CN109593171B - Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof - Google Patents
Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof Download PDFInfo
- Publication number
- CN109593171B CN109593171B CN201811525792.9A CN201811525792A CN109593171B CN 109593171 B CN109593171 B CN 109593171B CN 201811525792 A CN201811525792 A CN 201811525792A CN 109593171 B CN109593171 B CN 109593171B
- Authority
- CN
- China
- Prior art keywords
- polymer
- triarylamine
- multifunctional
- electrochromic
- solid
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent 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"
-
- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Optics & Photonics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nonlinear Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Materials Engineering (AREA)
- Plasma & Fusion (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a multifunctional triarylamine-containing oxazine polymer, and a preparation method and application thereof. The invention aims to solve the problems of poor heat resistance and poor film-adhering capability of an electrochromic polymer film of the traditional triarylamine polymer. The invention uses N 4 ,N 4 The polymer is synthesized by taking bisphenol A and paraformaldehyde as raw materials and performing condensation reaction on triphenylamine monomers under certain conditions, and has excellent electrochromic property and memory property, can be applied to the field of electrochromism, and has good performance in explosive detection; the invention is applied to the field of electrochromic polymers.
Description
Technical Field
The invention relates to a multifunctional triarylamine-containing oxazine polymer, and a preparation method and application thereof.
Background
Electrochromic polymers are polymers that can undergo a color change upon a change in voltage or current. Conductive polymers such as polythiophene, polypyrrole, polyacetylene and the like and certain liquid crystal polymers can be used as electrochromic materials. The conductive polymer is a delocalized conjugated structure, the energy gap between a valence band and conductivity is small, if the polymer is doped (an ionic compound of an electron donor or an acceptor), the energy band structure is changed, and the absorption of light is further changed by applying an external electric field, so that the color is changed. The electrochromic polymer has wide application prospect as a novel functional polymer material.
At present, the problems that the heat resistance of the electrochromic polymer is poor, the formed electrochromic polymer film is easy to fall off and the like still exist, and meanwhile, the electrochromic polymer mostly only explores the performance in the aspect of electrochromic, and besides the electrochromic performance, the polymer still has a plurality of performances which are worthy of development and exploration.
Disclosure of Invention
The invention provides a multifunctional triarylamine oxazine-containing polymer, a preparation method and application thereof, aiming at solving the problems of poor heat resistance and poor film adhering capability of an electrochromic polymer film of the conventional triarylamine oxazine-containing polymer.
The structural formula of the multifunctional triarylamine-containing oxazine polymer is as follows:
The invention relates to a preparation method of a multifunctional triarylamine-containing oxazine polymer, which comprises the following steps:
1. n, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine
At N 2 Under the atmosphere, adding N 4 ,N 4 Putting a di-naphthalene-2-yl-biphenyl-4, 4-diamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked flask, stirring while adding p-fluoronitrobenzene at a dropping speed of 1-2 drops per second, heating to 114-115 ℃, carrying out constant temperature reaction, and then cooling; putting the reaction product into water at 24-25 ℃ until a crude product is separated out, filtering out the crude product, washing the crude product with water at 99-100 ℃ for 2-3 times, putting the obtained crude product into a vacuum drying oven for drying, recrystallizing with ethanol, filtering out a crystallized product after recrystallization, and vacuum-drying the crystallized product to obtain powder M2; wherein the volume of the anhydrous N, N-dimethylformamide is related to the N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomers in a mass ratio (200 to 250) mL:4.50mmol; sodium hydride and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a mass ratio of 39.0mmol:4.50mmol; p-fluoronitrobenzene and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a molar ratio of 13.50mmol:4.50mmol; 24EVolume of water at 25 ℃ and N 4 ,N 4 -the ratio of the amount of substance of di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer (500 to 800) mL:4.50mmol; the temperature of the vacuum drying is 99-100 ℃, the time of the vacuum drying is 40-48 hours, and the pressure of the vacuum drying is-30 KPa to-29 KPa;
(2) adding absolute ethyl alcohol, pd/C and powder M2 into a three-mouth bottle at room temperature, and introducing N into the three-mouth bottle 2 Dripping hydrazine hydrate into the mixed solution in the three-mouth bottle by using a constant-pressure funnel at a dripping speed of 1-2 drops per second; heating until the solution reflows, stopping heating after the reflow reaction is finished, removing Pd/C by filtering at 79-80 ℃, pouring filtrate into water at 4-5 ℃, adding sodium chloride while stirring until solid is separated out, filtering and washing the solid with ethanol, and vacuum-drying the filtered solid to obtain solid M22;
wherein the volume mass ratio of the absolute ethyl alcohol to the powder M2 is (200-300) mL:2g of the total weight of the mixture; the mass ratio of Pd/C to the powder M2 is (0.70-0.80) g:2g of the total weight of the mixture; the volume mass ratio of the hydrazine hydrate to the powder M2 is (18-20) mL:2g of the total weight of the mixture; the volume ratio of the filtrate to the water with the temperature of 4-5 ℃ is 1 (3-4); the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
2. preparation of triarylamine-containing oxazine polymer
At N 2 Adding a mixed solution of absolute ethyl alcohol and dehydrated toluene into a three-necked bottle in an atmosphere, adding solid M22 and bisphenol fluorene, stirring for 10-20 min, adding polyformaldehyde into the three-necked bottle, heating to 85 ℃, and reacting for 48h to obtain a polymer solution; pouring the polymer solution into methanol according to the volume ratio of 7 to 40, separating out a product, washing with methanol, performing suction filtration, drying the obtained product in a vacuum drying oven, and performing Soxhlet extraction for purification to obtain a triarylamine-containing oxazine polymer; wherein the volume ratio of the solid M22 substance to the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 0.6mmol:13mL, wherein the volume ratio of the absolute ethyl alcohol to the dehydrated toluene in the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 1; solid M22 and bisThe mass ratio of the phenol fluorene is 0.6mmol:0.7mmol; the mass ratio of solid M22 to paraformaldehyde is 0.6mmol:2.6mmol; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, the time is controlled in the drying process, and the pressure of the vacuum drying is-30 to-29 KPa; the Soxhlet extraction temperature is 70 ℃, and the Soxhlet extraction time is 48h.
The invention relates to an application of a multifunctional triarylamine-containing oxazine polymer serving as an electrochromic layer in an electrochromic device in electrochromism.
The multifunctional triarylamine-group-containing oxazine polymer is used for detecting explosive 2,4, 6-trinitrotoluene.
The principle of the invention is as follows:
in the invention, firstly, triphenylamine monomers are prepared, and N is used in the invention 4 ,N 4 The method comprises the steps of taking-di-naphthalene-2-yl-biphenyl-4, 4-diamine as a raw material, then reacting with p-fluoronitrobenzene to realize nitration, then reducing nitro to amino, taking bisphenol A, paraformaldehyde and prepared triphenylamine monomers as raw materials, and synthesizing through a Mannich condensation reaction under a certain condition to synthesize a series of polymers with small relative molecular weight, wherein the polymers can be subjected to ring opening polymerization under the action of heating or a catalyst.
The invention has the following special effects:
1. the benzoxazine structure is introduced into the triphenylamine molecular formula with the electrochromic property, a series of polymers with the triphenylamine benzoxazine structure with new functions are designed and prepared, the performance of the electrochromic material is reserved, and meanwhile, the introduction of the benzoxazine structure can enable the polymer with higher rigidity to have better solubility in common organic solvents. During the heat treatment, the oxazine ring in the polymer can undergo a ring-opening reaction and cross-linking. The bonding strength of the coating and the substrate is improved, and the film forming property of the polymer is improved, so that the electrochemical test of the polymer is facilitated;
2. the polymer has excellent electrochromic property and memory property, can be applied to the field of electrochromic, and has good performance in explosive detection;
electrochromism refers to a phenomenon in which a substance undergoes an electrochemical redox reaction to cause color change under the drive of an external voltage or current. The triphenylamine group-containing polymer contains active sites for electron transport and electron transition, and when a certain voltage is applied to the polymer, the electron transition occurs in the polymer to generate a color change. The polymer of the invention has obvious color change within the voltage range of 0.60-1.80V, and the coloring time of the polymer of the invention is 1.7-1.9 s; bleaching for 1.8-2.0 s; the combination of the oxazine and the unit containing the triphenylamine group promotes the electron transfer between the oxazine and the unit containing the triphenylamine group, so that the color change of the conjugated polymer containing the triphenylamine group and the oxazine structure is more obvious; the color is dark blue to dark red when in coloring, and the color is nearly colorless when in bleaching, so the contrast ratio is very high when in electrochromism;
3. the polymer has strong fluorescence, and the fluorescence of the polymer gradually decreases until the polymer disappears after the polymer is contacted with a solution prepared from 2,4, 6-trinitrotoluene serving as an explosive, so that the polymer can be used for detecting the 2,4, 6-trinitrotoluene serving as the explosive;
4. according to the thermal weight loss curve, the triarylamine-containing oxazine polymer prepared by the method has good heat resistance.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of the multifunctional triarylamine-containing oxazine-based polymer prepared in the first example;
FIG. 2 is a cyclic voltammogram of the multifunctional triarylamine-containing oxazine-based polymer prepared in example one;
FIG. 3 is an electrochromic diagram of a multifunctional triarylamine-containing oxazine-based polymer prepared according to example one;
FIG. 4 is a graph of the thermal weight loss of the multifunctional triarylamine-containing oxazine-based polymer prepared according to example one;
FIG. 5 is a fluorescence plot of the response of the multifunctional triarylamine-containing oxazine-based polymer to TNT prepared according to example one;
FIG. 6 is a fluorescence plot of the response of the multifunctional triarylamine-containing oxazine-based polymer prepared according to example one to TNP;
FIG. 7 is a graph of memory performance of the multifunctional triarylamine-containing oxazine-based polymer prepared in example one.
Detailed Description
The technical solution of the present invention is not limited to the embodiments listed below, and includes any combination of the embodiments.
The first embodiment is as follows: the structural formula of the multifunctional triarylamine-containing oxazine polymer is as follows:
wherein n is an integer of 3 to 10.
In this embodiment, first, a triphenylamine-based monomer is prepared, and in this embodiment, N is used 4 ,N 4 The method comprises the steps of taking-di-naphthalene-2-yl-biphenyl-4, 4-diamine as a raw material, then reacting with p-fluoronitrobenzene to realize nitration, then reducing nitro to amino, taking bisphenol A, paraformaldehyde and prepared triphenylamine monomers as raw materials, and synthesizing through a Mannich condensation reaction under a certain condition to synthesize a series of polymers with small relative molecular weight, wherein the polymers can be subjected to ring opening polymerization under the action of heating or a catalyst.
The present embodiment has the following special effects:
1. the benzoxazine structure is introduced into the triphenylamine molecular formula with the electrochromic property, a series of polymers with the triphenylamine benzoxazine structure with new functions are designed and prepared, the performance of the electrochromic material is reserved, and meanwhile, the benzoxazine structure is introduced, so that the polymer with higher rigidity originally has better solubility in a common organic solvent. During the heat treatment process, the oxazine ring in the polymer can undergo a ring-opening reaction and undergo crosslinking. The bonding strength between the coating and the substrate is improved, and the film forming property of the polymer is improved, so that the electrochemical test of the polymer is facilitated;
2. the polymer of the embodiment has excellent electrochromic property and memory property, can be applied to the field of electrochromic, and has good performance in explosive detection;
electrochromism refers to a phenomenon in which a substance undergoes an electrochemical redox reaction to cause color change under the drive of an external voltage or current. The triphenylamine group-containing polymer contains active sites for electron transport and electron transition, and when a certain voltage is applied to the polymer, the electron transition occurs in the polymer to generate a color change. The polymer of the embodiment has obvious color change in the voltage range of 0.60-1.80V, and the coloring time of the polymer of the embodiment is 1.7-1.9 s; bleaching for 1.8-2.0 s; the combination of the oxazine and the unit containing the triphenylamine group promotes the electron transfer between the oxazine and the unit containing the triphenylamine group, so that the color change of the conjugated polymer containing the triphenylamine group and the oxazine structure is more obvious; the color is dark blue to dark red when in coloring, and the color is nearly colorless when in bleaching, so the contrast ratio is very high when in electrochromism;
3. the polymer of the embodiment has strong fluorescence, and the fluorescence of the polymer gradually decreases until disappears after the polymer of the embodiment is contacted with a solution prepared from 2,4, 6-trinitrotoluene serving as an explosive, so that the polymer of the embodiment can be used for detecting 2,4, 6-trinitrotoluene serving as an explosive;
4. according to the thermal weight loss curve, the triarylamine group-containing oxazine polymer prepared by the embodiment has good heat resistance.
The second embodiment is as follows: the preparation method of the multifunctional triarylamine-containing oxazine polymer in the embodiment comprises the following steps:
1. n, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine
In N 2 Under the atmosphere, adding N 4 ,N 4 Putting a di-naphthalene-2-yl-biphenyl-4, 4-diamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked flask, adding p-fluoronitrobenzene at a dripping speed of 1-2 drops per second while stirring, heating to 114-115 ℃, performing constant temperature reaction, and cooling; placing the reaction product at 24-2Separating out the crude product in water at 5 ℃, filtering out the crude product, washing the crude product for 2-3 times by using water at 99-100 ℃, drying the obtained crude product in a vacuum drying oven, recrystallizing by using ethanol, filtering out a crystallized product after recrystallization, and drying the crystallized product in vacuum to obtain powder M2; wherein the volume of the anhydrous N, N-dimethylformamide is equal to the volume of the anhydrous N, N-dimethylformamide 4 ,N 4 -the ratio of the amount of substance of di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer (200 to 250) mL:4.50mmol; sodium hydride and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a mass ratio of 39.0mmol:4.50mmol; p-fluoronitrobenzene and N 4 ,N 4 -di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a molar ratio of 13.50mmol:4.50mmol; volume of water at 24-25 ℃ and N 4 ,N 4 -the ratio of the amount of substance of di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer (500 to 800) mL:4.50mmol; the temperature of the vacuum drying is 99-100 ℃, the time of the vacuum drying is 40-48 hours, and the pressure of the vacuum drying is-30 KPa to-29 KPa;
(2) adding absolute ethyl alcohol, pd/C and powder M2 into a three-mouth bottle at room temperature, and introducing N into the three-mouth bottle 2 Dripping hydrazine hydrate into the mixed solution in the three-necked bottle by using a constant-pressure funnel at a dripping speed of 1-2 drops per second; heating until the solution reflows, stopping heating after the reflow reaction is finished, removing Pd/C by filtering at 79-80 ℃, pouring filtrate into water at 4-5 ℃, adding sodium chloride while stirring until solid is separated out, filtering and washing the solid with ethanol, and vacuum-drying the filtered solid to obtain solid M22;
wherein the volume-mass ratio of the absolute ethyl alcohol to the powder M2 is (200-300) mL:2g of the total weight of the mixture; the mass ratio of Pd/C to powder M2 is (0.70-0.80) g:2g of the total weight of the mixture; the volume mass ratio of hydrazine hydrate to the powder M2 is (18-20) mL:2g of the total weight of the mixture; the volume ratio of the filtrate to the water with the temperature of 4-5 ℃ is 1 (3-4); the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
2. preparation of triarylamine-containing oxazine polymer
In N 2 Adding a mixed solution of absolute ethyl alcohol and dehydrated toluene into a three-necked bottle in an atmosphere, adding solid M22 and bisphenol fluorene, stirring for 10-20 min, adding polyformaldehyde into the three-necked bottle, heating to 85 ℃, and reacting for 48h to obtain a polymer solution; pouring the polymer solution into methanol according to the volume ratio of 7 to 40, precipitating a product, washing with methanol, carrying out suction filtration, drying the obtained product in a vacuum drying oven, and then carrying out Soxhlet extraction for purification to obtain a triarylamine-containing oxazine polymer; wherein the volume ratio of the solid M22 substance to the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 0.6mmol:13mL, wherein the volume ratio of the absolute ethyl alcohol to the dehydrated toluene in the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 1; the mass ratio of the solid M22 to bisphenol fluorene was 0.6mmol:0.7mmol; the mass ratio of the solid M22 to paraformaldehyde is 0.6mmol:2.6mmol; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, the time control is paid attention to in the drying process, and the pressure of the vacuum drying is-30 KPa to-29 KPa; the Soxhlet extraction temperature is 70 ℃, and the Soxhlet extraction time is 48h.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: in the step one (1), the powder M2 is N, N '-bis (4-nitrophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: in the step one (2), the solid M22 is N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the second to fourth embodiments is: in the step one (2), the temperature rise speed is 9-10 ℃ per minute when the temperature rises to the reflux of the solution. The other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode is as follows: the multifunctional triarylamine-containing oxazine polymer is applied to electrochromism as an electrochromism layer in an electrochromism device.
The seventh embodiment: the sixth embodiment is different from the specific embodiment in that: the application method of the triarylamine oxazine polymer as an electrochromic layer in an electrochromic device in electrochromism comprises the following steps:
the triarylamine oxazine polymer is used as an electrochromic layer in an electrochromic device, the electrochromic layer is coated on a conductive substrate to prepare the electrochromic device, and the electrochromic layer generates electrochromic under the action of an external electric field. The rest is the same as the sixth embodiment.
The specific implementation mode is eight: the sixth or seventh embodiment is different from the sixth or seventh embodiment in that: the conductive substrate is conductive glass. The rest is the same as the sixth or seventh embodiment.
The specific implementation method nine: this embodiment is different from the sixth to eighth embodiment in that: the application method of the triarylamine oxazine polymer as an electrochromic layer in an electrochromic device comprises the following steps: the triarylamine oxazine polymer is used as an electrochromic layer in an electrochromic device, the electrochromic layer is coated on a conductive substrate to prepare the electrochromic device, and the electrochromic layer generates electrochromism under the action of an external electric field. The rest is the same as the sixth to eighth embodiments.
The detailed implementation mode is ten: the multifunctional triarylamine-containing oxazine polymer is used for detecting 2,4, 6-trinitrotoluene serving as an explosive.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the structural formula of the multifunctional triarylamine-containing oxazine polymer is as follows:
The preparation method of the multifunctional triarylamine-containing oxazine polymer comprises the following steps:
1. n, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine
At N 2 Under the atmosphere, adding N 4 ,N 4 Putting a di-naphthalene-2-yl-biphenyl-4, 4-diamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked flask, stirring while adding p-fluoronitrobenzene at a dropping speed of 1-2 drops per second, heating to 114-115 ℃, carrying out constant temperature reaction, and then cooling; putting the reaction product into water at 24-25 ℃ until a crude product is separated out, filtering out the crude product, washing the crude product with water at 99-100 ℃ for 2-3 times, putting the obtained crude product into a vacuum drying oven for drying, recrystallizing with ethanol, filtering out a crystallized product after recrystallization, and vacuum-drying the crystallized product to obtain powder M2; wherein the volume of the anhydrous N, N-dimethylformamide is related to the N 4 ,N 4 -the ratio of the amount of substance of di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer is 200mL:4.50mmol; sodium hydride and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a mass ratio of 39.0mmol:4.50mmol; p-fluoronitrobenzene and N 4 ,N 4 -di-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a molar ratio of 13.50mmol:4.50mmol; volume of water at 24-25 ℃ and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a mass ratio of 750mL:4.50mmol; the temperature of the vacuum drying is 99-100 ℃, the time of the vacuum drying is 40-48 hours, and the pressure of the vacuum drying is-30 to-29 KPa;
(2) adding absolute ethyl alcohol, pd/C and powder M2 into a three-mouth bottle at room temperature, and introducing N into the three-mouth bottle 2 Dripping hydrazine hydrate into the mixed solution in the three-mouth bottle by using a constant-pressure funnel at a dripping speed of 1-2 drops per second; heating until the solution is refluxed, stopping heating after the reflux reaction is finished, filtering to remove Pd/C at 79-80 ℃, pouring the filtrate into water at 4-5 ℃, stirring while adding sodium chloride until solid is separated out, filtering to remove the solid, washing with ethanol, and vacuum-drying the filtered solid to obtain a solid M22;
wherein the volume mass ratio of the absolute ethyl alcohol to the powder M2 is 250mL:2g of the total weight of the mixture; the mass ratio of Pd/C to powder M2 is (0.70-0.80) g:2g of the total weight of the mixture; the volume mass ratio of hydrazine hydrate to the powder M2 is (18-20) mL:2g of the total weight of the mixture; the volume ratio of the filtrate to the water with the temperature of 4-5 ℃ is 1 (3-4); the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, and the pressure of the vacuum drying is-30 KPa to-29 KPa;
2. preparation of triarylamine-containing oxazine polymer
At N 2 Adding a mixed solution of absolute ethyl alcohol and dehydrated toluene into a three-neck flask in an atmosphere, adding solid M22 and bisphenol fluorene, stirring for 10-20 min, adding polyformaldehyde into the three-neck flask, heating to 85 ℃, and reacting for 48h to obtain a polymer solution; pouring the polymer solution into methanol according to the volume ratio of 7 to 40, precipitating a product, washing with methanol, carrying out suction filtration, drying the obtained product in a vacuum drying oven, and then carrying out Soxhlet extraction for purification to obtain a triarylamine-containing oxazine polymer; wherein the volume ratio of the solid M22 substance to the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 0.6mmol:13mL, wherein the volume ratio of the absolute ethyl alcohol to the dehydrated toluene in the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 1; the mass ratio of the solid M22 to bisphenol fluorene was 0.6mmol:0.7mmol; the mass ratio of solid M22 to paraformaldehyde is 0.6mmol:2.6mmol; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, the time control is paid attention to in the drying process, and the pressure of the vacuum drying is-30 KPa to-29 KPa; the Soxhlet extraction temperature is 70 ℃, and the Soxhlet extraction time is 48h.
Wherein the powder M2 is N, N '-bis (4-nitrophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine, in a yield of 60%. The solid M22 was N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine and the yield was 60%.
In this example, step (1) was performed by thin layer chromatography to determine whether the isothermal reaction was completed, and step (2) was performed by thin layer chromatography to determine whether the reflux reaction was completed.
The triarylamine-containing oxazine polymer prepared by the embodiment is relatively easy to dissolve in a polar solvent, and 1.5 g of the triarylamine-containing oxazine polymer can be dissolved in 10 ml of the polar solvent; it is slightly soluble in nonpolar solvents, and is soluble in 0.2 g per 10 ml of polar solution.
FIG. 1 is a hydrogen nuclear magnetic spectrum of the multifunctional triarylamine-containing oxazine-based polymer prepared in the first example; as can be seen from FIG. 1, the chemical shift delta in FIG. 1 is shown at 4.50,5.30ppm, i.e. the chemical shift of the characteristic peak of oxazine, which illustrates that the example I synthesizes the triarylamine group-containing oxazine polymer;
FIG. 2 is a cyclic voltammogram of the multifunctional triarylamine-containing oxazine-based polymer prepared according to example one; as can be seen from FIG. 2, an oxidation peak and a reduction peak appear at 1.14V and 0.86V respectively; the multifunctional triarylamine-containing oxazine polymer prepared in the first example is subjected to redox reaction under the condition of voltage application, and the triarylamine-containing oxazine polymer can generate color change in the redox process, so that the triarylamine-containing oxazine polymer prepared in the first example has electrochromic property;
FIG. 3 is an electrochromic diagram of a multifunctional triarylamine-containing oxazine-based polymer prepared according to example one; in FIG. 3, curve 1 is a UV absorption curve at an applied voltage of 2.0V to 0.0V; as can be seen from FIG. 3, the triarylamine group-containing oxazine-based polymer prepared in example one has an absorption peak at 330nm before no voltage is applied, and when the applied voltage is from 0.0V to 2.0V, new absorption peaks appear at 450nm and 850nm and gradually rise; the triarylamine group-containing oxazine polymer prepared in the first embodiment has an electrochromic function, and the color of the polymer is from light yellow to orange red to dark blue to bright red;
FIG. 4 is a graph of the thermogravimetric plot of the multifunctional triarylamine-containing oxazine-based polymer prepared in example one; as can be seen from fig. 4, the multifunctional triarylamine group-containing oxazine polymer prepared in example one starts to lose a large amount of weight at about 300 ℃, and has a residual carbon content of 95% at 395 ℃ and 90% at 442 ℃; when the temperature is 546 ℃, the residual carbon content is 80 percent, and when the temperature reaches 800 ℃, the residual carbon content of the multifunctional triarylamine group-containing oxazine polymer prepared in the first embodiment is 67 percent; further, the series of polymers have good thermal stability and can work in high-temperature environments, such as the aerospace field.
Dissolving 1 mg of triarylamine-containing oxazine polymer in 20mL of N-methylpyrrolidone to obtain a triarylamine-containing oxazine polymer solution with a concentration of 1 x 10 < -5 > M, and adding a solvent to the solution2 microliter of picric acid is added into the oxazine polymer solution; FIG. 5 is a fluorescence plot of the response of the multifunctional triarylamine-containing oxazine-based polymer to TNT prepared according to example one; in the figure, curve 1 is the fluorescence intensity curve of the triarylamine oxazine polymer solution without TNT, and curves 2 to 8 are respectively added with 2 microliter of 1 × 10 -10 M、1×10 -9 M、1×10 -8 M、1×10 -7 M、1×10 -6 M、1×10 -5 M、1×10 -4 M, the fluorescence intensity curve of TNT triarylamine oxazine polymer solution containing the TNT; it can be seen from fig. 5 that the fluorescence intensity of the polymer solution gradually decreases with the increase of the TNT concentration; indicating that the polymer can respond to TNT, namely judging whether TNT exists or not by judging whether the polymerization fluorescence is reduced or not;
dissolving 1 mg of triarylamine-containing oxazine polymer in 20mL of N-methylpyrrolidone to obtain 1 x 10 < -5 > M triarylamine-containing oxazine polymer solution, and adding 2 microliters of trinitrophenol into the triarylamine-containing oxazine polymer solution; FIG. 6 is a fluorescence plot of the response of the multifunctional triarylamine-containing oxazine-based polymer prepared according to example one to TNP; in the figure, curve 1 is the fluorescence intensity curve of the triarylamine oxazine polymer solution without adding TNP, and curves 2 to 8 are respectively added with 2 microliter of 1 multiplied by 10 -10 M、1×10 -9 M、1×10 -8 M、1×10 -7 M、1×10 -6 M、1×10 -5 M、1×10 -4 Fluorescence intensity curve of the triarylamine oxazine polymer solution containing TNP of M; it can be seen from FIG. 6 that the fluorescence intensity of the polymer solution gradually decreases with the increase of the TNP concentration; further, the polymer can respond to TNP, and whether TNP exists or not is judged through whether the polymerization fluorescence is reduced or not;
FIG. 7 is a graph of the memory performance of the multifunctional triarylamine-containing oxazine-based polymer prepared according to example one; it can be seen from fig. 7 that in the first voltage sweep, from 0 to-8V (sweep 2), a sharp increase in current is observed when the negative threshold voltage is-2.8V and the memory device switches from the low conductivity state (OFF) to the high conductivity state (ON). This conversion process can be used as a "write" process for ITO/Polymer/Al devices. During the next scan (scan 3), the current remains in the ON state and the device remains in the high ON state. In the third scan from 0 to +8V (scan 4), a sudden drop in current at a threshold voltage of +3.2V indicates that the memory device is undergoing a transition from the ON state to the original OFF state. This transition from ON to OFF may be as an "erase" process. As forward bias is applied, the current remains in the low on state in the subsequent voltage sweep (sweep 1). Thus, the memory devices fabricated with the polymer are binary flash data storage devices.
Claims (9)
1. A preparation method of a multifunctional triarylamine-containing oxazine polymer is characterized in that the preparation method of the triarylamine-containing oxazine polymer comprises the following steps:
1. n, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine
(1) In N 2 Under the atmosphere, adding N 4 ,N 4 Putting a di-naphthalene-2-yl-biphenyl-4, 4-diamine monomer, sodium hydride and anhydrous N, N-dimethylformamide into a three-necked flask, adding p-fluoronitrobenzene at a dripping speed of 1-2 drops per second while stirring, heating to 114-115 ℃, performing constant temperature reaction, and cooling; putting the reaction product into water at 24-25 ℃ until a crude product is separated out, filtering out the crude product, washing the crude product with water at 99-100 ℃ for 2-3 times, putting the obtained crude product into a vacuum drying oven for drying, recrystallizing with ethanol, filtering out a crystallized product after recrystallization, and vacuum-drying the crystallized product to obtain powder M2; wherein the volume of the anhydrous N, N-dimethylformamide is related to the N 4 ,N 4 -di-naphthalen-2-yl-biphenyl-4, 4-diamine monomers in a mass ratio of 200 to 250mL:4.50mmol; sodium hydride and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a mass ratio of 39.0mmol:4.50mmol; p-fluoronitrobenzene and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomer in a molar ratio of 13.50mmol:4.50mmol; volume of water at 24-25 ℃ and N 4 ,N 4 -bis-naphthalen-2-yl-biphenyl-4, 4-diamine monomers in a mass ratio of 500 to 800mL:4.50mmol; the vacuumThe drying temperature is 99-100 ℃, the vacuum drying time is 40-48 hours, and the vacuum drying pressure is-30 to-29 KPa;
(2) adding absolute ethyl alcohol, pd/C and powder M2 into a three-mouth bottle at room temperature, and introducing N into the three-mouth bottle 2 Dripping hydrazine hydrate into the mixed solution in the three-necked bottle by using a constant-pressure funnel at a dripping speed of 1-2 drops per second; heating until the solution is refluxed, stopping heating after the reflux reaction is finished, filtering to remove Pd/C at 79-80 ℃, pouring the filtrate into water at 4-5 ℃, stirring while adding sodium chloride until solid is separated out, filtering to remove the solid, washing with ethanol, and vacuum-drying the filtered solid to obtain a solid M22;
wherein the volume mass ratio of the absolute ethyl alcohol to the powder M2 is 200-300 mL:2g of the total weight of the mixture; the mass ratio of Pd/C to powder M2 is 0.70-0.80 g:2g of the total weight of the mixture; the volume mass ratio of hydrazine hydrate to the powder M2 is 18-20 mL:2g of the total weight of the mixture; the volume ratio of the filtrate to water at 4-5 ℃ is 1; the Pd/C is a Pd-doped C composite material, and the mass fraction of Pd in the Pd/C is 10%; the temperature of the vacuum drying is 29-30 ℃, the time of the vacuum drying is 24 hours, and the pressure of the vacuum drying is-30 KPa to-29 KPa;
2. preparation of triarylamine-containing oxazine polymer
At N 2 Adding a mixed solution of absolute ethyl alcohol and dehydrated toluene into a three-necked bottle in an atmosphere, adding solid M22 and bisphenol fluorene, stirring for 10-20 min, adding polyformaldehyde into the three-necked bottle, heating to 85 ℃, and reacting for 48h to obtain a polymer solution; pouring the polymer solution into methanol according to the volume ratio of 7 to 40, separating out a product, washing with methanol, performing suction filtration, drying the obtained product in a vacuum drying oven, and performing Soxhlet extraction for purification to obtain a triarylamine-containing oxazine polymer; wherein the volume ratio of the solid M22 substance to the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 0.6mmol:13mL, wherein the volume ratio of the absolute ethyl alcohol to the dehydrated toluene in the mixed solution of the absolute ethyl alcohol and the dehydrated toluene is 1; the ratio of the amount of solid M22 to bisphenol fluorene material was 0.6mmol:0.7mmol; the mass ratio of solid M22 to paraformaldehyde is 0.6mmol:2.6mmol; the temperature of the vacuum drying is 29-30 ℃, and the temperature isThe air drying time is 24 hours, the control of the time is noticed in the drying process, and the pressure of the vacuum drying is-30 to-29 KPa; the Soxhlet extraction temperature is 70 ℃, and the Soxhlet extraction time is 48h.
2. The method for preparing a multifunctional triarylamine-containing oxazine polymer as claimed in claim 1, wherein in step one (1), the powder M2 is N, N '-bis (4-nitrophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine.
3. The method for preparing the multifunctional triarylamine-containing oxazine polymer as claimed in claim 1, wherein the solid M22 in the step (2) is N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine.
4. The method for preparing a multifunctional triarylamine group-containing oxazine polymer as claimed in claim 1, wherein the temperature rise rate of the solution heated to reflux in the step one (2) is 9-10 ℃ per minute.
5. The use of the multifunctional triarylamine-containing oxazine polymer of claim 1, wherein the triarylamine-containing oxazine polymer is used for electrochromic as an electrochromic layer in an electrochromic device.
6. The application of the multifunctional triarylamine-containing oxazine polymer of claim 5, wherein the application method of the triarylamine-containing oxazine polymer as an electrochromic layer in an electrochromic device is as follows:
the triarylamine oxazine polymer is used as an electrochromic layer in an electrochromic device, the electrochromic layer is coated on a conductive substrate to prepare the electrochromic device, and the electrochromic layer generates electrochromic under the action of an external electric field.
7. The use of the multifunctional triarylamine group-containing oxazine-based polymer of claim 6, wherein the conductive matrix is conductive glass.
8. The use of the multifunctional triarylamine group-containing oxazine polymer of claim 6, wherein the voltage of the applied electric field is 0.60-1.80V.
9. The use of the multifunctional triarylamine-containing oxazine polymer of claim 1, wherein the triarylamine-containing oxazine polymer is used for detection of explosive 2,4, 6-trinitrotoluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811525792.9A CN109593171B (en) | 2018-12-13 | 2018-12-13 | Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811525792.9A CN109593171B (en) | 2018-12-13 | 2018-12-13 | Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109593171A CN109593171A (en) | 2019-04-09 |
| CN109593171B true CN109593171B (en) | 2023-02-21 |
Family
ID=65961896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811525792.9A Active CN109593171B (en) | 2018-12-13 | 2018-12-13 | Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109593171B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019125B (en) * | 2019-12-23 | 2022-05-03 | 黑龙江大学 | Multifunctional triarylamine polyamide containing fused ring naphthyl side group structure and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896867A (en) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof |
-
2018
- 2018-12-13 CN CN201811525792.9A patent/CN109593171B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896867A (en) * | 2014-03-21 | 2014-07-02 | 哈尔滨工程大学 | N-full-aromatic hydrocarbon diamine-bisphenol tetrafunctional fluorenyl benzoxazine and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Novel near-infrared and multi-colored electrochromic polybenzoxazines with electroactive triarylamine moieties";Lu-Chi Lin等;《Journal of Materials Chemistry C》;20141231;第2卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109593171A (en) | 2019-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109593172B (en) | Benzoxazine structure-containing triarylamine polymer and preparation method and application thereof | |
| CN108559066B (en) | Conjugated polymer containing triarylamine and fluorene units, and preparation method and application thereof | |
| Qin et al. | Synthesis and electrochromic properties of polyacrylate functionalized poly (3, 4-ethylenedioxythiophene) network films | |
| CN108623788B (en) | Triphenylamine group-containing isoindigo polymer, preparation method thereof and application thereof in electrochromism | |
| CN105860033B (en) | Side chain contains polythiophene of hydrophilic radical and preparation method thereof | |
| Kuo et al. | Electrochemical fluorescence switching properties of conjugated polymers composed of triphenylamine, fluorene, and cyclic urea moieties | |
| CN114907551B (en) | Red electrochromic polymer, preparation method, film and device | |
| CN109336787B (en) | Preparation method and application of multifunctional polyurethane derivative containing triarylamine structure and tetraphenylethylene group | |
| CN102746514B (en) | Hyper branched polysiloxane modified polyaniline (PANI) and preparation method thereof | |
| CN114853987B (en) | Electrochromic copolymer containing dioxythiophene and 9,9' -spirobifluorene structure, preparation method thereof and polymer film | |
| CN108623790B (en) | Preparation method and application of conjugated polymer containing triarylamine and fluorene units | |
| CN109593171B (en) | Multifunctional triarylamine-containing oxazine polymer and preparation method and application thereof | |
| CN114853988B (en) | Electrochromic polymer containing thiophene embedded units, preparation method, film and device | |
| CN114349937B (en) | Water-alcohol-soluble electrochromic polymer and preparation method and application thereof | |
| CN108641067B (en) | Carbazolyl-containing isoindigo polymer, preparation method thereof and application thereof in electrochromism | |
| CN109651284B (en) | Triarylamine-containing oxazine polymer and preparation method and application thereof | |
| Park et al. | Synthesis and photovoltaic properties of side‐chain liquid‐crystal click polymers for dye‐sensitized solar‐cells application | |
| CN108794731B (en) | Application of conjugated polymer containing triarylamine and fluorene units | |
| CN108623789B (en) | Di-tert-butyl carbazolyl-containing isoindigo polymer, preparation method thereof and application thereof in electrochromism | |
| CN110982064B (en) | Triarylamine polyamide containing fused ring anthracenyl side group structure and preparation method and application thereof | |
| CN111019125B (en) | Multifunctional triarylamine polyamide containing fused ring naphthyl side group structure and preparation method and application thereof | |
| CN115521442B (en) | Solution-processable red-to-transparent electrochromic polymer and preparation method and application thereof | |
| CN108676162A (en) | Polyimide derivatives and its preparation method and application containing double tetra-tert aniline structures and naphthalimide fluorophore | |
| KR101619130B1 (en) | Manufacturing method of conductive polymer solution and device manufacturing for the same | |
| KR101656991B1 (en) | Production of conductive polymer solution by viscosity control and cured product thereby |
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 |