CN113698306A - Diamine compound containing symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof - Google Patents

Diamine compound containing symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof Download PDF

Info

Publication number
CN113698306A
CN113698306A CN202111041734.0A CN202111041734A CN113698306A CN 113698306 A CN113698306 A CN 113698306A CN 202111041734 A CN202111041734 A CN 202111041734A CN 113698306 A CN113698306 A CN 113698306A
Authority
CN
China
Prior art keywords
catalyst
polyamide
reaction
diamine compound
dinitro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111041734.0A
Other languages
Chinese (zh)
Other versions
CN113698306B (en
Inventor
王大明
李晓倩
苏凯欣
赵晓刚
周宏伟
陈春海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202111041734.0A priority Critical patent/CN113698306B/en
Publication of CN113698306A publication Critical patent/CN113698306A/en
Application granted granted Critical
Publication of CN113698306B publication Critical patent/CN113698306B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/58—Naphthylamines; N-substituted derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/94—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a diamine compound containing a symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof, and belongs to the technical field of electric control fluorescence. In the diamine compound structure provided by the invention, the highly symmetrical double triphenylamine group is used as a derivative structure of triphenylamine, the stability of a single cation free radical can be obviously enhanced due to the resonance coupling effect between two N atoms in the derivative structure of the double triphenylamine, and compared with the single triphenylamine, the derivative structure of the double triphenylamine has higher HOMO energy level and lower oxidation potential and obviously enhances the electrochemical stability. In addition, the polymer prepared from the diamine compound has high fluorescence contrast and short fluorescence switching time.

Description

Diamine compound containing symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof
Technical Field
The invention relates to the technical field of electric control fluorescence, in particular to a diamine compound containing a symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof.
Background
The electric control fluorescence refers to the phenomenon that the fluorescence of the material is reversibly switched on or off or discolored under the action of an external electric field, and has potential application value in the fields of optical display, information encryption, information communication and the like due to the advantages of good controllability, good reversibility, environmental friendliness and the like.
The polymer has the advantages of strong processability and easily modified structure, the polyamide and the polyimide have excellent physical and chemical properties, and star-shaped Triphenylamine (TPA) derivatives are introduced into the polyamide and the polyimide, so that the solubility of the polyamide and the polyimide is effectively improved, and the polymer has photoelectric properties. However, the single triphenylamine structure reported to be synthesized at present is low in electrochemical stability because of the lack of N atoms capable of resonance stabilization, high oxidation potential (>1.0V), and easy occurrence of side reactions. In addition, when a single fluorophore is connected with triphenylamine, the strong pi-pi stacking effect among molecules causes low fluorescence contrast and long conversion time, and practical application of the fluorescence is limited.
Disclosure of Invention
The invention aims to provide a diamine compound containing a symmetrical double-fluorophore structure, preparation and application thereof, polyamide and polyimide, preparation and application thereof, wherein the diamine compound has high electrochemical stability, and a polymer prepared from the diamine compound has high fluorescence contrast and short fluorescence switching time.
The invention provides a diamine compound containing a symmetrical double-fluorophore structure, wherein in the structure of the diamine compound, a highly symmetrical double triphenylamine group is used as a derivative structure of triphenylamine, the stability of a single cation free radical can be obviously enhanced due to the resonance coupling effect between two N atoms in the derivative structure of the double triphenylamine, and the longer conjugation length enables the diamine compound to have a higher HOMO energy level and a lower oxidation potential compared with single triphenylamine, so that the electrochemical stability is obviously enhanced.
In addition, due to the fact that triphenylamine enhanced fluorescence is weak, the double fluorophore (R) is introduced into the diamine structure, and the double fluorophore is introduced into a polymer chain, so that the fluorescence intensity of the prepared polymer is remarkably enhanced, the high fluorescence contrast of the polymer is ensured, the close packing between the polymer chains can be weakened due to the synergistic effect of the double fluorophore and the double triphenylamine structure, the electrolyte ion transmission speed is accelerated, the fluorescence switching time of the polymer is remarkably shortened, the dissolving film forming capacity is remarkably enhanced, and the commercial application of the polymer processed into a device is facilitated.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a diamine compound prepared in example 2;
FIG. 2 is a H-H cosy NMR spectrum of the diamine prepared in example 2;
FIG. 3 is an IR spectrum of the dinitro compound N, N '-bis (4-nitrophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2;
FIG. 4 is an IR spectrum of the diamine compound N, N '-bis (4-aminophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2;
FIG. 5 is a nuclear magnetic spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (naphthyl) -1, 4-p-phenylenediamine prepared in example 1;
FIG. 6 is an IR spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (anthracenyl) -1, 4-p-phenylenediamine prepared in example 3;
FIG. 7 is a nuclear magnetic spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (6-methoxynaphthyl) -1, 4-p-phenylenediamine prepared in example 4;
FIG. 8 is a H nuclear magnetic spectrum of a polyamide produced in application example 1;
FIG. 9 is an IR spectrum of a polyamide produced in application example 1;
FIG. 10 is an infrared spectrum of a polyamide produced in application example 2;
FIG. 11 is an IR spectrum of a polyimide produced in application example 3;
FIG. 12 is an IR spectrum of a polyimide prepared in application example 4
FIG. 13 is a DSC chart of the polyamide produced in application example 1;
FIG. 14 is a cyclic voltammogram of the polyamide prepared in application example 1;
FIG. 15 is a graph showing the stability of the polyamide prepared in application example 1 in a first heavy redox state;
FIG. 16 is an electronically controlled fluorescence spectrum of a polyamide prepared in application example 1;
FIG. 17 is an electrically controlled fluorescence response time spectrum of the polyamide prepared in application example 1;
FIG. 18 is a graph of the electrically controlled fluorescence response time of the polyamide prepared in application example 1 at different cycle times.
Detailed Description
The invention provides a diamine compound containing a symmetrical double-fluorophore structure, which has a structure shown in a formula I:
Figure BDA0003249545620000031
wherein R is
Figure BDA0003249545620000032
Figure BDA0003249545620000033
The invention provides a preparation method of a diamine compound containing a symmetrical double-fluorophore structure, which comprises the following steps:
mixing p-phenylenediamine, p-fluoronitrobenzene, a first catalyst and an organic solvent, and carrying out substitution reaction to obtain a dinitro monomer;
mixing the dinitro monomer, the brominated fluorescent compound, a second catalyst and a polar solvent, and performing a coupling reaction to obtain a dinitro compound;
mixing the dinitro compound, a third catalyst, a reducing agent and a mixed solvent, and carrying out reduction reaction to obtain a diamine compound containing a symmetrical double-fluorophore structure and having a structure shown in a formula I;
the dinitro monomer has a structure represented by formula II-1:
Figure BDA0003249545620000041
the structural formula of the brominated fluorescent compound is Br-R;
the dinitro compound has a structure shown as a formula II-2;
Figure BDA0003249545620000042
r is
Figure BDA0003249545620000043
Figure BDA0003249545620000044
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, p-phenylenediamine, p-fluoronitrobenzene, a first catalyst and an organic solvent are mixed for substitution reaction to obtain a dinitro monomer. In the present invention, the first catalyst is preferably a composite catalyst, the composite catalyst preferably includes a main catalyst and a sub-catalyst, and the main catalyst preferably includes triethylamine, tripropylamine, tributylamine, or potassium hydroxide; the secondary catalyst preferably comprises cyclodextrin, tetrabutylammonium bromide or a quaternary ammonium base.
In the invention, the molar ratio of the p-phenylenediamine, the p-fluoronitrobenzene, the main catalyst and the auxiliary catalyst is preferably 1 (2.2-2.5): 4-8): 0.5-1.2, and more preferably 1 (2.3-2.4): 4.5-6.5): 0.6-0.9.
In the present invention, the organic solvent is preferably sulfolane, diphenyl ether sulfone, or diphenyl ether; the solid content of the system obtained by mixing the p-phenylenediamine, the p-fluoronitrobenzene, the first catalyst and the organic solvent is preferably 25-40 wt%, and more preferably 28-35 wt%; the process of mixing the p-phenylenediamine, the p-fluoronitrobenzene, the first catalyst and the organic solvent is not particularly limited in the invention, and the materials are uniformly mixed according to the process well known in the art.
In the invention, the substitution reaction is preferably carried out under the microwave condition, the temperature of the substitution reaction is preferably 160-200 ℃, more preferably 175-185 ℃, and the reaction time is preferably 4-10 h, more preferably 6-8 h. In the substitution reaction process, nucleophilic substitution is carried out on the active hydrogen of diamine on p-phenylenediamine and the fluorine atom on p-fluoronitrobenzene to generate the dinitro compound shown as a formula II-1.
After the substitution reaction is finished, preferably, the obtained material is cooled to room temperature, discharged into ice water, and subjected to suction filtration, drying and recrystallization in sequence to obtain a dinitro monomer; the reagent used for recrystallization is preferably a DMSO/ethanol solution with the volume ratio of 1: 3; the number of the recrystallization is preferably 3; the discharging, the amount of ice water, the suction filtration and the drying process are not particularly limited, and the process is carried out according to the process well known in the art.
In the present invention, the dinitro monomer has a structure represented by formula II-1:
Figure BDA0003249545620000051
after obtaining the dinitro monomer, the invention mixes the dinitro monomer, the bromo-fluorescent compound, the second catalyst and the polar solvent to carry out coupling reaction, thus obtaining the dinitro compound. In the present invention, the second catalyst preferably comprises a copper catalyst, a cocatalyst and a phase transfer catalyst; the copper catalyst is preferably copper powder or cuprous iodide, the cocatalyst is preferably potassium carbonate, sodium carbonate, potassium hydride or sodium cyanide, and the phase transfer catalyst is preferably 18 crown-6 or 15 crown-5; the molar ratio of the dinitro monomer, the brominated fluorescent compound, the copper catalyst, the cocatalyst and the phase transfer catalyst is preferably 1 (2.0-2.5) to 3-10 to 3-12 to 0.4-1, and more preferably 1 (2.0-2.3): (5-7): (4-9): (0.5 to 0.7).
In the invention, the structural formula of the brominated fluorescents is Br-R; r is the same as above and is not described herein.
In the present invention, the polar solvent is preferably o-dichlorobenzene or 1,2, 4-trichlorobenzene; the total solid content of the system obtained by mixing the dinitro monomer, the brominated fluorescent compound, the copper catalyst, the cocatalyst, the phase transfer catalyst and the polar solvent is preferably 30-45 wt%, and more preferably 32-40 wt%. The mixing process is not particularly limited in the present invention, and the materials are uniformly mixed according to the process known in the art.
In the present invention, the coupling reaction is preferably carried out under a nitrogen atmosphere; the temperature of the coupling reaction is preferably 160-175 ℃, more preferably 160-168 ℃, and the reaction time is preferably 20-36 hours, more preferably 22-25 hours. In the coupling reaction process, active hydrogen on a-NH bond in the dinitro compound reacts with bromine atoms on a brominated fluorophore, and dehydrogenation and debromination coupling are carried out to form the dinitro compound shown in a formula II-2.
After the coupling reaction is completed, the invention preferably filters the obtained product system while the product system is hot to remove the catalyst and salt, obtains a solid crude material by pouring a poor solvent into the obtained filtrate or distilling to remove the solvent, and obtains the dinitro compound by recrystallization or column chromatography purification. The selection of the poor solvent and the distillation mode, and the types and the proportion of the solvent used for recrystallization and the developing agent used for column chromatography are not particularly limited, and the method can be carried out according to the common processes in the field. In the embodiment of the invention, ethanol solution is poured into the obtained filtrate to separate out coarse material, and ethanol and DMAc solution with the volume ratio of 4:1 or ethanol/DMF solution with the volume ratio of 5:1 are used for recrystallization twice to obtain dinitro compound; or distilling the obtained filtrate under reduced pressure, and then adding dichloromethane/petroleum ether with the volume ratio of 2:1 or a mixture of dichloromethane and petroleum ether with the volume ratio of 6: and (3) performing column chromatography purification by using petroleum ether/ethyl acetate as a developing agent to obtain the dinitro compound.
In the present invention, the dinitro compound has a structure represented by the formula II-2;
Figure BDA0003249545620000071
after obtaining the dinitro compound, the third catalyst, the reducing agent and the mixed solvent are mixed for reduction reaction to obtain the diamine compound containing the symmetrical double-fluorophore structure with the structure shown in the formula I. In the invention, the third catalyst is preferably Pd/C, and the Pd/C is preferably Pd/C with the mass fraction of 10% sold on the market; the reducing agent is preferably hydrazine hydrate, and the hydrazine hydrate is preferably a hydrazine hydrate solution with the mass fraction of 85% sold in the market; the mass ratio of the dinitro compound to Pd/C is preferably 1 (0.2-0.4), more preferably 1: (0.25-0.30), the molar ratio of the dinitro compound to the reducing agent is preferably 1 (10-40), more preferably 1: (26-32).
In the present invention, the mixed solvent is preferably a mixed solution of 1, 4-dioxane and ethanol; the volume ratio of the dioxane to the ethanol is preferably 1 (0.5-1.5), more preferably 1: (0.5 to 1.0). In the invention, the total solid content of the system obtained by mixing the dinitro compound and the mixed solvent is preferably 4-20 wt%, and more preferably 5-12 wt%. The process of mixing the dinitro compound, the third catalyst, the reducing agent and the mixed solvent is not particularly limited in the present invention, and the materials are uniformly mixed according to a process well known in the art.
In the present invention, the reduction is carried outThe reaction is preferably carried out under a nitrogen atmosphere and under reflux conditions; the temperature of the reduction reaction is preferably 80-110 ℃, more preferably 90-100 ℃, and the reaction time is preferably 10-36 hours, more preferably 16-25 hours. During the reduction reaction, -NO in the dinitro compound2The group is reduced into-NH by hydrazine hydrate under the catalysis of Pd/C2The radical, the dinitro compound, is reduced to the diamine compound of formula I.
After the reduction reaction is completed, the invention preferably carries out hot filtration on the obtained system to remove the catalyst, concentrates the obtained filtrate with water to the original volume of 1/3 or 1/4 or 1/6 or 1/7, and precipitates the obtained solid to obtain the diamine compound containing the symmetrical double-fluorophore structure and having the structure shown in the formula I. The process of the hot filtration and concentration is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the present invention, the substitution reaction, the coupling reaction, and the reduction reaction have the reaction formula:
Figure BDA0003249545620000081
the invention provides application of the diamine compound containing the symmetrical double-fluorophore structure in the technical scheme or the diamine compound containing the symmetrical double-fluorophore structure prepared by the preparation method in the technical scheme in preparation of polyamide or polyimide.
The invention provides polyamide, which has a structure shown in a formula III:
Figure BDA0003249545620000082
wherein n is 10-200 and n is an integer; ar is
Figure BDA0003249545620000083
R is
Figure BDA0003249545620000084
Figure BDA0003249545620000085
Figure BDA0003249545620000091
In the present invention, the polyamide is preferably
Figure BDA0003249545620000092
n＝155
Or
Figure BDA0003249545620000093
n＝180。
The invention provides a preparation method of polyamide in the technical scheme, which comprises the following steps:
mixing the diamine compound containing the symmetrical double-fluorophore structure, diacid, a cosolvent, a condensing agent, a catalyst and a reaction solvent, and carrying out polycondensation reaction to obtain polyamide;
the diacid is terephthalic acid, trans-1, 4-cyclohexanedicarboxylic acid or 4,4' -diphenyldicarboxylic acid.
In the present invention, the structural formula of the diacid is HOOC-Ar-COOH, and the Ar is the same as that in the polyamide structure, and is not described again.
In the invention, the cosolvent is preferably calcium chloride, magnesium chloride, calcium iodide or magnesium fluoride, the condensing agent is preferably a mixture of triphenyl phosphite and a pyridine compound, and the pyridine compound is preferably pyridine, piperidine or 2-methylpyridine; the catalyst and the reaction solvent are both preferably N-methyl pyrrolidone; the preferable dosage ratio of the diamine compound, the diacid, the cosolvent, the triphenyl phosphite and the pyridine compound is 1mmol (0.9-1.1 mmol) to 0.12-0.18 g (0.8-1.2) mL (0.4-0.6) m L; the solid content of the reaction system obtained by mixing the diamine compound, the diacid, the cosolvent, the condensing agent, the catalyst and the reaction solvent is preferably 18-35 wt%, and more preferably 20-30 wt%. The process for mixing the diamine compound, the diacid, the cosolvent, the condensing agent, the catalyst and the reaction solvent is not particularly limited in the present invention, and the mixing may be carried out according to a process well known in the art.
In the invention, the polycondensation reaction is preferably carried out in a nitrogen atmosphere, the temperature of the polycondensation reaction is preferably 105-110 ℃, and the reaction time is preferably 3-4 h.
In the present invention, the reaction formula of the polycondensation reaction is:
Figure BDA0003249545620000101
after the polycondensation reaction is finished, preferably discharging the obtained material into ethanol, refluxing and washing the obtained light green fibrous product with ethanol and water for 3 times in sequence, and drying in vacuum to obtain polyamide; the temperature of the vacuum drying is preferably 110 ℃; the present invention is not particularly limited to other processes, and may be carried out according to processes known in the art.
The invention provides polyimide, which has a structure shown in a formula IV:
Figure BDA0003249545620000102
wherein m is 20-100 and m is an integer; ar' is
Figure BDA0003249545620000103
Figure BDA0003249545620000104
R is
Figure BDA0003249545620000105
Figure BDA0003249545620000111
In the present invention, the structural formula of the polyimide is preferably:
Figure BDA0003249545620000112
m＝95
or
Figure BDA0003249545620000113
m＝80。
The invention provides a preparation method of polyimide in the technical scheme, which comprises the following steps:
mixing a diamine compound containing a symmetrical double-fluorophore structure, dianhydride and an organic solvent, carrying out a polymerization reaction, mixing the obtained polyamic acid solution, acetic anhydride and pyridine, and carrying out chemical imidization to obtain polyimide; the dianhydride is 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (H-PMDA) or hexafluoro dianhydride (6-FDA).
In the invention, the structural formula of the dianhydride is shown as
Figure BDA0003249545620000121
The Ar 'is the same as Ar' in the polyimide, and the description is omitted.
In the invention, the dosage ratio of the diamine compound to the dianhydride, the acetic anhydride and the pyridine is preferably 1.0mmol (0.9-1.1) mmol (2-4) mL (1-2) mL, more preferably 1.0mmol (0.95-1.05) mmol: (2-3) mL: (1-1.5) mL; the organic solvent is preferably N, N-dimethylacetamide; the solid content of the system obtained by mixing the diamine compound, the dianhydride and the organic solvent is preferably 8-30 wt%, and more preferably 10-20 wt%. The mixing process is not particularly limited in the present invention, and the mixing may be performed according to a process well known in the art.
In the present invention, the polymerization reaction is preferably carried out under stirring conditions; the polymerization temperature is preferably room temperature and the time is preferably 24 h.
In the present invention, the reaction formula of the polymerization reaction is:
Figure BDA0003249545620000122
in the present invention, the procedure for mixing the polyamic acid solution, acetic anhydride, and pyridine is not particularly limited, and the mixing may be performed according to a procedure well known in the art.
In the present invention, the temperature of the chemical imidization is preferably 120 ℃ and the time is preferably 12 hours; and (3) completing the thermal imidization, preferably cooling the obtained product system to room temperature, discharging the obtained reaction solution into water, and refluxing and washing the obtained light gray yellow fiber with ethanol, water and methanol for three times to obtain the polyimide. The process of discharging and washing is not particularly limited in the present invention and may be performed according to a process well known in the art.
The invention provides application of the polyamide or the polyimide in the technical scheme in the field of electric control fluorescence. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation of monomer N, N' -di (4-nitrophenyl) -1, 4-p-phenylenediamine has the following structure:
Figure BDA0003249545620000131
21.6g (200mmol) of p-phenylenediamine and 64.9g (460 mmol) of p-phenylenediamine were charged in a 1000mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser under nitrogen atmosphere) Adding 424mL of sulfolane, wherein the solid content of the obtained system is 30.3 wt%, reacting at 180 ℃ for 7h under the microwave condition, cooling the obtained product system to room temperature, discharging the product into 2000mL of ice water, performing suction filtration and drying to obtain a reddish brown crude material, and recrystallizing the crude material by using a DMSO/ethanol solution with the volume ratio of 1:3 for three times to obtain 29.4g of mauve N, N' -bis (4-nitrophenyl) -1, 4-p-phenylenediamine powder, wherein the yield is 42%.1H NMR(300 MHz,DMSO-d6)δ9.29(s,1H),8.14–8.03(d,2H),7.27(s,2H),7.09–6.97(d, 2H).
The preparation of diamine monomer N, N' -di (4-aminophenyl) -N, -di (naphthyl) -1, 4-p-phenylenediamine has the structure:
Figure BDA0003249545620000132
5.3g (15.0mmol) of N, N ' -bis (4-nitrophenyl) -1, 4-p-phenylenediamine, 7.0g (33.7mmol) of 2-bromonaphthalene, 4.8g (75mmol) of copper powder, 6.3g (60mmol) of sodium carbonate and 2.8g (10.5mmol) of 18 crown ether-6 are added to a 250mL three-necked flask equipped with a mechanical stirring device, a thermometer and a condenser under a nitrogen atmosphere, 28mL of 1,2, 4-trichlorobenzene is then added, the resulting system has a solid content of 39 wt%, the reaction is carried out at 160 ℃ for 22h, copper powder and salts are removed by hot filtration, an ethanol solution is poured into the resulting filtrate, a brown crude is precipitated, and recrystallization is carried out twice with a solution of ethanol and DMAc in a volume ratio of 4:1 to give 3.8g of the red dinitro compound N, N ' -bis (4-nitrophenyl) -N, N ' -bis (4-naphthyl) -1, 4-p-phenylenediamine, the yield is 42.2%;
under the protection atmosphere, 2g (3.3mmol) of dinitro compound is added into a 250mL three-neck flask provided with a magnetic stirring bar and a condensation tube, the dinitro compound is heated to the reflux state in a mixed solution (solid content is 6.6 wt%) of 20mL dioxane and 10mL ethanol, 0.6g Pd/C with the mass fraction of 10% is added, 5.7g hydrazine hydrate solution with the mass fraction of 85% is slowly dripped under the reflux state, the reaction is carried out for 16h at 95 ℃, the Pd/C is removed by hot suction filtration, the filtrate is concentrated to 1/4 with water in the original volume, 1.3g of light green fine diamine powder is separated out, and the yield is 72.2%.
Example 2
The preparation of diamine monomer N, N '-di (4-aminophenyl) -N, N' -di (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine has the structure:
Figure BDA0003249545620000141
under nitrogen atmosphere, 4.2g (12mmol) of N, N '-bis (4-nitrophenyl) -1, 4-p-phenylenediamine prepared in example 1, 9.8g (24.8mmol) of 2-bromo-9, 9' spirodi (9H-fluorene), 3.8g (60mmol) of copper powder, 13.2g (96mmol) of potassium carbonate and 1.9g (7.2mmol) of 18 crown ether-6 are added to a 250mL three-necked flask equipped with a mechanical stirring device, a thermometer and a condenser, 50mL of o-dichlorobenzene is added, the obtained system has a solid content of 33.5 wt%, and the reaction is carried out at 160 ℃ for 24 hours, copper powder and salts are removed by filtration while hot, the filtrate is removed by reduced pressure distillation, column chromatography is carried out by using dichloromethane/petroleum ether as a developing agent in a volume ratio of 2:1, and 6.1g of orange-yellow dinitro compound is obtained, the yield is 52.0%;
under the protection of nitrogen, 3.0g (3.1mmol) of dinitro compound is added into a 250mL three-neck flask provided with a magnetic stirring bar and a condensing tube, the dinitro compound is heated to a reflux state in a mixed solution (solid content is 5.1 wt%) of 35mL dioxane and 25mL ethanol, 0.8g Pd/C with the mass fraction of 10% is added, 5.9g hydrazine hydrate solution with the mass fraction of 85% is dropwise added under the reflux state, the reaction is carried out for 22h at 92 ℃, the obtained product is thermally filtered to remove the Pd/C, the obtained filtrate is concentrated to 1/6 with water in the original volume, 1.0g of bright yellow diamine powder is separated out, and the yield is 35.7%.
Example 3
The preparation of diamine monomer N, N '-di (4-aminophenyl) -N, N' -di (anthryl) -1, 4-p-phenylenediamine has the following structure:
Figure BDA0003249545620000151
6.5g (18.5mmol) of N, N' -bis (4-nitrophenyl) -1, 4-p-phenylenediamine prepared in example 1, 10.0g (38.9mmol) of 2-bromo-anthracene, 22.9g (120mmol) of cuprous iodide powder, 22.2g (160mmol) of potassium carbonate and 2.6g (12mmol) of 15 crown-5 were charged in a 250mL three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser under nitrogen atmosphere, and 73mL of 1,2,4 trichlorobenzene was further charged, the solid content of the resulting system was 37.8% by weight, the reaction was carried out at 165 ℃ for 25 hours, the cuprous iodide powder and salts were removed by hot filtration, 1,2,4 trichlorobenzene was removed by distillation under reduced pressure, and column chromatography purification was carried out using a petroleum ether/ethyl acetate mixture in a volume ratio of 6:1 as a developing solvent to obtain 7.7g of a red dinitro compound with a yield of 59%.
Under the protection of nitrogen, 5g (7.1mmol) of dinitro compound is added into a 250mL three-neck flask provided with a magnetic stirring bar and a condensation tube, the dinitro compound is heated to a reflux state in a mixed solution (solid content is 9.7 wt%) of 30mL dioxane and 20mL ethanol, 1.3g of Pd/C with the mass fraction of 10% is added, 10.6g of hydrazine hydrate solution with the mass fraction of 85% is dropwise added under the reflux state, the reaction is carried out for 25h at 100 ℃, the obtained product is subjected to heat suction filtration to remove the Pd/C, the filtrate is concentrated to 1/7 with water in the original volume, light orange diamine powder 2.2g is separated out, and the yield is 48.1%.
Example 4
The preparation of diamine monomer N, N '-di (4-aminophenyl) -N, N' -di (6-methoxy naphthyl) -1, 4-p-phenylenediamine has the structure:
Figure BDA0003249545620000161
5.3g (15mmol) of N, N' -bis (4-nitrophenyl) -1, 4-p-phenylenediamine prepared in example 1, 8.0g (33.7mmol) of 2-bromo-6-methoxynaphthalene, 14.3g (75mmol) of cuprous iodide powder, 2.4g (60mmol) of potassium hydride and 2.3g (10.5mmol) of 15 crown-5 are introduced into a 250mL three-necked flask with a mechanical stirrer, thermometer and condenser under nitrogen, 40mL of o-dichlorobenzene is added, the resulting system has a solids content of 38.2 wt%, reaction is carried out at 166 ℃ for 25h, cuprous iodide powder and salts are removed by filtration while hot, ethanol is added to the filtrate, a dark brown crude is precipitated, and recrystallization is carried out twice with a 5:1 volume ratio ethanol/DMF solution to give 3.8g of an orange dinitro compound in a yield of 38.2%;
under the protection of nitrogen, 2g (3.0mmol) of dinitro compound is added into a 250mL three-neck flask provided with a magnetic stirring bar and a condensation tube, the dinitro compound is heated to a reflux state in a mixed solution (solid content is 9.9 wt%) of 10mL dioxane and 10mL ethanol, 0.55g Pd/C with the mass fraction of 10% is added, 5.5g hydrazine hydrate solution with the mass fraction of 85% is dropwise added under the reflux state, the reaction is carried out for 20 hours at the temperature of 92 ℃, the Pd/C is removed by hot suction filtration of the obtained product, the obtained filtrate is concentrated to 1/3 with water in the original volume, 1.4g of bright green diamine powder is separated out, and the yield is 76.9%.
Application example 1
Semi-aromatic polyamide was prepared by polycondensation of the diamine compound N, N '-bis (4-aminophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2 with trans 1,4 cyclohexanedicarboxylic acid:
a25 mL three-necked flask equipped with a magnetic stirrer was charged with 0.9191g (1mmol) of the diamine compound prepared in example 3, 0.1722g (1mmol) of trans-1, 4-cyclohexanedicarboxylic acid, 0.15g of calcium chloride, 1mL of triphenyl phosphite, 0.5mL of pyridine and 3.6mL of LN-methylpyrrolidone, the solid content of the obtained reaction system was 25 wt%, the reaction was carried out at 105 ℃ for 3.5 hours under a nitrogen atmosphere, the product was discharged into ethanol to obtain a pale yellow-green fibrous product, the product was washed with ethanol and water under reflux in turn, and dried at 100 ℃ under vacuum to obtain 0.6g of the target polyamide with the structural formula:
Figure BDA0003249545620000171
n＝155。
application example 2
Example 4 condensation polymerization of the diamine compound N, N '-bis (4-aminophenyl) -N, N' -bis (6-methoxynaphthyl) -1, 4-p-phenylenediamine prepared in the above reaction with terephthalic acid to prepare a wholly aromatic polyamide:
a25 mL three-necked flask equipped with a magnetic stirrer was charged with 0.6027g (1mmol) of the diamine compound prepared in example 4, 0.1661g (1mmol) of 1, 4-terephthalic acid, 0.16g of calcium chloride, 1.1mL of triphenyl phosphite, 0.4mL of pyridine and 3.1mL of LN-methyl pyrrolidone, the solid content of the obtained reaction system was 23 wt%, reacted at 110 ℃ for 3 hours under a nitrogen atmosphere, discharged in ethanol to obtain a pale green fibrous product, which was then washed with ethanol and water under reflux, and dried at 110 ℃ under vacuum to obtain 0.42g of polyamide having the structural formula:
Figure BDA0003249545620000172
n＝180。
application example 3
The diamine compound N, N '-bis (4-aminophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2 was reacted with 1,2,4, 5-cyclohexanetetracarboxylic dianhydride to prepare a semi-aromatic polyimide:
adding 0.9191g (1mmol) of diamine compound prepared in example 2 into a 25mL three-necked bottle equipped with a magnetic stirrer, adding 5mL of MAc, stirring under the protection of nitrogen until the diamine compound is completely dissolved, slowly adding 0.2242g (1mmol) of 1,2,4, 5-cyclohexane tetracarboxylic dianhydride in batches to form a solution with a solid content of 20 wt%, stirring at normal temperature for 24h to obtain viscous polyamic acid, adding 2mL of acetic anhydride and 1.0mL of pyridine into the polyamic acid, heating to 120 ℃, reacting for 12h, cooling to room temperature, discharging the obtained product into water, and washing the obtained light gray yellow fiber with ethanol, water and methanol in sequence for three times to obtain 0.7g of polyimide powder, wherein the structural formula is as follows:
Figure BDA0003249545620000181
m＝95。
application example 4
The diamine monomer N, N' -bis (4-aminophenyl) -N, -bis (naphthyl) -1, 4-p-phenylenediamine prepared in example 1 was polymerized with 6-fluoro dianhydride to prepare a wholly aromatic polyimide: adding 0.5427g (1mmol) of diamine compound prepared in example 1 into a 25mL three-necked bottle equipped with a magnetic stirrer, adding 6mL DMAc, stirring under the protection of nitrogen until the diamine compound is completely dissolved, adding 0.4442g (1mmol) of 6-fluoro dianhydride in batches to form a solution with a solid content of 15 wt%, stirring at normal temperature for 24h to obtain viscous polyamic acid, adding 2.5mL of acetic anhydride and 1.2mL of pyridine into the polyamic acid, heating to 120 ℃ for reaction for 12h, cooling to room temperature, discharging the obtained product into water, and washing the obtained light green fiber with ethanol, water and methanol in sequence for three times to obtain 0.5g of polyimide powder, wherein the structural formula is as follows:
Figure BDA0003249545620000182
m＝80。
characterization and Performance testing
1) Performing nuclear magnetic characterization on the diamine prepared in example 2, wherein the obtained hydrogen nuclear magnetic spectrum is shown in figure 1; as can be seen from FIG. 1, the chemical shift assignments of H atoms are clear and can correspond one to one, thus proving that the target diamine monomer is successfully synthesized.
FIG. 2 is a H-H cosy NMR spectrum of the diamine prepared in example 2; as can be seen in fig. 2, the coupling between adjacent H atoms is evident and can correspond one to one, further confirming the successful preparation of the diamine monomer.
FIG. 3 is an IR spectrum of the dinitro compound N, N '-bis (4-nitrophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2. As can be seen from FIG. 3, 1586cm-1And 1316cm-1Are each-NO2The successful preparation of the dinitro compound is demonstrated by the antisymmetric and symmetric stretching vibrations.
FIG. 4 is an IR spectrum of diamine N, N '-bis (4-aminophenyl) -N, N' -bis (9,9 spirobifluorenyl) -1, 4-p-phenylenediamine prepared in example 2; as can be seen from FIG. 4, 3456cm-1And 3374cm-1Respectively, the antisymmetric and symmetric stretching vibration of the N-H bond proves the successful synthesis of the diamine monomer.
FIG. 5 is a nuclear magnetic spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (naphthyl) -1, 4-p-phenylenediamine prepared in example 1; as can be seen from FIG. 5, all hydrogen atoms are assigned in a well-defined, one-to-one correspondence, illustrating the successful preparation of diamine monomers.
FIG. 6 is an IR spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (anthracenyl) -1, 4-p-phenylenediamine prepared in example 3; as can be seen from FIG. 6, 3457cm-1And 3368cm-1Respectively, the antisymmetric and symmetric stretching vibration of the N-H bond proves the successful synthesis of the diamine monomer.
FIG. 7 is a nuclear magnetic spectrum of the diamine N, N '-bis (4-aminophenyl) -N, N' -bis (6-methoxynaphthyl) -1, 4-p-phenylenediamine prepared in example 4; as can be seen from fig. 7, all signal peaks are clearly assigned and correspond to hydrogen atoms, confirming the successful synthesis of diamine monomers.
FIG. 8 is a H nuclear magnetic spectrum of the polyamide prepared in application example 1, wherein the chemical shift distribution of H in the nuclear magnetic hydrogen spectrum is clear and the assignment is clear, which proves the successful polymerization of the semi-aromatic polyamide.
FIG. 9 is an IR spectrum of a polyamide produced in application example 1, wherein 3320cm-1Is N-H stretching vibration absorption peak, 1668cm-1The C ═ O stretching vibration absorption peak proved that the polymer structure contained amide bond, and the polymer was polyamide.
2) FIG. 10 is an IR spectrum of a polyamide produced in application example 2, which is 3323cm, as seen in FIG. 16-1Is N-H stretching vibration absorption peak, 1678cm-1The C ═ O stretching vibration absorption peak proved that the polymer structure contained amide bond, and the polymer was polyamide.
FIG. 11 is an IR spectrum of a polyimide produced in application example 3. Wherein, 1784cm-1、1726cm-1Respectively, an asymmetric stretching vibration peak and a symmetric stretching vibration peak of a C ═ O bond, and it was confirmed that the polymer prepared in application example 3 was polyimide.
FIG. 12 is an IR spectrum of a polyimide produced in application example 4. Wherein, 1782cm-1、1722cm-1Asymmetric stretching vibration peak and symmetric stretching vibration peak of C ═ O bond, respectively, prove that the polymer prepared in application example 4 is polyimide.
3) DSC tests were carried out on the polyamide prepared in example 1, and the results are shown in FIG. 13; as can be seen from fig. 13, the glass transition temperature of polyamide is 266 ℃, which exhibits good high temperature resistance, and is beneficial to high temperature processing to form a film and applied to the preparation of heat-resistant materials. ..
4) Cyclic voltammetry testing was performed on the polyamide prepared in example 1, the testing method being: dissolving a polymer in DMAc to enable the concentration of the polymer solution to be 3mg/mL, dripping the polymer solution on an ITO glass plate, drying at 110 ℃, enabling the thickness of the obtained film to be 200 micrometers to 1 nanometer, taking the ITO glass coated with the polymer solution as a working electrode, a platinum wire as a counter electrode, Ag/AgCl as a reference electrode, and taking 0.1mol/L acetonitrile solution of tetrabutylammonium perchlorate as an electrolyte solution; based on the three-electrode system, a constant range of voltage was applied to the working electrode in the cyclicvoltimametry mode, and the results are shown in fig. 14. As can be seen from fig. 14, the polyamide has two aligned reversible redox peaks, and a lower initial oxidation potential (0.36V), which indicates that the introduction of the bis-triphenylamine group can significantly enhance the coupling effect between N atoms and reduce the oxidation potential.
5) FIG. 15 is a stability curve for the polyamide prepared in application example 1 in a first heavy redox state, as tested by: in the above 4) test system and mode, a voltage of 0-0.8V is applied and the cycle is 1000 cycles, and the curve shown in fig. 15 is obtained, and it can be seen from fig. 15 that the oxidation potential of the polymer is reduced due to the strong conjugation of the structure of the extended conjugated triphenylamine derivative tetraphenyl p-phenylenediamine, and the attenuation after 1000 cycles is small, so as to endow the polymer with excellent electrochemical stability.
6) FIG. 16 is an electrically controlled fluorescence spectrum of the polyamide prepared in application example 1, the test method being: the three-electrode system of 4) is built in a fluorescence cuvette, the fluorescence cuvette is placed in a fluorescence spectrophotometer, different voltages are applied to the working electrode in an Amperometric i-t Curve mode, the fluorescence spectrophotometer is used for monitoring the change of emission spectra under different wavelengths, a Curve shown in a figure 16 is obtained, as can be seen from figure 16, when the applied voltage is increased to 0.80V, the fluorescence is completely quenched, the reverse applied voltage is subjected to fluorescence reversion, the polymer is proved to have reversible fluorescence modulation behavior, and meanwhile, the polymer can be judged to have high fluorescence contrast by the fluorescence intensity ratio at the maximum wavelength.
7) Fig. 17 is an electrically controlled fluorescence response time spectrum of the polyamide film prepared in application example 1, and the test method is as follows: in the electric control fluorescence test system built in the 6), a square wave voltage under 0-0.75V is applied to the working electrode in a Chronoamperometry mode in an electrochemical workstation, the obtained result is shown in figure 17, and as can be seen from figure 17, when the cycle time is 10s, the fluorescence switching time is 2.1/0.6s, which proves that the synergy between distorted three-dimensional non-coplanar spirobifluorene and bistriphenylamine structures weakens the stacking degree between polymer molecular chains, accelerates the embedding/extracting speed of electrolyte ions, and enables the polymer to have a faster fluorescence switching speed.
8) Fig. 18 is an electrically-controlled fluorescence response time spectrum of the polyamide film prepared in application example 1 under different cycle times, and the test method is as follows: the square wave voltage is 0-0.75V; the application times were gradually shortened from a period of 120s to 80, 60, 40, 20, 10s, the results are shown in fig. 18; as can be seen from fig. 18, as the period of time for which the voltage was applied was shortened, the time required for the polyamide film to reach 90% optical change was gradually reduced due to incomplete redox reaction of the polyamide occurring in a short time; however, the fluorescence intensity of the polyamide is hardly attenuated, and when the duration is 20s, the fluorescence on/off time is short (2.1/0.6s), which shows that the polyamide provided by the invention has the characteristics of slow attenuation rate and fast response speed. The reason is that the highly conjugated bistriphenylamine group and the distorted non-planar spirobifluorene structure can effectively weaken the close packing of molecular chains, and are beneficial to the embedding and extraction of electrolyte ions, so that the polyamide has the characteristics of low attenuation rate and high response speed.
9) The fluorescence quantum yield of the polyamide prepared in application example 1 was measured using an integrating sphere, and table 1 shows the fluorescence quantum yield of the polyamide prepared in application example 1 in the NMP diluted solution state and the thin film state.
Table 1: fluorescence quantum yield of trans-1, 4-cyclohexanediacid-type polyamide in application example 1
Figure BDA0003249545620000211
As can be seen from table 1, the polymer film has brighter fluorescence in the solution state, which demonstrates that the introduction of the double fluorophore significantly enhances the fluorescence intensity of the polymer film.
9) Respectively dissolving 10mg of polyamide or polyimide powder prepared in application examples 1-3 in 1mL of different solvents at room temperature, standing for 24h at room temperature to observe the polyamide dissolution degree, and obtaining results shown in Table 2; wherein the symbols have the meaning: ++: soluble at room temperature; +: heating to dissolve; + -: partially dissolving the part by heating; -: heating for insolubilization.
Table 2: solubility of Polyamide and polyimide prepared in application examples 1 to 3 in 6 solvents
Figure BDA0003249545620000221
As can be seen from Table 2, the presence of bistriphenylamine and a symmetric fluorophore weakens the close packing of polymer molecular chains, enhances the solubility of the polymer, and facilitates the processing into a thin film for use.
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 compound containing a symmetrical double-fluorophore structure, having a structure represented by formula I:
Figure FDA0003249545610000011
wherein R is
Figure FDA0003249545610000012
Figure FDA0003249545610000013
2. A method for preparing a diamine compound containing a symmetric double fluorophore structure as defined in claim 1, comprising the steps of:
mixing p-phenylenediamine, p-fluoronitrobenzene, a first catalyst and an organic solvent, and carrying out substitution reaction to obtain a dinitro monomer;
mixing the dinitro monomer, the brominated fluorescent compound, a second catalyst and a polar solvent, and performing a coupling reaction to obtain a dinitro compound;
mixing the dinitro compound, a third catalyst, a reducing agent and a mixed solvent, and carrying out reduction reaction to obtain a diamine compound containing a symmetrical double-fluorophore structure and having a structure shown in a formula I;
the dinitro monomer has a structure represented by formula II-1:
Figure FDA0003249545610000021
the structural formula of the brominated fluorescent compound is Br-R;
the dinitro compound has a structure shown as a formula II-2;
Figure FDA0003249545610000022
r is
Figure FDA0003249545610000023
Figure FDA0003249545610000024
3. The preparation method according to claim 2, wherein the first catalyst is a composite catalyst comprising a main catalyst and a sub-catalyst, the main catalyst comprising triethylamine, tripropylamine, tributylamine, or potassium hydroxide; the secondary catalyst comprises cyclodextrin, tetrabutylammonium bromide or quaternary ammonium base; the molar ratio of the p-phenylenediamine to the fluoronitrobenzene to the main catalyst to the auxiliary catalyst is 1 (2.2-2.5) to (4-8) to (0.5-1.2); the temperature of the substitution reaction is 160-200 ℃, and the reaction time is 4-10 h;
the second catalyst comprises a copper catalyst, a cocatalyst and a phase transfer catalyst, wherein the copper catalyst is copper powder or cuprous iodide, the cocatalyst is potassium carbonate, sodium carbonate, potassium hydride or sodium cyanide, and the phase transfer catalyst is 18 crown-6 or 15 crown-5; the molar ratio of the dinitro monomer to the brominated fluorescent compound to the copper catalyst to the cocatalyst to the phase transfer catalyst is 1 (2.0-2.5) to (3-10) to (3-12) to (0.4-1), the temperature of the coupling reaction is 160-175 ℃, and the reaction time is 20-36 hours.
4. The method according to claim 2, wherein the third catalyst is Pd/C, and the reducing agent is hydrazine hydrate; the reduction reaction is carried out in a nitrogen atmosphere; the mass ratio of the dinitro compound to the third catalyst is 1 (0.2-0.4), and the molar ratio of the dinitro compound to the reducing agent is 1 (10-40); the temperature of the reduction reaction is 80-110 ℃, and the reaction time is 10-36 h.
5. Use of the diamine compound containing a symmetric double-fluorophore structure according to claim 1 or the diamine compound containing a symmetric double-fluorophore structure prepared by the preparation method according to any one of claims 2 to 4 in preparation of polyamide or polyimide.
6. A polyamide having a structure represented by formula III:
Figure FDA0003249545610000031
wherein n is 10-200 and n is an integer; ar is
Figure FDA0003249545610000032
R is
Figure FDA0003249545610000033
Figure FDA0003249545610000041
7. A process for producing a polyamide as claimed in claim 6, which comprises the steps of:
mixing the diamine compound containing the symmetrical double-fluorophore structure of claim 1, diacid, a cosolvent, a condensing agent, a catalyst and a reaction solvent, and carrying out polycondensation reaction to obtain polyamide;
the diacid is terephthalic acid, trans-1, 4-cyclohexanedicarboxylic acid or 4,4' -diphenyldicarboxylic acid.
8. A polyimide having a structure according to formula IV:
Figure FDA0003249545610000042
wherein m is 20-100 and m is an integer; ar' is
Figure FDA0003249545610000043
Figure FDA0003249545610000044
R is
Figure FDA0003249545610000045
Figure FDA0003249545610000051
9. The method for producing a polyimide according to claim 8, comprising the steps of:
mixing a diamine compound containing a symmetrical double-fluorophore structure according to claim 1, dianhydride and an organic solvent, performing a polymerization reaction, mixing the obtained polyamic acid solution, acetic anhydride and pyridine, and performing chemical imidization to obtain polyimide;
the dianhydride is 1,2,4, 5-cyclohexane tetracarboxylic dianhydride or hexafluoro dianhydride.
10. Use of a polyamide according to claim 6 or a polyimide according to claim 8 in the field of electrically controlled fluorescence.
CN202111041734.0A 2021-09-07 2021-09-07 Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof Active CN113698306B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111041734.0A CN113698306B (en) 2021-09-07 2021-09-07 Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111041734.0A CN113698306B (en) 2021-09-07 2021-09-07 Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN113698306A true CN113698306A (en) 2021-11-26
CN113698306B CN113698306B (en) 2022-07-22

Family

ID=78660724

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111041734.0A Active CN113698306B (en) 2021-09-07 2021-09-07 Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN113698306B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115611787A (en) * 2022-11-13 2023-01-17 杭州师范大学 Organic luminescent material with double fluorescence emission characteristics and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584600A (en) * 2012-01-17 2012-07-18 黑龙江大学 Polyaniline derivative, preparation method of reduced polySchiff base thereof and application of polyaniline derivative
CN102675636A (en) * 2012-05-24 2012-09-19 黑龙江大学 Preparation method of bismaleimide resin with electrochromism and preparation method of film of bismaleimide resin
CN103145987A (en) * 2013-03-29 2013-06-12 黑龙江大学 Polyimide and graphene oxide compounded photoelectric material and preparation method thereof
CN103159952A (en) * 2013-03-29 2013-06-19 黑龙江大学 Polyamide and graphene oxide combined photoelectric material and preparation method thereof
CN104072474A (en) * 2014-07-03 2014-10-01 黑龙江大学 Thiophene-containing triphenylamine conjugated aromatic amide as well as preparation method and application thereof
CN105924361A (en) * 2016-06-20 2016-09-07 吉林大学 Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure
CN111423333A (en) * 2020-04-17 2020-07-17 吉林大学 Diamine monomer containing heptaphenyltriamine-double fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102584600A (en) * 2012-01-17 2012-07-18 黑龙江大学 Polyaniline derivative, preparation method of reduced polySchiff base thereof and application of polyaniline derivative
CN102675636A (en) * 2012-05-24 2012-09-19 黑龙江大学 Preparation method of bismaleimide resin with electrochromism and preparation method of film of bismaleimide resin
CN103145987A (en) * 2013-03-29 2013-06-12 黑龙江大学 Polyimide and graphene oxide compounded photoelectric material and preparation method thereof
CN103159952A (en) * 2013-03-29 2013-06-19 黑龙江大学 Polyamide and graphene oxide combined photoelectric material and preparation method thereof
CN104072474A (en) * 2014-07-03 2014-10-01 黑龙江大学 Thiophene-containing triphenylamine conjugated aromatic amide as well as preparation method and application thereof
CN105924361A (en) * 2016-06-20 2016-09-07 吉林大学 Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure
CN111423333A (en) * 2020-04-17 2020-07-17 吉林大学 Diamine monomer containing heptaphenyltriamine-double fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HSIAO, SHENG-HUEI等，: "Synthesis and Optoelectronic Properties of Novel Polyamides with 2-Naphthyldiphenylamine Units", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 *
SUN, NINGWEI等: "Synergistic effect between electroactive tetraphenyl-p-phenylenediamine and AIE-active tetraphenylethylene for highly integrated", 《JOURNAL OF MATERIALS CHEMISTRY C: MATERIALS FOR OPTICAL AND ELECTRONIC DEVICES 》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115611787A (en) * 2022-11-13 2023-01-17 杭州师范大学 Organic luminescent material with double fluorescence emission characteristics and preparation method and application thereof
CN115611787B (en) * 2022-11-13 2023-12-22 杭州师范大学 Organic luminescent material with double fluorescence emission characteristics and preparation method and application thereof

Also Published As

Publication number Publication date
CN113698306B (en) 2022-07-22

Similar Documents

Publication Publication Date Title
CN111423333B (en) Diamine monomer containing heptaphenyltriamine-double fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof
Quante et al. Novel perylene‐containing polymers
CN110903204B (en) Diamine compound containing diarylamine-pyrene structure and preparation method thereof, polyamide and polyimide and application thereof
Sun et al. Novel polyamides with fluorene-based triphenylamine: electrofluorescence and electrochromic properties
CN108863824B (en) Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof
Sun et al. Synergistic effect between electroactive tetraphenyl-p-phenylenediamine and AIE-active tetraphenylethylene for highly integrated electrochromic/electrofluorochromic performances
Hsiao et al. Electroactive aromatic polyamides and polyimides with adamantylphenoxy-substituted triphenylamine units
Sun et al. High-contrast electrochromic and electrofluorescent dual-switching materials based on 2-diphenylamine-(9, 9-diphenylfluorene)-functionalized semi-aromatic polymers
CN102993082B (en) Difluoro monomer with carbazole group and application thereof in preparing polyarylether polymer containing carbazole side group
CN105924361B (en) Tetraphenyl-p-phenylenediamine structure diamine monomer of the substitution of dimethyl amine containing 4-, preparation method and applications
CN105884707A (en) Diamine monomer containing triphenylamine-phenoxazine structure, preparation method and application of diamine monomer
Hsiao et al. Highly stable electrochromic polyamides based on N, N‐bis (4‐aminophenyl)‐N′, N′‐bis (4‐tert‐butylphenyl)‐1, 4‐phenylenediamine
Hsiao et al. Fluorescent and electrochromic aromatic polyamides with 4‐tert‐butyltriphenylamine chromophore
CN113698306B (en) Diamine compound containing symmetric double-fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof
Liou et al. Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1, 2‐phenylenediamine moiety
CN108929243B (en) Diamine monomer containing asymmetric fluorophore structure and preparation method and application thereof
CN110903202B (en) Diamine monomer and preparation method thereof, polyamide and preparation method and application thereof
Wang et al. Multicolor electrochromic poly (amide-imide) s with N, N-diphenyl-N′, N′-di-4-tert-butylphenyl-1, 4-phenylenediamine moieties
Anannarukan et al. Soluble polyimides containing trans-diaminotetraphenylporphyrin: Synthesis and photoinduced electron transfer
CN107759775B (en) Donor-receptor type alternating polymer containing sulfone-based fused ring structure and having strong two-photon effect, preparation method and application
Shao et al. An unexpected discovery of a one-pot synthesis for carbazole-based diamine and the electrochromic properties of the derived polymers
CN111333524B (en) Diamine compound containing bis (diphenylamine) -tetraphenylethylene structure and preparation method thereof, and polyamide and preparation method thereof
CN112745236B (en) Diamine monomer containing tetraphenylethylene-triphenylamine structure, preparation method and application of diamine monomer in preparation of colorless polyimide
Zhu et al. Synthesis, characterization and photophysical properties of novel fluorene-based copolymer with pendent urea group: Fluorescent response for anions through H-bonding interaction
CN104530266B (en) The polymer of imidizate comprising luminophore and their method of acquisition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant