CN108676162B - Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application - Google Patents
Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application Download PDFInfo
- Publication number
- CN108676162B CN108676162B CN201810439476.3A CN201810439476A CN108676162B CN 108676162 B CN108676162 B CN 108676162B CN 201810439476 A CN201810439476 A CN 201810439476A CN 108676162 B CN108676162 B CN 108676162B
- Authority
- CN
- China
- Prior art keywords
- tert
- naphthalimide
- containing double
- double tetra
- aniline structures
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
-
- 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
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application, the present invention relates to containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application, the present invention provides a kind of containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application, the present invention synthesizes the polyimide precursor containing double tetra-tert aniline structures, then the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are prepared, application of the material as photoelectric material, including electrochromic material, fluorescent sensing material, acid causes sensing material, hole mobile material, third-order non-linear material, anti-fake material, camouflage material, automobile rearview mirror material；It can also be used in ion detection, the preparation of explosive detection and memory performance original part.Present invention application polyimides field.
Description
Technical field
The present invention relates to a kind of polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore
And its preparation method and application.
Background technique
Polyimides (PI) is the outstanding high temperature polymeric materials of a kind of comprehensive performance, has good chemical stabilization
Property, excellent dielectric properties, excellent mechanical property and radiation resistance etc. can be prepared into film, high-temperature resistant coating, compound
Material, insulated paint, sound-absorbing material are widely used in the fields such as aerospace, electrochromism, precision machinery, microelectronics.Although poly-
Acid imide excellent combination property, but traditional PI is there are some disadvantages, as difficulty of processing is high, dissolubility is poor, film strength and transparent
Property poor, flexible difference it is easy to break the problems such as, which has limited the application of polyimide material industrially.Therefore, recent years, more
The preparation of polyimides is begun to focus on come more researchers and is modified the research of reverse side and the application of associated materials.
Summary of the invention
The present invention provides containing double tetra-tert aniline structures and naphthalimide fluorophore polyimide derivatives and
Preparation method and application.
The structural formula of polyimide derivatives of the present invention containing double tetra-tert aniline structures and naphthalimide fluorophore
It is as follows:
, n is 3~10 in formula integer.
The preparation side of polyimide derivatives of the present invention containing double tetra-tert aniline structures and naphthalimide fluorophore
Method are as follows: one, polyimide precursor of the synthesis containing double tetra-tert aniline structures
By double tetra-tert aniline diamine monomers, 3,3'- dihydroxy aniline, the double acid anhydrides of hexafluoro and solvent N-methyl pyrilidone
Mixing is stirred at reflux 5-10h under room temperature, and mixing speed is 800r/min~900r/min, adds acetic anhydride and catalysis
Agent pyridine, is warming up to 100-150 DEG C, is stirred at reflux 10-15h, pours into methanol after cooling, after filtering, the solid formation that will obtain
Vacuum drying, obtains polyimide precursor；
Two, the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are prepared
By polyimide precursor, solvent N-methyl pyrilidone, the naphthalimide derivative containing hydroxyl structure, isonitrile
Acid esters MDI and catalyst dibutyltin dilaurylate are added in there-necked flask, are warming up to 40-50 DEG C and are stirred at reflux 10-15h, cooling
After pour into methanol, using filter, dry, obtain containing the polyamides of double tetra-tert aniline structures and naphthalimide fluorophore Asia
Amine derivative；
Wherein the double acid anhydride molar ratios of double tetra-tert aniline diamine monomers in step 1,3,3'- dihydroxy aniline, hexafluoro are
1:1:(1.5-2.5)；
The amount of solvent N-methyl pyrilidone in step 1 and the volume ratio of double tetra-tert aniline diamine monomers are
10mL:(1.0-1.5)g；
The volume ratio of acetic anhydride and double tetra-tert aniline diamine monomers in step 1 is (2-3) mL:(1.0-1.5) g；
The volume ratio of pyridine and double tetra-tert aniline diamine monomers in step 1 is (1-2) mL:(1.0-1.5) g；
Naphthalimide, isocyanide ester MDI and the catalyst dibutyltin cinnamic acid of polyimide precursor, hydroxyl in step 2
The molar ratio of dibutyl tin is (80-120): (180-220): (180-220)；
The amount of solvent N-methyl pyrilidone in step 2 and the volume ratio of polyimide precursor are 10mL:(0.5-
1.0)g。
Beneficial effects of the present invention:
The present invention extends the application range of electrochromic material, aromatic polyimide polymer material, since its is excellent
Different heat resistance and mechanical performance causes the great interest of researcher.To there is the triarylamine for destroying bulk property
Group is introduced into polyimide structures, is not only able to maintain the high thermal stability of original polyimides, but also be capable of increasing its solubility
Enhance film forming ability, this be not only advantageous to manufacture large area film electrochromic device, additionally provide electric activity center with
Promote the processing and application of electrochromic device；Polyimide derivatives prepared by the present invention are single with the triaryl amine of propeller type
Body can be effectively reduced the strong effect power between polymer molecular chain, increase the dissolubility of polymer, while triaryl amine is easy
The triaryl amine different from middle condition is showed in forming radical cation.In the present invention containing double tetra-tert aniline structures and
The polyimide derivatives of naphthalimide fluorophore have very high performance resistant to high temperature, generally under the atmosphere of nitrogen, decompose
Temperature is suitble to use in the devices at 350 DEG C or more.By the present invention containing double tetra-tert aniline structures and naphthalimide fluorescent base
Film is made in the polyimide derivatives material of group, does not have big clustering phenomena and Fragmentation Phenomena on ITO substrate, serves as a contrast in ITO
Good wet ability is also shown on bottom.This means that preparation is containing double tetra-tert aniline structures and naphthalimide fluorophore
Polyimide derivatives material has good film Formation and characteristics, can be used to make the film of large area.After application of a voltage,
The transmitance of film still can achieve 40%, and transparency is relatively good, and thin polymer film can during applying voltage
It keeps circulating ring to have good stability, is recycled 20 times or more and transparency is constant.
The electrochromic property of polyimide derivatives of the invention has following superiority in practical applications: (1) having
There is good electrochemical redox invertibity, is still able to maintain after tens redox cycles reversible；(2) color becomes
The response time of change is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is reversible；(4)
Color change high sensitivity；(5) there is higher cycle life；(6) have storing memory function, before responding after, can be steadily
State after being maintained at reset condition or discoloration, can maintain several months to several years after discoloration, in this experiment after electrochromism
Color can be remained unchanged up to as long as half a year；(7) there is a preferable chemical stability in material discoloration front and back, empty under normal temperature and pressure
It may be stabilized in gas.(8) to acid-base property pH and explosive TNT, picric acid has response.
Detailed description of the invention
Fig. 1 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The infrared spectrum of biology；
Fig. 2 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The hydrogen nuclear magnetic spectrogram of biology；
Fig. 3 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The figure of the atomic force microscope of biology；
Fig. 4 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The cyclic voltammogram of biology；
Fig. 5 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
Biological stability and transmitance figure after application of a voltage；
Fig. 6 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The electrochromism figure of biology；
Fig. 7 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The electroluminescent fluorescent figure of biology；
Fig. 8 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The thermogravimetric curve figure of biology；
Fig. 9 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
Biology to PH response diagram；
Figure 10 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The detection picric to explosive of derivative is schemed；
Figure 11 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The detection figure to explosive TNT of derivative；
Figure 12 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The memory performance figure of derivative.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, further include each specific embodiment it
Between any combination.
Specific embodiment 1: polyamides of the present embodiment containing double tetra-tert aniline structures and naphthalimide fluorophore
The structural formula of imine derivative is as follows:
,
The integer that n is 3~10 in formula.
Present embodiment extends the application range of electrochromic material, aromatic polyimide polymer material, due to
Its excellent heat resistance and mechanical performance cause the great interest of researcher.To there are three virtues for destroying bulk property
Amine groups are introduced into polyimide structures, are not only able to maintain the high thermal stability of original polyimides, but also it is molten to be capable of increasing its
Xie Du enhances film forming ability, this is not only advantageous to the film electrochromic device of manufacture large area, additionally provides in electroactive
The heart is to promote the processing and application of electrochromic device；The polyimide derivatives of present embodiment preparation are with the three of propeller type
Arylamine is monomer, and the strong effect power between polymer molecular chain can be effectively reduced, increase the dissolubility of polymer, simultaneously
Triaryl amine is easily formed radical cation and shows triaryl amine different from middle condition.Contain double four tertiary fourths in present embodiment
The polyimide derivatives of base aniline structure and naphthalimide fluorophore have very high performance resistant to high temperature, generally in nitrogen
Under atmosphere, decomposition temperature is suitble to use in the devices at 350 DEG C or more.Present embodiment is contained into double tetra-tert aniline structures
And film is made in the polyimide derivatives material of naphthalimide fluorophore, do not have on ITO substrate big clustering phenomena and
Fragmentation Phenomena also shows good wet ability on ITO substrate.This means that sub- containing double tetra-tert aniline structures and naphthoyl
The polyimide derivatives material of amine fluorophor has good film Formation and characteristics, can be used to make the film of large area.
After application of a voltage, the transmitance of film still can achieve 20%, and transparency is relatively good, and gather during applying voltage
Conjunction object film is able to maintain circulating ring and has good stability, and is recycled 20 times or more and transparency is constant.
The electrochromic property of the polyimide derivatives of present embodiment has following superiority in practical applications:
(1) there is good electrochemical redox invertibity, be still able to maintain after tens redox cycles reversible；(2)
The response time of color change is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is reversible
's；(4) color change high sensitivity；(5) there is higher cycle life；(6) have storing memory function, before responding after, can be with
State after being stably maintained at reset condition or discoloration, can maintain several months to several years after discoloration, in this experiment electroluminescent
Color can be remained unchanged up to as long as half a year after discoloration；(7) there are preferable chemical stability, normal temperature and pressure in material discoloration front and back
Under, it may be stabilized in air.(8) to acid-base property pH and explosive TNT, picric acid has response.
Specific embodiment 2: polyamides of the present embodiment containing double tetra-tert aniline structures and naphthalimide fluorophore
Imine derivative the preparation method comprises the following steps: one, synthesis the polyimide precursor containing double tetra-tert aniline structures
By double tetra-tert aniline diamine monomers, 3,3'- dihydroxy aniline, the double acid anhydrides of hexafluoro and solvent N-methyl pyrilidone
Mixing is stirred at reflux 5-10h under room temperature, and mixing speed is 800r/min~900r/min, adds acetic anhydride and catalysis
Agent pyridine, is warming up to 100-150 DEG C, is stirred at reflux 10-15h, pours into methanol after cooling, after filtering, the solid formation that will obtain
Vacuum drying, obtains polyimide precursor；
Two, the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are prepared
By polyimide precursor, solvent N-methyl pyrilidone, the naphthalimide derivative containing hydroxyl structure, isonitrile
Acid esters MDI and catalyst dibutyltin dilaurylate are added in there-necked flask, are warming up to 40-50 DEG C and are stirred at reflux 10-15h, cooling
After pour into methanol, using filter, dry, obtain containing the polyamides of double tetra-tert aniline structures and naphthalimide fluorophore Asia
Amine derivative；
Wherein the double acid anhydride molar ratios of double tetra-tert aniline diamine monomers in step 1,3,3'- dihydroxy aniline, hexafluoro are
1:1:(1.5-2.5)；
The amount of solvent N-methyl pyrilidone in step 1 and the volume ratio of double tetra-tert aniline diamine monomers are
10mL:(1.0-1.5)g；
The volume ratio of acetic anhydride and double tetra-tert aniline diamine monomers in step 1 is (2-3) mL:(1.0-1.5) g；
The volume ratio of pyridine and double tetra-tert aniline diamine monomers in step 1 is (1-2) mL:(1.0-1.5) g；
Naphthalimide, isocyanide ester MDI and the catalyst dibutyltin cinnamic acid of polyimide precursor, hydroxyl in step 2
The molar ratio of dibutyl tin is (80-120): (180-220): (180-220)；
The amount of solvent N-methyl pyrilidone in step 2 and the volume ratio of polyimide precursor are 10mL:(0.5-
1.0)g。
Specific embodiment 3: present embodiment is unlike specific embodiment two: described in step 1 double four
The double acid anhydride molar ratios of tert-butyl aniline diamine monomer, 3,3'- dihydroxy aniline, hexafluoro are 1:1:2.With specific embodiment two-phase
Together.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: the polyamides in step 2
Imines presoma, the naphthalimide of hydroxyl, isocyanide ester MDI and catalyst dibutyltin dilaurylate molar ratio be 100:
200:200:1.Other are identical as specific embodiment two or three.
Specific embodiment 5: polyamides of the present embodiment containing double tetra-tert aniline structures and naphthalimide fluorophore
Application of the imine derivative as photoelectric material.
Specific embodiment 6: present embodiment is unlike specific embodiment five: containing double tetra-tert aniline knots
The polyimide derivatives of structure and naphthalimide fluorophore are as the preparation method of electrochromic material: polyimides is spread out
Biology is dissolved in organic solvent, obtains polyimide derivatives solution, then by polyimide derivatives solution in electro-conductive glass
Upper carry out film, obtains electrochromic material；Wherein organic solvent be tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N,
N '-dimethylformamide or N-Methyl pyrrolidone.Other are identical as specific embodiment five.
Specific embodiment 7: polyamides of the present embodiment containing double tetra-tert aniline structures and naphthalimide fluorophore
Application of the imine derivative as ion detection material.
Specific embodiment 8: present embodiment is unlike specific embodiment seven: containing double tetra-tert aniline knots
Application method of the polyimide derivatives of structure and naphthalimide fluorophore as ion detection are as follows: double tetra-tert benzene will be contained
The polyimide derivatives of amine structure and naphthalimide fluorophore are dissolved in the organic solvent containing proton, are obtained containing double four uncles
The polyimide derivatives solution of butylaniline structure and naphthalimide fluorophore, it is then that the buffering with different PH is molten
Drop is added in polyimide derivatives solution, and the pH value of solution is detected using the variation of solution fluorescence intensity.Other with
Specific embodiment seven is identical.
Specific embodiment 9: polyamides of the present embodiment containing double tetra-tert aniline structures and naphthalimide fluorophore
Application of the imine derivative as explosive detection material.
Specific embodiment 10: present embodiment is unlike specific embodiment nine: containing double tetra-tert aniline knots
Application method of the polyimide derivatives of structure and naphthalimide fluorophore as explosive detection are as follows: double tetra-terts will be contained
The polyimide derivatives of aniline structure and naphthalimide fluorophore are dissolved in organic solvent, are obtained containing double tetra-tert aniline
Then the polyimide derivatives solution of structure and naphthalimide fluorophore the solution containing explosive is added dropwise in polyamides Asia
In amine derivative solution, detected using the variation of solution fluorescence intensity in solution with the presence or absence of explosive.Other and specific reality
It is identical to apply mode nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: the preparation of the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore
Method are as follows:
One, the polyimide precursor containing double tetra-tert aniline structures is synthesized
By double tetra-tert aniline diamine monomers (0.245g, 1.5mmol), 3,3'- dihydroxy aniline (0.470g,
1.5mmol), the double acid anhydrides (0.336g, 3mmol) of hexafluoro and solvent N-methyl pyrilidone (NMP) 10mL, which are added, has reflux unit
There-necked flask in, be stirred at reflux 10h under room temperature, mixing speed 800r/min obtains polyamic acid.After the reaction was completed,
2.5mL acetic anhydride and catalyst pyridine 1mL are added in the reaction system, is warming up to 120 DEG C, are stirred at reflux 12h, are fallen after cooling
Enter in 40mL methanol, it is after filtering, obtained solid formation is dry under 50 DEG C of vacuum conditions, it obtains containing double tetra-tert aniline knots
The polyimide precursor of structure；
Two, the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are prepared
Double tetra-tert aniline structures (0.556g, 1.66mmol), solvent N-methyl pyrilidone (NMP) 20mL will be contained
It naphthalimide derivative (0.56g, 3.22mmol), isocyanide ester MDI (0.81g, 3.22mmol) containing hydroxyl structure and urges
Agent dibutyl tin dilaurate 0.01g is added in there-necked flask, is warming up to 40 DEG C and is stirred at reflux 10h, pours into methanol after cooling,
It is using filter, drying, obtained solid formation is dry under 50 DEG C of vacuum conditions, it obtains containing double tetra-tert aniline structures and naphthalene
The polyimide derivatives of imide fluorescent group, structural formula are as follows:
,
The integer that n is 3~10 in formula.
Polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are as electrochromism material
The preparation method of material is: polyimide derivatives being dissolved in organic solvent, polyimide derivatives solution is obtained, then will be gathered
Imide derivative solution carries out film on electro-conductive glass, obtains electrochromic material；Wherein organic solvent be tetrahydrofuran,
Chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.
Polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are as ion detection
Application method are as follows: the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are dissolved in containing matter
In the organic solvent of son, it is molten to obtain the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore
Then buffer solution with different PH is added dropwise in polyimide derivatives solution, utilizes solution fluorescence intensity by liquid
Change to detect the pH value of solution.
Polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are as explosive detection
Application method are as follows: the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are dissolved in organic
In solvent, the polyimide derivatives solution containing double tetra-tert aniline structures and naphthalimide fluorophore is obtained, then will
Solution containing explosive is added dropwise in polyimide derivatives solution, is detected in solution using the variation of solution fluorescence intensity
With the presence or absence of explosive.
Test the dissolubility of the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore, knot
Fruit is as shown in table 1, and solubility is dissolved in 1 milliliter of solution with 10 milligrams of samples and is measured.++, dissolve in room temperature.+, it heats molten
Solution.The part of+- during heating is solvable.It is insoluble.As shown in Table 1, the present embodiment containing double tetra-tert aniline structures and
The polyimide derivatives of naphthalimide fluorophore have good dissolubility.
Table 1
It forms a film being coated containing the polyimide derivatives of double tetra-tert aniline structures and naphthalimide fluorophore, to it
Performance is tested:
Fig. 1 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The infrared spectrum of biology；From fig. 1, it can be seen that in 3316~3321cm-1The characteristic absorption peak at place is stretched corresponding to N-H key in amide
Contracting vibration peak, in 2915-2918cm-1Neighbouring peak is the stretching vibration peak of methyl, in 1715-1725cm-1The characteristic peak at place is
The stretching vibration peak of C=O key.
Fig. 2 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The hydrogen nuclear magnetic spectrogram of biology；As can be seen from Figure 2,1H-NMR (DMSO, TMS): the peak at δ=10.32ppm is the change of the H on CO-NH
Displacement study, chemical shift of the δ=7.01-8.25ppm for H on phenyl ring, δ=2.75,2.12,1.80ppm, it is methyl, H in ethyl
Chemical shift, embodiment one has synthesized derivative containing the polyimides of double tetra-tert aniline structures and naphthalimide fluorophore
Object.
Fig. 3 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The figure of the atomic force microscope of biology, it is shown that smooth film does not have big clustering phenomena on ITO substrate and is crushed existing
As also showing good wet ability on ITO substrate.This explanation is containing double tetra-tert aniline structures and naphthalimide fluorescent base
The polyimide derivatives of group have good film Formation and characteristics, can be used to make the film of large area；
Fig. 4 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The cyclic voltammogram of biology；As can be seen from Figure 4, occur an oxidation peak at 1.11V, occur a reduction at 0.86V
Peak.Fig. 5 is the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
Stability and transmitance figure after application of a voltage；As shown in Figure 5, after application of a voltage, containing double tetra-tert aniline structures and
The transmitance of the polyimide derivatives film of naphthalimide fluorophore still can achieve 40%, illustrate that transparency compares
It is good, and thin polymer film is able to maintain circulating ring and has good stability during applying voltage, is recycled 20 times or more and saturating
Lightness is constant.
Fig. 6 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The electrochromism figure of biology；As can be seen from Figure 6, before not applying voltage, prepared by embodiment one contains double tetra-tert aniline structures
And the polyimide derivatives of naphthalimide fluorophore have absorption peak at 352nm, when applied voltage is from 0.0V to 1.5V,
Absorption peak is gradually increasing at 352nm, is occurred new absorption peak at 655nm and is gradually increasing；Electrochromic color is from sallow
Color is to blackish green.
Fig. 7 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The electroluminescent fluorescent figure of biology；Before not applying voltage, fluorescence intensity reaches highest level, as applied voltage is by 0.0V to 1.5V
When, the fluorescence intensity of polymer is gradually reduced, and finally almost levels off to zero.
Fig. 8 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The thermogravimetric curve figure of biology；As it can be observed in the picture that the preparation of embodiment one contains double tetra-tert aniline structures and naphthalimide fluorescence
The polyimide derivatives of group about start a large amount of weightlessness at 400 DEG C or so, when temperature is at 404 DEG C, weight loss 5%,
When temperature is 442 DEG C, weight loss 10%；When temperature is 599 DEG C, weight loss 20%, the reality when temperature reaches 800 DEG C
The polyimide derivatives carbon residual volume containing fluorine-triphenylamine structure and naphthalimide fluorophore for applying the preparation of example one is 60%.Have
Preferable high temperature resistance.
Fig. 9 is that the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one spreads out
The fluorogram that biology responds PH；As seen from Figure 9 when pH value rises to 8.2 by 5.8, the fluorescence intensity of polymer is gradually
Decline.
Figure 10 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The fluorogram that derivative responds picric acid；As seen from Figure 10 with the increase of bitter taste acid concentration, polymer solution it is glimmering
Luminous intensity gradually weakens.
Figure 11 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The fluorogram that derivative responds TNT；As seen from Figure 11 with the increase of TNT concentration, the fluorescence intensity of polymer solution
Gradually weaken.
Figure 12 is the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore prepared by embodiment one
The memory performance figure of derivative；As seen from Figure 12 in first time voltage scanning, from 0 to -6V (scanning 1), work as negative threshold value
Voltage is that -4.8V and memory device observe electric current when being switched to highly conductive state (ON) from low conductivity state (OFF)
It sharply increases.This conversion process can be used as " write-in " process of ITO/PI/Al device.(the scanning during scan next time
2), electric current still keeps high on state still in ON state, device.In the third time scanning of from 0 to+6V (scanning 3), we
Observe the unexpected decline of the electric current under the threshold voltage of+1.5V, this shows memory device experience from ON state to original OFF shape
The transformation of state.This conversion from ON to OFF can be used as " erasing " process.As forward bias is applied, electric current is subsequent
Voltage scanning (scanning 4) in still remain in low on state.Therefore, the storage equipment manufactured with PI is binary system flash memory number
According to storage equipment.
By above-mentioned test it is found that polyimide derivatives manufactured in the present embodiment are using the triaryl amine of propeller type as monomer,
The strong effect power between polymer molecular chain can be effectively reduced, increase the dissolubility of polymer, while triaryl amine is easy to
It forms radical cation and shows the triaryl amine different from middle condition.Contain double tetra-tert aniline structures and naphthalene in the present invention
The polyimide derivatives of imide fluorescent group have very high performance resistant to high temperature, generally under the atmosphere of nitrogen, decompose temperature
Degree is suitble to use in the devices at 350 DEG C or more.By the present invention containing double tetra-tert aniline structures and naphthalimide fluorophore
Polyimide derivatives material film is made, there is no big clustering phenomena and Fragmentation Phenomena on ITO substrate, in ITO substrate
On also show good wet ability.This means that PI material has good film Formation and characteristics, can be used to make large area
Film.After application of a voltage, the transmitance of film still can achieve 40%, and transparency is relatively good, and alive applying
Thin polymer film is able to maintain circulating ring and has good stability in the process, is recycled 20 times or more and transparency is constant.
The electrochromic property of the polyimide derivatives of the present embodiment has following superiority in practical applications: (1)
With good electrochemical redox invertibity, still it is able to maintain after tens redox cycles reversible；(2) color
The response time of variation is fast, after making alive, can change colour rapidly within 0.8 second；(3) variation of color is reversible；
(4) color change high sensitivity；(5) there is higher cycle life；(6) have storing memory function, before responding after, can stablize
Ground is maintained at the state after reset condition or discoloration, can maintain after discoloration several months to several years, in this experiment in electrochromism
Color can be remained unchanged up to as long as half a year afterwards；(7) there is a preferable chemical stability in material discoloration front and back, under normal temperature and pressure,
It may be stabilized in air.(8) to acid-base property pH and explosive TNT, picric acid has response.
Claims (10)
1. the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore, it is characterised in that polyamides is sub-
The structural formula of amine derivative is as follows:
,
The integer that n is 3~10 in formula.
2. preparing the polyimides as described in claim 1 containing double tetra-tert aniline structures and naphthalimide fluorophore to spread out
The method of biology, it is characterised in that this method are as follows: one, polyimide precursor of the synthesis containing double tetra-tert aniline structures
By N, bis- (4- the tert-butyl-phenyl) -1,4- phenylenediamines of N- bis- (4- aminophenyl)-N ', N ' -, 3,3 '-dihydroxy -4,4 ' connection
The double acid anhydrides of phenylenediamine, hexafluoro are mixed with solvent N-methyl pyrilidone, are stirred at reflux 5-10h under room temperature, mixing speed is
800r/min~900r/min adds acetic anhydride and catalyst pyridine, is warming up to 100-150 DEG C, is stirred at reflux 10-15h, cold
But it pours into methanol afterwards, after filtering, obtained solid formation is dried in vacuo, polyimide precursor is obtained；
Two, the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are prepared
Polyimide precursor, solvent N-methyl pyrilidone, N- ethoxy -4- (N methyl piperazine base) -1,8- naphthoyl is sub-
Amine, methyl diphenylene diisocyanate and catalyst dibutyltin dilaurylate are added in there-necked flask, are warming up to 40-50 DEG C of stirring
Flow back 10-15h, pours into methanol after cooling, using filter, drying, obtains containing double tetra-tert aniline structures and naphthalimide
The polyimide derivatives of fluorophor；
The wherein N in step 1, N- bis- (4- aminophenyl)-N ', N '-bis- (4- tert-butyl-phenyl) -1,4- phenylenediamines, 3,3 ' -
The double acid anhydride molar ratios of the benzidine of dihydroxy -4,4 ', hexafluoro are 1:1:(1.5-2.5)；
The amount and N of solvent N-methyl pyrilidone in step 1, bis- (the 4- tert-butyl benzenes of bis- (4- the aminophenyl)-N ', N '-of N-
Base) -1,4- phenylenediamine volume ratio be 10mL:(1.0-1.5) g；
Acetic anhydride and N in step 1, bis- (4- the tert-butyl-phenyl) -1,4- phenylenediamines of N- bis- (4- aminophenyl)-N ', N ' -
Volume ratio is (2-3) mL:(1.0-1.5) g；
Pyridine and N in step 1, the body of bis- (4- the tert-butyl-phenyl) -1,4- phenylenediamines of N- bis- (4- aminophenyl)-N ', N ' -
Product is than being (1-2) mL:(1.0-1.5) g；
Polyimide precursor, N- ethoxy -4- (N methyl piperazine base) -1,8- naphthalimide, diphenylmethyl in step 2
The molar ratio of alkane diisocyanate and catalyst dibutyltin dilaurylate is (80-120): (180-220): (180-220)；
The amount of solvent N-methyl pyrilidone in step 2 and the volume ratio of polyimide precursor are 10mL:(0.5-1.0)
g。
3. according to claim 2 derivative containing the polyimides of double tetra-tert aniline structures and naphthalimide fluorophore
The preparation method of object, it is characterised in that bis- (the 4- tert-butyl benzenes of bis- (4- the aminophenyl)-N ', N '-of N described in step 1, N-
Base) -1,4- phenylenediamine, the 3,3 '-benzidines of dihydroxy -4,4 ', the double acid anhydride molar ratios of hexafluoro are 1:1:2.
4. according to claim 2 derivative containing the polyimides of double tetra-tert aniline structures and naphthalimide fluorophore
The preparation method of object, it is characterised in that polyimide precursor, N- ethoxy -4- (N methyl piperazine base) -1 in step 2,
The molar ratio of 8- naphthalimide, methyl diphenylene diisocyanate and catalyst dibutyltin dilaurylate is 100:200:200:
1。
5. the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore as described in claim 1
Application, it is characterised in that the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are as light
The application of electric material.
6. the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore according to claim 4
Derivative application, it is characterised in that it is derivative containing the polyimides of double tetra-tert aniline structures and naphthalimide fluorophore
Object is as the preparation method of electrochromic material: polyimide derivatives being dissolved in organic solvent, polyimides is obtained and spreads out
Then polyimide derivatives solution is carried out on electro-conductive glass film, obtains electrochromic material by biological solution；Wherein have
Solvent is tetrahydrofuran, chloroform, N, N '-dimethyl acetamide, N, N '-dimethylformamide or N-Methyl pyrrolidone.
7. the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore as described in claim 1
Application, it is characterised in that the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore be used as from
The application of son detection material.
8. according to claim 7 derivative containing the polyimides of double tetra-tert aniline structures and naphthalimide fluorophore
The application of object, it is characterised in that the polyimide derivatives conduct containing double tetra-tert aniline structures and naphthalimide fluorophore
The application method of ion detection are as follows: by the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore
It is dissolved in the organic solvent containing proton, obtains the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore
Then derivative solution the buffer solution with different PH is added dropwise in polyimide derivatives solution, glimmering using solution
Luminous intensity changes to detect the pH value of solution.
9. the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore as described in claim 1
Application, it is characterised in that the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore are as quick-fried
The application of fried analyte detection material.
10. the polyimides according to claim 9 containing double tetra-tert aniline structures and naphthalimide fluorophore spreads out
The application of biology, it is characterised in that make containing the polyimide derivatives of double tetra-tert aniline structures and naphthalimide fluorophore
For the application method of explosive detection are as follows: the polyimides containing double tetra-tert aniline structures and naphthalimide fluorophore spreads out
Biology is dissolved in organic solvent, obtains the polyimide derivatives containing double tetra-tert aniline structures and naphthalimide fluorophore
Then solution containing explosive is added dropwise in polyimide derivatives solution, utilizes the variation of solution fluorescence intensity by solution
To detect in solution with the presence or absence of explosive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810439476.3A CN108676162B (en) | 2018-05-09 | 2018-05-09 | Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810439476.3A CN108676162B (en) | 2018-05-09 | 2018-05-09 | Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108676162A CN108676162A (en) | 2018-10-19 |
| CN108676162B true CN108676162B (en) | 2019-09-10 |
Family
ID=63806004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810439476.3A Expired - Fee Related CN108676162B (en) | 2018-05-09 | 2018-05-09 | Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108676162B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796613B (en) * | 2019-01-11 | 2020-05-22 | 华南理工大学 | Fluorine ion color development sensing polyimide film and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101922061A (en) * | 2010-08-06 | 2010-12-22 | 东华大学 | Polyimide fiber and preparation method thereof |
| CN102675637A (en) * | 2012-05-24 | 2012-09-19 | 黑龙江大学 | Electrochromatic polyimide and preparation method thereof |
| CN104974090A (en) * | 2015-06-26 | 2015-10-14 | 山东理工大学 | Naphthalene diimide derivative, preparation method and applications thereof |
-
2018
- 2018-05-09 CN CN201810439476.3A patent/CN108676162B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101922061A (en) * | 2010-08-06 | 2010-12-22 | 东华大学 | Polyimide fiber and preparation method thereof |
| CN102675637A (en) * | 2012-05-24 | 2012-09-19 | 黑龙江大学 | Electrochromatic polyimide and preparation method thereof |
| CN104974090A (en) * | 2015-06-26 | 2015-10-14 | 山东理工大学 | Naphthalene diimide derivative, preparation method and applications thereof |
Non-Patent Citations (5)
| Title |
|---|
| A highly selective fluorescent sensor for Fe3+ based on covalently immobilized derivative of naphthalimide;Jun-Hong Xu,et al.;《Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy》;20130418;第112卷;第116-124页 |
| A hydrophilic fluorescent polymer containing naphthalimide moiety as chemosensor for microbioreactors;SHEN LiangJun,et al.;《Science in China Series B: Chemistry》;20091231;第52卷(第6期);第821-826页 |
| Preparation and properties of novel soluble aromatic polyimides from 4, 4′‐diaminotriphenylamine and aromatic tetracarboxylic dianhydrides;YOSHlYUKl OISHI,et al.;《Journal of Polymer Science Part A: Polymer Chemistry》;19921231;第30卷(第6期);第1027-1035页 |
| Synthesis and photophysical properties of fluorescent polystyrene containing 1, 8-naphthalimide via atom transfer polymerization;Jin Zhengneng,et al.;《e-Polymers》;20070115;第7卷(第1期);第1-8页 |
| Synthesis of cardo containing asymmetric poly(ether-naphthalimide-phthalimide)s;Nafeesa Mushtaq,et al.;《Polymer International》;20170811;第66卷(第11期);第1633-1639页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108676162A (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | AIE-active polyamide containing diphenylamine-TPE moiety with superior electrofluorochromic performance | |
| Christopherson et al. | 1, 8-Naphthalimide-based polymers exhibiting deep-red thermally activated delayed fluorescence and their application in ratiometric temperature sensing | |
| Wang et al. | Synthesis, photoluminescence, and electrochromism of polyamides containing (3, 6‐di‐tert‐butylcarbazol‐9‐yl) triphenylamine units | |
| Hsiao et al. | High contrast ratio and rapid switching electrochromic polymeric films based on 4-(dimethylamino) triphenylamine-functionalized aromatic polyamides | |
| He et al. | Tetraphenylethene-functionalized conjugated helical poly (phenyl isocyanide) with tunable light emission, assembly morphology, and specific applications | |
| CN111423333B (en) | Diamine monomer containing heptaphenyltriamine-double fluorophore structure, preparation and application thereof, polyamide and polyimide, and preparation and application thereof | |
| CN109336787A (en) | Multifunctional polyurethane derivative and its preparation method and application containing tertiary aromatic amine structure and tetraphenyl ethylene group | |
| Sun et al. | Novel aromatic polyamides containing 2‐diphenylamino‐(9, 9‐dimethylamine) units as multicolored electrochromic and high‐contrast electrofluorescent materials | |
| Hsiao et al. | Fluorescent and electrochromic aromatic polyamides with 4‐tert‐butyltriphenylamine chromophore | |
| Hsiao et al. | Solution‐processable transmissive‐to‐green switching electrochromic polyamides bearing 2, 7‐bis (diphenylamino) naphthalene units | |
| CN108864423B (en) | The application for tetraphenyl-p-phenylenediamine structure diamine monomer that dimethyl amine containing 4- replaces | |
| Sun et al. | High-contrast electrochromic and electrofluorescent dual-switching materials based on 2-diphenylamine-(9, 9-diphenylfluorene)-functionalized semi-aromatic polymers | |
| Bejan et al. | n-Type Polyimides with 1, 3, 4-Oxadiazole-Substituted Triphenylamine Units—An Innovative Structural Approach | |
| CN108676162B (en) | Containing double tetra-tert aniline structures and the polyimide derivatives of naphthalimide fluorophore and its preparation method and application | |
| Hao et al. | Grafting triphenylamine groups onto polysiloxanes to improve interaction between the electrochromic films and ITO | |
| Hsiao et al. | Novel organosoluble aromatic polyetheramides bearing triphenylamine moieties: synthesis, electrochemistry, and electrochromism | |
| CN109575230A (en) | A kind of multifunctional polyurethane derivative and its preparation method and application | |
| Peterson et al. | Surface‐Grafted conjugated polymers for hybrid cellulose materials | |
| CN108623790A (en) | A kind of conjugated polymer and its preparation method and application containing triaryl amine and fluorenes unit | |
| Kung et al. | Pyrenylamine‐functionalized aromatic polyamides as efficient blue‐emitters and multicolored electrochromic materials | |
| Du et al. | A new V-shaped 2H-imidazole-based spirocyclic fluorophore: Aggregation-induced emission, twisted intramolecular charge transfer, and high responsiveness to trace water and acid | |
| CN108559082A (en) | The polyimide derivatives and its preparation method and application of amine structure containing carbazole and naphthalimide fluorophore | |
| Xiang et al. | Dipicolylamine functionalized Polyfluorene based gel with lower critical solution temperature: preparation, characterization, and application | |
| CN109400836A (en) | Urethane derivative and its preparation method and application containing tertiary aromatic amine structure and tetraphenyl ethylene group | |
| Wang et al. | Multicolor electrochromic poly (amide-imide) s with N, N-diphenyl-N′, N′-di-4-tert-butylphenyl-1, 4-phenylenediamine moieties |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190910 Termination date: 20210509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |