred using stirring condition well known to those skilled in the art.
After the completion of polymerization reaction, the present invention preferably post-processes obtained product system, it is described post-processing include with Lower step:
The product system is mixed with ethyl alcohol, is washed, is dry, obtains polyimides.
The present invention is mixed using mixing condition well known to those skilled in the art to the no any special restriction of mixing Conjunction；It in the present invention, is that polyimides is precipitated by the purpose that the product system is mixed with ethyl alcohol.
In the present invention, the cleaning solution of the washing is preferably ethyl alcohol；The present invention does not have any spy to the mode of washing Different restriction is washed using mode of washing well known to those skilled in the art, and in the present invention, the washing can be specific For reflux washing；The present invention does not have any special restriction to the number of the washing, the polyimides washes clean that will be obtained ?.
The present invention any special restriction no to the drying, using drying condition well known to those skilled in the art into Row is dry.
Below with reference to embodiment to a kind of diamine monomer and its preparation containing asymmetric fluorophore structure provided by the invention Method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene, structural formula It is as follows:
Under a nitrogen atmosphere, to equipped with the 4- fluorine that 35.3g (250mmol) is added in churned mechanically 500mL three-neck flask Nitrobenzene, the P-nethoxyaniline of 40.0g (325mmol), 32.9g (325mmol) triethylamine, 273mL is then added Dimethyl sulfoxide, 85 DEG C of reaction 38h.Room temperature bottom discharge filters in mixture of ice and water, filter cake ethyl alcohol and N, N- dimethyl methyl Amide recrystallizes (V:V=1:1), obtains the 4- nitro -4'- methoxy diphenylamine 45g of orange red acicular crystal, yield 74%；
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask in 10.0g is added The 1- bromine pyrene of (35.6mmol), the 4- methoxyl group -4'- nitrodiphenylamine of 9.2g (37.4mmol), 9.0g (142.2mmol) copper Powder, 19.6g (142.2mmol) potassium carbonate, crown ether -6 4.7g (17.8mmol) 18-, then be added 220ml o-dichlorohenzene, 160 DEG C reaction 18h；It filters while hot, is evaporated under reduced pressure out o-dichlorohenzene, gained crude product ethyl alcohol and n,N-dimethylacetamide (V:V =1:2) recrystallization, obtain 4- nitrobenzophenone -4'- methoxyphenyl -1- amino pyrene 9.6g, yield 60%；
The 4- nitrobenzene of 7.0g (15.6mmol) is added into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Base -4'- methoxyphenyl -1- amino pyrene, 70mL dioxane, 2.4g Pd mass fraction be 10% Pd/C, be heated to back After stream, it is 85% that the mass fraction for being 10:1 with 4- nitrobenzophenone -4'- methoxyphenyl -1- amino pyrene molar ratio, which is slowly added dropwise, Hydrazine hydrate, the reaction was continued under reflux state 18h；Filtering reacting liquid removes Pd/C while hot, and filtrate is concentrated under reduced pressure to original volume 1/3, it is cooling in a nitrogen atmosphere to be precipitated, obtain 4- aminophenyl -4'- methoxyphenyl -1- amino pyrene 6.2g, yield 89%；
Stirring, nitrogen protection under conditions of, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask The middle 4- aminophenyl -4 '-methoxyphenyl -1- amino pyrene and 1.6g (15.4mmol) triethyl group that 5.8g (14.0mmol) is added Amine and 20mLN, in dinethylformamide.Then the DNBC 3,5 dinitrobenzoylchloride of 3.5g (15.4mmol) is dissolved in 10mLN, After dinethylformamide, it is slowly dropped into three-neck flask with rubber head dropper.After stirring at normal temperature 3h, it is warming up to 140 DEG C React 16h；Room temperature bottom discharge filters in ethyl alcohol, and filter cake ethyl alcohol and n,N-dimethylacetamide recrystallization obtain N-4- first Phenyl-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino pyrene 7.3g, yield 85%；
The N-4- methoxyl group of 5.2g (8.6mmol) is added into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Phenyl-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino pyrene, 50mL dioxane, 2.0g mass fraction are 10% Pd/C, after being heated to reflux, be slowly added dropwise and N-4- methoxyphenyl-N-4- (3,5- dinitrobenzamide base) phenyl- The hydrazine hydrate that the mass fraction that 1- amino pyrene molar ratio is 20:1 is 85%, the reaction was continued under reflux state 25h；Filtering is anti-while hot It answers liquid to remove Pd/C, filtrate is concentrated under reduced pressure to the 2/5 of original volume, cooling precipitation, obtains N-4- methoxybenzene in a nitrogen atmosphere Base-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene 4.0g, yield 84%；
Fig. 1 is the proton magnetic spectrum of N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene Figure, as seen from the figure, the chemical shift ownership of H atom are clear, can correspond, and are gained N-4- methoxyphenyl-N-4- (3,5- Diaminobenzene formamido) phenyl -1- amino pyrene structure.
Embodiment 2
The preparation of N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino naphthalenes, knot Structure formula is as follows:
Under a nitrogen atmosphere, to equipped with the 4- fluorine that 35.3g (250mmol) is added in churned mechanically 500mL three-neck flask Nitrobenzene, the naphthalidine of 46.5g (325mmol), 32.9g (325mmol) triethylamine, then be added 273mL dimethyl Sulfoxide, 85 DEG C of reaction 38h.Room temperature bottom discharge filters in mixture of ice and water, filter cake ethyl alcohol and n,N-Dimethylformamide weight It crystallizes (V:V=1:1), obtains the 4- nitrobenzophenone -1'- naphthylamines 50.1g of orange red acicular crystal, yield 76%；
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask in 8.30g is added 4- nitrobenzophenone -1 '-naphthylamines, the 9.0g of the bromo- 2- methoxynaphthalene of the 1- of (35.0mmol), 9.9g (37.4mmol) The copper powder of (142.2mmol), 19.6g (142.2mmol) potassium carbonate, crown ether -6 4.7g (17.8mmol) 18-, are then added The o-dichlorohenzene of 220ml, 160 DEG C of reaction 18h；It filters while hot, is evaporated under reduced pressure out o-dichlorohenzene, gained crude product ethyl alcohol and N, N- dimethyl acetamide (V:V=1:2) recrystallization, obtains 4- nitrobenzophenone -1'- methoxyl group naphthalene -1- amino naphthalenes 11.5g, produces Rate 78%；
The 4- nitrobenzene of 8.4g (20.0mmol) is added into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Base -1'- methoxyl group naphthalene -1- amino naphthalenes, 70mL dioxane, 3.0g Pd mass fraction be 10% Pd/C, be heated to back After stream, it is 85% that the mass fraction for being 10:1 with 4- nitrobenzophenone -1'- methoxyl group naphthalene -1- amino naphthalenes molar ratio, which is slowly added dropwise, Hydrazine hydrate, the reaction was continued under reflux state 18h；Filtering reacting liquid removes Pd/C while hot, and filtrate is concentrated under reduced pressure to original volume 1/3, it is cooling in a nitrogen atmosphere to be precipitated, obtain 4- aminophenyl -1 '-methoxyl group naphthalene -1- amino naphthalenes 6.9g, yield 88%；
Stirring, nitrogen protection under conditions of, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask Middle 4- aminophenyl-the 1 '-methoxyl group naphthalene -1- amino naphthalenes and 1.6g (15.4mmol) triethyl group that 6.0g (15.4mmol) is added Amine and 20mLN, in dinethylformamide.Then the DNBC 3,5 dinitrobenzoylchloride of 3.5g (15.4mmol) is dissolved in 10mLN, After dinethylformamide, it is slowly dropped into three-neck flask with rubber head dropper.After stirring at normal temperature 3h, it is warming up to 140 DEG C React 16h；Room temperature bottom discharge filters in ethyl alcohol, and filter cake ethyl alcohol and n,N-dimethylacetamide recrystallization obtain N-1- first Oxygroup naphthalene-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino naphthalenes 7.5g, yield 83%；
The N-1- methoxy of 6.0g (10.3mmol) is added into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Base naphthalene-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino naphthalenes, 50mL dioxane, 2.0g mass fraction are 10% Pd/C after being heated to reflux, is slowly added dropwise and N-1- methoxyl group naphthalene-N-4- (3,5- dinitrobenzamide base) benzene The hydrazine hydrate that the mass fraction that base -1- amino naphthalenes molar ratio is 20:1 is 85%, the reaction was continued under reflux state 25h；It crosses while hot It filters reaction solution and removes Pd/C, filtrate is concentrated under reduced pressure to the 2/5 of original volume, cooling precipitation, obtains N-1- methoxy in a nitrogen atmosphere Base naphthalene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino naphthalenes 4.2g, yield 79%.
Embodiment 3
The preparation of N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene, structural formula are as follows It is shown:
Under a nitrogen atmosphere, to equipped with the 4- fluorine that 35.3g (250mmol) is added in churned mechanically 500mL three-neck flask Nitrobenzene, the 1- amino anthracene of 62.7g (325mmol), 32.9g (325mmol) triethylamine, then be added 273mL diformazan Base sulfoxide, 85 DEG C of reaction 38h.Room temperature bottom discharge filters in mixture of ice and water, filter cake ethyl alcohol and n,N-Dimethylformamide It recrystallizes (V:V=1:1), obtains the 4- nitro -1'- anthranylamine 50.1g of orange red acicular crystal, yield 76%；
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask in 10.0g is added The 4- bromine pyrene of (35.6mmol), 4- nitro -1 '-anthranylamine of 11.7g (37.4mmol), 9.0g (142.2mmol) copper powder, 19.6g (142.2mmol) potassium carbonate, crown ether -6 4.7g (17.8mmol) 18-, then be added 220ml o-dichlorohenzene, 160 DEG C React 18h；It filters while hot, is evaporated under reduced pressure out o-dichlorohenzene, gained crude product ethyl alcohol and n,N-dimethylacetamide (V:V= It 1:2) recrystallizes, obtains 4- nitrobenzophenone -1 '-anthranylamine -4- amino pyrene 12.5g, yield 68%；
The 4- nitrobenzene of 12.0g (23.4mmol) is added into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Base -1 '-anthranylamine -4- amino pyrene, 70mL dioxane, 2.5g Pd mass fraction be 10% Pd/C, after being heated to reflux, The hydrazine hydrate that the mass fraction for being 10:1 with 4- nitrobenzophenone -1 '-anthranylamine -4- amino pyrene molar ratio is 85% is slowly added dropwise, returns The reaction was continued under stream mode 18h；Filtering reacting liquid removes Pd/C while hot, and filtrate is concentrated under reduced pressure to the 1/3 of original volume, in nitrogen gas It is cooling under atmosphere to be precipitated, obtain 4- aminophenyl -1 '-anthranylamine -4- amino pyrene 9.8g, yield 86%；
Stirring, nitrogen protection under conditions of, to equipped with magnetic stir bar, thermometer, condenser pipe 250mL three-neck flask It is middle be added 9.0g (18.6mmol) 4- aminophenyl -1 '-anthranylamine -4- amino pyrene and 3.2g (30.8mmol) triethylamine and In 20mL N,N-dimethylformamide.Then the DNBC 3,5 dinitrobenzoylchloride of 7.0g (30.8mmol) is dissolved in 10mLN, N- After dimethylformamide, it is slowly dropped into three-neck flask with rubber head dropper.After stirring at normal temperature 3h, it is warming up to 140 DEG C instead Answer 16h；Room temperature bottom discharge filters in ethyl alcohol, and filter cake ethyl alcohol and n,N-dimethylacetamide recrystallization obtain N-1- amino Anthracene-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino pyrene 10.9g, yield 85%；
The N-1- amino of 10g (10.3mmol) is added dropwise into the 250mL three-neck flask equipped with magnetic stir bar, condenser pipe Anthracene-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino pyrene, 50mL dioxane, 2.0g mass fraction are 10% Pd/C after being heated to reflux, is slowly added to and N-1- amino anthracene-N-4- (3,5- dinitrobenzamide base) phenyl -1- amino The hydrazine hydrate that the mass fraction that pyrene molar ratio is 20:1 is 85%, the reaction was continued under reflux state 25h；Filtering reacting liquid removes while hot Pd/C is removed, filtrate is concentrated under reduced pressure to the 2/5 of original volume, cooling precipitation, obtains N-4- methoxyphenyl-N-4- in a nitrogen atmosphere (3,5- diaminobenzene formamido) phenyl -1- amino pyrene 4.0g, yield 84%.
Embodiment 4
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and terephthalic acid (TPA) are poly- Conjunction prepares polyamide:
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in be added N-4- methoxyphenyl-N-4- made from 0.5502g (1mmol) embodiment 1 (3,5- diaminobenzene formamido) phenyl -1- ammonia Base pyrene, the terephthalic acid (TPA) of 0.1661g (1mmol), 0.15g CaCl2, 1.0mL triphenyl phosphite, 0.5mL pyridine and The N-Methyl pyrrolidone of 2.5mL reacts 3h at 120 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, successively use ethyl alcohol, water It is heated to reflux washing 30min with ethyl alcohol, 120 DEG C of drying finally obtain N-4- methoxyphenyl-N-4- (3,5- diaminobenzenes Formamido) phenyl -1- amino pyrene and terephthaldehyde's acid type polyamide 0.6731g, it is labeled as 9a.
Embodiment 5
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and cyclohexanetetracarboxylic acid Dianhydride polymerization prepares polyimides
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.5502g made from 1 (1mmol) N-1- aminobenzene-N-4- methoxyphenyl-N '-benzene -3,5- diaminobenzene formamide, The N-Methyl pyrrolidone of 0.2181g (1mmol) cyclohexanetetracarboxylic acid dianhydride, 2.0mL after reacting 12h under room temperature, is added The isoquinolin of 0.05ml reacts 12h at 180 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, be heated to reflux washing with ethyl alcohol Twice, each 30min, drying, finally obtains N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- ammonia Base pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides.Labeled as 9b, quality 0.7134g.
Fig. 2 is the N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene The infrared spectrum of alkane tetracarboxylic acid dianhydride type polyimides, 3343cm-1For the stretching vibration absworption peak of N-H, 1790cm-1For C=O Asymmetric stretching vibration absworption peak, 1725cm-1For the symmetrical stretching vibration absorption peak of C=O, 1346cm-1For the flexible of C-N Vibration absorption peak, it was demonstrated that resulting polymers are N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- Amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides；
Fig. 3 is the N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene The TGA curve graph of alkane tetracarboxylic acid dianhydride type polyimides, as seen from the figure, in a nitrogen atmosphere, 5% weightless temperature is 453 DEG C, 10% weightless temperature is 473 DEG C, illustrates it with good thermal stability；
Fig. 4 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene four The cyclic voltammetry curve figure of formic acid dianhydride type polyimides, as seen from the figure, the oxidation-reduction process of the polyimides are reversible , and the stability with height；
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- that testing example 5 is prepared The spectroelectrochemistry performance of amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides, the specific method is as follows:
The polyimides is dissolved in n,N-dimethylacetamide, the concentration of polyimide solution is 3mg/mL, will Its drop coating is on ito glass plate, being used as working electrode after 90~120 DEG C of drying, platinum filament is used as to electrode, and Ag/AgCl is as ginseng Three-electrode system is constructed using the acetonitrile solution of 0.1M tetrabutylammonium perchlorate (TBAP) as electrolyte than electrode.Pass through electrification It learns work station and applies incremental voltage, monitor the variation of its absorption spectrum with ultraviolet-visual spectrometer in the process；
Fig. 5 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene four The electrochromism spectrogram of formic acid dianhydride type polyimides, when applied voltage rises to 1.1V from 0V, the color of film is become from yellow Purple；
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- that testing example 5 is prepared The performance that the electrochromism of amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides is converted, the specific method is as follows:
Based on above-mentioned three-electrode system, square-wave voltage is applied by electrochemical workstation, uses ultraviolet spectra in the process Instrument monitors the variation of absorption spectrum at its maximum absorption band.
Fig. 6 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene four The electrochromism response time spectrogram of formic acid dianhydride type polyimides, as seen from the figure, square-wave voltage 0-1.1V, ultraviolet spectra prison The variation for surveying absorption spectrum at its 785nm, when the duration is 20s, coloring/fading time is 4.37/1.61s, is illustrated not Symmetrical structure can weaken the sedimentation of polymer, conducive to the insertion and extraction of electrolyte ion；
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- that testing example 5 is prepared The automatically controlled fluorescence property of amino pyrene and cyclohexanetetracarboxylic acid dianhydride type polyimides, the specific method is as follows:
Based on above-mentioned three-electrode system, apply incremental voltage by electrochemical workstation, in the process with fluorescence light Spectrometer monitors the variation of its fluorescence intensity.
Fig. 7 is N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and hexamethylene four The automatically controlled fluorogram of formic acid dianhydride type polyimides, it is as seen from the figure, glimmering at 518nm when applied voltage rises to 1.1V from 0V Luminous intensity gradually decreases, and the yellow fluorescence of film is quenched, and when reversely applying voltage, the yellow fluorescence of film restores, it was demonstrated that this is poly- Acid imide has reversible automatically controlled Fluorescence behaviour；At 518nm, fluorescent contrast 106, illustrate that loose dissymmetrical structure can subtract Degree is quenched in solid state fluorescence caused by weak accumulation, enhances fluorescent switch contrast.
Embodiment 6
N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and terephthalic acid (TPA) and 1,4 cyclohexanedicarboxylic acid copolymerization prepares polyamide
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.5502g made from 1 (1mmol) N-1- aminobenzene-N-4- methoxyphenyl-N '-benzene -3,5- diaminobenzene formamide, The terephthalic acid (TPA) of 0.0831g (0.5mmol), the 1,4 cyclohexanedicarboxylic acid of 0.0861 (0.5mmol), 0.15g CaCl2、 The N-Methyl pyrrolidone of 1.0mL triphenyl phosphite, 0.5mL pyridine and 2.5mL reacts 3h at 120 DEG C.It discharges in ethyl alcohol Yellow fibrous is presented, is successively heated to reflux washing 30min with ethyl alcohol, water and ethyl alcohol, 120 DEG C of drying finally obtain N-4- Methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and terephthalic acid (TPA) and 1,4- hexamethylene two Formic acid type copolyamide.Labeled as 9c, quality 0.6129g.
Embodiment 7
N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino naphthalenes and terephthaldehyde Sour polymerization prepares polyamide
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.5246g made from 2 (1mmol) N-1- aminobenzene-N-4- methoxyphenyl-N '-benzene -3,5- diaminobenzene formamide, Terephthalic acid (TPA), the 0.15g CaCl of 0.1661g (1mmol)2, 1.0mL triphenyl phosphite, 0.5mL pyridine and 2.5mL N- Methyl pyrrolidone reacts 3h at 120 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, successively with ethyl alcohol, water and ethyl alcohol heating 30min is washed to reflux, 120 DEG C of drying finally obtain N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamides Base) phenyl -1- amino naphthalenes and terephthaldehyde's acid type polyamide.Labeled as 10a, quality 0.5981g.
Embodiment 8
N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino naphthalenes and hexamethylene four Formic acid dianhydride polymerization prepares polyimides
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.5246g made from 2 (1mmol) N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino Naphthalene, 0.2181g (1mmol) cyclohexanetetracarboxylic acid dianhydride, 2.0mL N-Methyl pyrrolidone, after reacting 12h under room temperature, be added The isoquinolin of 0.05ml reacts 12h at 180 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, be heated to reflux washing with ethyl alcohol Twice, each 30min, drying, finally obtains N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl- 1- amino naphthalenes and cyclohexanetetracarboxylic acid dianhydride type polyimides.Labeled as 10b, quality 0.7113g.
Embodiment 9
N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene polymerize system with terephthalic acid (TPA) Standby polyamide
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.6787g made from 4 (1mmol) N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene, Terephthalic acid (TPA), the 0.15g CaCl of 0.1661g (1mmol)2, 1.0mL triphenyl phosphite, 0.5mL pyridine and 2.5mL N- Methyl pyrrolidone reacts 3h at 120 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, successively with ethyl alcohol, water and ethyl alcohol heating 30min is washed to reflux, 120 DEG C of drying finally obtain N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl- 1- amino pyrene and terephthaldehyde's acid type polyamide.Labeled as 11a, quality 0.7018g.
Embodiment 10
N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene and cyclohexanetetracarboxylic acid dianhydride Polymerization prepares polyimides
Under a nitrogen atmosphere, to equipped with magnetic stir bar, thermometer, condenser pipe 50mL three-neck flask in embodiment is added 0.6787g made from 4 (1mmol) N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene, The N-Methyl pyrrolidone of 0.2181g (1mmol) cyclohexanetetracarboxylic acid dianhydride, 2.0mL after reacting 12h under room temperature, is added The isoquinolin of 0.05ml reacts 12h at 180 DEG C.It discharges and yellow fibrous is presented in ethyl alcohol, be heated to reflux washing with ethyl alcohol Twice, each 30min, drying, finally obtains N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene With cyclohexanetetracarboxylic acid dianhydride type polyimides.Labeled as 11b, quality 0.7623g.
Embodiment 11
The polyamide or polyimides be prepared to embodiment 4~10 is in N-Methyl pyrrolidone (NMP), dimethyl second Amide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and chloroform (CHCl3) in Dissolubility is tested, and test result is as shown in table 1:
Table 1: the dissolubility of polyamide and polyimides prepared by embodiment 4~10 in 6 kinds of common solvents
Note: being 10mg/mL for measuring deliquescent solution concentration；
++: it is solvable at room temperature；+: heating is solvable；+-: part is solvable；: heating is insoluble.
As seen from the above embodiment, the diamine monomer provided by the present invention containing asymmetric fluorophore structure is prepared Polyamide or polyimides have stable electroactive, and dissolubility is more preferable, and fluorescent contrast is higher, fluorescence and discoloration electroresponse speed Degree is faster.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of diamine monomer containing asymmetric fluorophore structure has structure shown in formula I:
In formula I, R1For
R2For
2. the diamine monomer as described in claim 1 containing asymmetric fluorophore structure, which is characterized in that described containing asymmetric glimmering The diamine monomer of light blob structure include N-4- methoxyphenyl-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene, N-1- (2- methoxyl group naphthalene)-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino naphthalenes or N-1- amino anthracene-N-4- (3,5- diaminobenzene formamido) phenyl -1- amino pyrene.
3. the preparation method of the diamine monomer of any of claims 1 or 2 containing asymmetric fluorophore structure, comprising the following steps:
By 4- fluoronitrobenzene, R2-NH2, triethylamine and dimethyl sulfoxide mixing, occur nucleophilic substitution I, obtain with formula The compound of structure shown in II；
By compound, copper powder, potassium carbonate, the 18- crown ether -6, R with structure shown in formula II1- X and o-dichlorohenzene mixing, hair Raw ullmann reaction, obtains the compound with structure shown in formula III；The R1X is Cl, Br or I in-X；
The compound with structure shown in formula III, Pd/C, hydrazine hydrate and dioxane are mixed, reduction reaction I occurs, obtains To the compound with structure shown in formula IV；
By compound, triethylamine, N,N-dimethylformamide and DNBC 3,5 dinitrobenzoylchloride with structure shown in formula IV Mixing occurs nucleophilic substitution II, obtains the compound with structure shown in formula V；
Compound, Pd/C, hydrazine hydrate and dioxane with structure shown in formula V are mixed, reduction reaction II occurs, obtains Compound with structure shown in formula I；
4. preparation method as claimed in claim 3, which is characterized in that the temperature of the nucleophilic substitution I is 80~100 DEG C, the time of the nucleophilic substitution I is 30~45h.
5. preparation method as claimed in claim 3, which is characterized in that the temperature of the ullmann reaction is 140~180 DEG C, The time of the ullmann reaction is 12~20h.
6. preparation method as claimed in claim 3, which is characterized in that the temperature of the reduction reaction I is 70~90 DEG C, described The time of reduction reaction I be 1~for 24 hours.
7. preparation method as claimed in claim 3, which is characterized in that the temperature of the nucleophilic substitution II is 135~145 DEG C, the time of the nucleophilic substitution II is 3~8h.
8. preparation method as claimed in claim 3, which is characterized in that the temperature of the reduction reaction II is 75~95 DEG C, institute The time for stating reduction reaction II is 3~30h.
9. the diamine monomer of any of claims 1 or 2 containing asymmetric fluorophore structure is in electrochromism and automatically controlled fluorescent material In application, the electrochromism and automatically controlled fluorescent material are polyamide or polyimides.
10. application as claimed in claim 9, which is characterized in that the preparation method of the polyamide the following steps are included:
The diamine monomer containing asymmetric fluorophore structure and the compound with structure shown in formula a are mixed, polymerize Reaction, obtains polyamide；
Ar is in the formula a
The preparation method of the polyimides the following steps are included:
The diamine monomer containing asymmetric fluorophore structure is mixed with the compound with structure shown in formula b, is polymerize Reaction, obtains polyimides；
Ar' is in the formula b
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110878140A (en) * 2019-08-28 2020-03-13 江苏爱姆欧光电材料有限公司 Novel aromatic polyimide containing imide flexible group and preparation method thereof
CN112625240A (en) * 2020-12-16 2021-04-09 常州大学 Fluorescent polymer, preparation and application
CN115490858A (en) * 2022-10-08 2022-12-20 潍坊科技学院 Dark brown high-temperature-resistant polyimide containing heteropyrene structure and synthesis method thereof

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CN102675637A (en) * 2012-05-24 2012-09-19 黑龙江大学 Electrochromatic polyimide and preparation method thereof
CN105085281A (en) * 2015-08-07 2015-11-25 吉林大学 Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation

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CN105085281A (en) * 2015-08-07 2015-11-25 吉林大学 Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation

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CN110878140A (en) * 2019-08-28 2020-03-13 江苏爱姆欧光电材料有限公司 Novel aromatic polyimide containing imide flexible group and preparation method thereof
CN112625240A (en) * 2020-12-16 2021-04-09 常州大学 Fluorescent polymer, preparation and application
CN115490858A (en) * 2022-10-08 2022-12-20 潍坊科技学院 Dark brown high-temperature-resistant polyimide containing heteropyrene structure and synthesis method thereof
CN115490858B (en) * 2022-10-08 2023-06-23 潍坊科技学院 Dark brown high-temperature-resistant polyimide containing hetero pyrene structure and synthesis method thereof

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