CN1613961A - Organic electroluminescent materials containing difluorene segments and its synthesis - Google Patents
Organic electroluminescent materials containing difluorene segments and its synthesis Download PDFInfo
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- CN1613961A CN1613961A CN 200410054196 CN200410054196A CN1613961A CN 1613961 A CN1613961 A CN 1613961A CN 200410054196 CN200410054196 CN 200410054196 CN 200410054196 A CN200410054196 A CN 200410054196A CN 1613961 A CN1613961 A CN 1613961A
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Abstract
The invention relates to a luminescent material produced by the organic electrolyte and containing fluorine fragment. It is produced by: linking fluorine of p type, n type or p-n double inlaying fragment to the conjugate polymeric monomer, then getting the target monomer by the specific function group to cape the end, last polymerizing again to get product. It is mainly used for profucing organic electroluminescent elements and photovoltaic batteries, information storage units, TFTs and so on.
Description
Technical field
The invention belongs to the electroluminescent organic material technical field, be specifically related to a kind of segmental electroluminescent organic material of difluorene and synthetic method thereof of containing.
Background content
Organic/polymer electroluminescent device (Organic/Polymer Light-Emitting Device, OLED/PLED) be one of the focus forward position of current scientific research, the indicating meter made from it has high image quality, screen size can arbitrarily be adjusted, energy consumption is low, and light weight and approaching adopts the flexible macromolecule substrate collapsible, advantages such as tooling cost is low, thus represented the development trend of following technique of display.In display of organic electroluminescence, realize that the big area full color shows that stable red, green and blue three primary colours must be arranged.But have only red at present and greenly just have necessary luminous efficiency of business development and life-span, the high stable, high-level efficiency of realizing the material blue emission at present or a difficult problem.The common material that is used to prepare organic electroluminescent LED has benzene, fluorenes, carbazole, to phenylacetylene support, thiophene and their derivative etc.Poly-fluorenes is a kind of compound with rigid plane biphenyl modular construction, can go up limited several reflecting points by ring, and particularly the carbon on No. 9 positions obtains a series of derivatives.
Poly-fluorenes is to be obtained by human iron trichloride oxidative coupling fluorenes such as Fukuda the earliest, and this polymkeric substance is because molecular weight is low, branching is more serious, and because residual iron ion strong absorption exciton, finally causes the polymer materials can't be luminous and do not have a practical value.Through constantly improving, on the polymer manufacture of fluorenes, obtained significant progress afterwards.The wherein ground-breaking work of tool is that people such as Suzuki finish.The poly-fluorenes molecular weight height that they obtain, the degree of branching is little, and molecular weight distribution is narrow.Wherein the poly-fluorenes photodiode of green light can be 22cm/W in peak efficient, under the situation of driving voltage less than 6V, and the luminous continuously 10000cd/m that surpasses
2
In order to make blue light material can satisfy the needs of practicability early, the various countries scientist drops into great amount of manpower and material resources aspect the synthetic and performance study of organic blue light material.Fluorenes is as the extremely favor of each side especially of a kind of traditional blue light material.Fluorenes and derivative thereof can become the research focus of luminescent material, and this mainly is the energy gap owing to the fluorenes broad, higher characteristics such as luminous efficiency.But the electron affinity of fluorenes is little, and the solvability of poly-fluorenes is limited.No. 9 position carbon atoms of fluorenes become carbonyl again than being easier to oxidation, this easily forms " trap " to the exciton that electronics, hole-recombination produced and certain " cancellation " effect is arranged, and can reduce the luminescent lifetime of device.In order to improve the comprehensive electroluminescent properties of fluorenes, mainly at present adopt preparation small molecules fluorenes fluorescent material, introduce on fluorenes that different side group post polymerization prepares fluorenes homopolymer, fluorenes monomer and other monomer copolymerizations and preparation is derived and next methods such as branch-shape polymer by fluorenes.Reactive mode commonly used has Suzuki reaction, Yamamoto reaction, Wittig reaction and Stille reaction etc., wherein more with Suzuki reaction and Wittig reaction usefulness again.
Summary of the invention
The objective of the invention is to propose a kind of luminous efficiency height, and can improve device performance contain segmental electroluminescent organic material of difluorene and preparation method thereof.
The present invention proposes a kind ofly to contain segmental electroluminescent organic material of difluorene and synthetic method thereof, and is used to prepare corresponding photodiode.Preparation methods is, on the conjugation polymerisable monomer, connect the side group that contains the two blocks of different lengths p type, n type or p-n based on the difluorene fragment, obtain comonomer with group end capping with specific function, pass through polyreaction again, just obtain having the electroluminescent organic material of difluorene fragment structure.
In order to improve the solvability of such organic polymer material, and the thermostability that improves material, on side group, introduce a certain amount of spacer groups, for example alkyl, phenyl ring etc., or their derivative.Both can be identical, also can be different.
The present invention propose to contain the segmental electroluminescent organic material of difluorene, be to be chief component with the difluorene fragment, on the linear polymeric main chain that connects continuously, introduce non-rectilinear conjugation fragment, become the polymkeric substance that the conjugated structure part of main chain is interrupted.The structure of such material can be expressed as:
Wherein, Ar can be a kind of of following unit: the benzene analog derivative of fluorenes, duplex fluorenes, three difluorenes, ethene or person's oxadiazole etc.; R be not meant one single, but form by fragment, spacer groups, end group X.Specifically, R can be by fluorenes and derivative thereof, thiophene, carbazole, vinylbenzene etc. is passed the good monomer of ability to the hole, Yi Ji oxadiazole, thiazole, benzothiazole, benzo pyridine, quinoline, hydroxyquinoline and derivative thereof etc. to one or more formations in the good monomer of electron transport ability.End group can be sterically hindered big group, and Bao Kuo oxadiazole, phenyl ring and the triphenylamine that the hole is had better transmission performance perhaps contain the benzene analog derivative of cyano group etc.
In the above-mentioned fragment of the present invention, can three difluorenes be chief component.It can be gone up by 9 of fluorenes in the middle of three difluorenes and obtain by the reaction with p-bromobenzaldehyde.
Benzene analog derivative that contains oxazole and trifluoromethyl in the above-mentioned monomer of the present invention etc. belongs to short of electricity subclass fragment (being the n type), and the benzene analog derivative and the fluorenes class that contain carbazole belong to electron rich class fragment (being the p type).Particularly, the desirable following fragment of unit Ar of the present invention a kind of: (I) 9,9-2 12 alkane-2,7-fluorenyl, (II) 9,9,9 ', 9 '-4 12 alkane-2,7 '-two fluorenyls, (III) 9,9,9 ', 9 '; 9 " 9 " alkane-2,7-6 12 "-three fluorenyls, (IV) 2,5-two fluorine-based-phenyl, (V) 1, two pairs of phenyl of 3--oxadiazole base.Its structural formula is respectively as follows:
9,9-2 12 alkane-2,7-fluorenyl 9,9,9 ', 9 '-4 12 alkane-2,7 '-two fluorenyls
9,9,9 ', 9 ', 9 ", 9 "-6 12 alkane-2,7 "-three fluorenyls
2,5-dicyano-phenyl 1, two pairs of phenyl of 3-,-oxadiazole bases
Among the present invention, unit R can adopt 9,9,9 " 9 "-4 12 alkane-9 ' 9 ' ,-two-1,4 benzene-2,7 "-two X-three fluorenyls, its structural formula is shown below:
9,9,9 ", 9 "-4 12 alkane-9 ' .9 ' ,-two-1,4 benzene-2,7 "-two X-three fluorenyls
X wherein can be one of following group: hydrogen base, trifluoromethyl, N-carbazyl, 3-4 tert.-butylbenzene-oxadiazole bases etc.
The side group that changes on main chain composition and the three difluorene fragments just obtains a series of different electroluminescent organic materials.
The preparation method of the electroluminescent organic material that the present invention proposes can be divided into 2 kinds of synthesis routes:
Route I, the synthetic earlier segmental monomer of three difluorenes that has different side groups passes through the Glich condensation reaction of Wittig or the phenmethyl bromine under sodium tert-butoxide catalysis then in trichloromethane, above-mentioned monomer polymerization is become superpolymer, pass through purifying again, can obtain target compound.
Route II is earlier by wittig reaction or the synthetic further macromolecular material of functionalization group that contains of Suzuki reaction, then by further reaction kinetic and purifying; Can obtain the subject polymer material.
The synthetic route apportion of two kinds of methods is as follows:
Embodiment
Below the present invention will be further described by some embodiment, but embodiment does not limit covering scope of the present invention:
Embodiment 1
' diiodo-three difluorenes and other benzene micromolecular derivatives with triphenyl phosphorus palladium (O) title complex/carbonic acid reaction, just can arrive target compound 1 to choose 2,7.Concrete synthetic method is:
1: in the 50mL two-neck bottle of magneton and nitrogen conduit is housed, add 2.6 grams 9,9-2 dodecane-2,7-dibromo fluorenes, anhydrous and oxygen-free is handled, and adds the tetrahydrofuran (THF) dissolving of 25mL anhydrous and oxygen-free with the dry syringe of crossing, and stirs.Adding dry ice-propanone bathes, after treating that temperature-stable arrives-78 ℃, in 30 minutes, slowly splash into the butyllithium 2.5mL of 1.6M, after-78 ℃ of following continuously stirring are reacted 1 hour, the syringe of crossing with drying once adds the trimethylchlorosilane of 0.6mL, remove acetone bath, continuously stirring reaction at room temperature 1 hour.Adding go out reaction back of a large amount of shrends and obtain organic phase dry the separation with petroleum ether extraction, revolve to steam and obtain being flaxen liquid, is that eluent carries out column chromatography and just can obtain colourless transparent liquid with sherwood oil, and generally productive rate can reach more than 90%.
2: single fluorenes product of protecting of above-mentioned 2.38 grams that obtain is dissolved in the tetrahydrofuran (THF) of 25mL; all the other operations are the same; after the triisopropyl boric acid ester that adds 1.3mL; continuously stirring reaction at room temperature obtained white emulsion liquid in 24 hours later on; after big water gaging quencher reaction; after separating drying with an amount of extracted with diethyl ether, revolve to steam and obtain thick liquid after desolventizing.With volume ratio is that 2: 1 sherwood oil and ethyl acetate mixed solution are that eluent carries out column chromatography and just can obtain a certain amount of white solid.
3: with 1.9 grams 2,7-dibromo fluorenone and the single protection of 7.1 grams boration fluorenes join the stirring magneton are housed, and in the three-necked bottle of 250mL spherical condensation tube and nitrogen conduit, the anhydrous and oxygen-free operation is carried out in sealing.Add an amount of triphenyl phosphorus palladium catalyst in glove box, lucifuge is handled, and adds the aqueous sodium carbonate of the 2M of the toluene of 150mL and 25mL with syringe, and in 90 ℃ oil bath, the continuously stirring reaction is 48 hours under the nitrogen protection.With after the dichloromethane extraction separation drying, obtain the white three difluorene solids of two protections for the eluent column chromatography with the sherwood oil after having reacted.
4: above-mentioned 2.88 grams, three difluorenes that obtain are dissolved in the tetracol phenixin of 50mL, under bathing, cryosel splashes into the iodine chloride hexane solution 3mL of 1.0M, stirring reaction is after half hour, and pouring reactant into a large amount of mass concentrations is that 5% Sulfothiorine is colourless to reactant.After the dichloromethane extraction washing drying, can obtain three difluorenes of two iodos with methanol wash.
5: three difluorene ketone of boration product that contains different side groups that will obtain according to the method described above and the two iodos that obtain carry out the Suzuki reaction just can obtain the middle fragment that contains Fluorenone.5: obtain lithium for single protection phenyl aldehyde according to step 1 with the 1-bromobenzaldehyde of 4-oxa-butyl, with a certain amount of 2 of tetrahydrofuran (THF) that anhydrous and oxygen-free handled that is dissolved in, the 7-dibromo fluorenone, stirring at room is reacted and is spent the night.Separate after the purification; with the tetrachloroethane is flux, under nitrogen protection, is catalyzer with trifluoromethanesulfonic acid; stirring at room reaction adds the shrend reaction of going out after 40 minutes, be that 8: 1 sherwood oil methylene dichloride mixed solution is that the eluent column chromatography just can obtain pure dialdehyde monomer with volume ratio.
6: will provide for oneself 2,7-two brooethyls-9,92 12 alkyl fluorenes and equimolar triethyl-phosphite reflux stirring reaction 3 hours in chloroform, steam desolventize after, use the toluene recrystallization, in 110 ℃ of baking ovens, be put in the moisture eliminator gained crystal stand-by after dry 1 hour.7: with the dialdehyde monomer and the step 6 gained phosphorus bromide of mol ratios such as strictness is solvent with the dimethyl formamide, in the there-necked flask that stirs magneton, dropping funnel and reflux condensing tube is housed, under high degree of agitation, the sodium ethylate sodium solution of a certain amount of new work is slowly splashed in the reaction solution, keep little boiling.Continued stirring reaction 1 hour after dropwising, obtain subject polymer with the methanol wash post precipitation.
Compound 1
Concrete synthesis step is:
Embodiment 2
Other are with embodiment 1, with 2,7 ' diiodo-three difluorenes are skeleton, by its with the 4-methyl bromobenzene trifluoride be composite catalyst at triphenyl phosphorus palladium (O) title complex/yellow soda ash, the Suzuki reaction under 90 ℃ of temperature, carried out with toluene solvant, prepare a series of fragment, productive rate about 78%.The phosphonium ylide that generates by the reaction of triethyl-phosphite and bromomethyl and the Wittig condensation reaction of aldehyde just can obtain target compound 2 then.
Compound 2
Embodiment 3
Other are with embodiment 1, with 2,7 ' diiodo-three difluorenes are skeleton, by its with 4 carbazole bromobenzenes be composite catalyst at triphenyl phosphorus palladium (O) title complex/yellow soda ash, the Suzuki reaction under 90 ℃ of temperature, carried out with toluene solvant, prepare a series of fragment, productive rate about 78%.The phosphonium ylide that generates by the reaction of triethyl-phosphite and bromomethyl and the Wittig condensation reaction of aldehyde just can obtain target compound 3 then.
Compound 3
Embodiment 4
Choose 2, the small molecules derivative of 7-dibromo fluorenes and other fluorenes is that catalyzer, temperature are carried out the Suzuki reaction under 90 ℃ at triphenyl phosphorus palladium (O) title complex/yellow soda ash, prepares a series of fragment, productive rate about 78%.Then 1 of connection three fluorenes fragments by containing dialdehyde-based and phosphitylation, the 4-dimethyl, 2, the Wittig reaction of 5-dicyanobenzenes just can obtain target oligomer 4.
Compound 4
Concrete synthesis step is:
Embodiment 5
Other are with embodiment 4, connection three fluorenes fragments by containing dialdehyde-based and 2,7 two brooethyls of phosphitylation then, and 9, the Wittig reaction of 9-12 fluorenes just can obtain target oligomer 5.
Compound 5
Embodiment 6
Other are with embodiment 4, and the connection three fluorenes fragments by containing dialdehyde-based and the unitary Wittig reaction of biphenyl of phosphitylation De Han oxadiazole just can obtain target oligomer 6 then.
Compound 6
Embodiment 7
Choose 4-trifluoromethylbenzene generation three difluorenes as the reaction parent, just can obtain monomer, the Glich reaction of above-mentioned monomer under sodium tert-butoxide catalysis just can homopolymerization be obtained target compound 7 by grignard reaction and follow-up NBS bromination reaction.
Compound 7
Concrete synthesis step is:
Embodiment 8
Other choose benzene generation three difluorenes as the reaction parent with embodiment 7, just can obtain monomer by grignard reaction and follow-up NBS bromination reaction, and the Glich reaction of above-mentioned monomer under sodium tert-butoxide catalysis just can homopolymerization be obtained target compound 8.
Compound 8
Embodiment 9
Other are with embodiment 7, three difluorenes of choosing the replacement of 4-carbazole are as the reaction parent, just can obtain monomer by grignard reaction and follow-up NBS bromination reaction, the Glich reaction homopolymerization of above-mentioned monomer under sodium tert-butoxide catalysis just can be obtained target compound 9.
Compound 9
For further clear and definite patent of the present invention proposes the material covering scope, below some other structure of such material can simply be represented:
Compound 10
Compound 11
Compound 12
Compound 13
Compound 14
Compound 15
Compound 16
Compound 17
Synthetic method can reference example 1 described method be carried out.
Claims (10)
1, a kind of segmental electroluminescent organic material of difluorene that contains, it is characterized in that j with the difluorene fragment as chief component, on the linear polymeric main chain that connects continuously, introduce non-rectilinear conjugation fragment, the polymkeric substance that the conjugated structure part of formation main chain is interrupted, its structural formula is:
Wherein, Ar is a kind of of following unit: the benzene analog derivative of fluorenes, duplex fluorenes, three difluorenes, ethene or person's oxadiazole; R is made up of fragment, spacer groups, end group X.
2, electroluminescent organic material according to claim 1, it is characterized in that described unit R by fluorenes and derivative thereof, thiophene, carbazole, to vinylbenzene, Yi is Ji one or more formations in oxadiazole, thiazole, benzothiazole, benzo pyridine, quinoline, hydroxyquinoline and the derivative thereof.
3, electroluminescent organic material according to claim 1 is characterized in that described unit R is by obtaining by reaction and subsequent reactions with p-bromobenzaldehyde on 9 of the middle fluorenes of three difluorenes.
4, electroluminescent organic material according to claim 1 is characterized in that described end group is made up of Han oxazole, phenyl ring and carbazole or the benzene analog derivative group that contains trifluoromethyl.
5, electroluminescent organic material according to claim 1 is characterized in that also containing the long chain alkane that improves material dissolves on described comonomer Ar and the R.
6, a kind of preparation method of electroluminescent organic material according to claim 1, it is characterized in that on the conjugation polymerisable monomer, connecting the side group that contains the two blocks of different lengths p type, n type or p-n based on the difluorene fragment, obtain comonomer with group end capping with specific function, pass through polyreaction again, just obtain having the electroluminescent organic material of difluorene fragment structure.
7, preparation method according to claim 6 is characterized in that synthetic route is the one of the following kind:
Route I, the synthetic earlier segmental monomer of three difluorenes that has different side groups passes through the Glich condensation reaction of Wittig or the phenmethyl bromine under sodium tert-butoxide catalysis then in trichloromethane, above-mentioned monomer polymerization is become superpolymer, pass through purifying again, can obtain target compound;
Route II by wittig reaction or the synthetic further macromolecular material of functionalization group that contains of Suzuki reaction, by further reaction kinetic and purifying, can obtain the subject polymer material earlier then.
8, compound as claimed in claim 1 is as electroluminescent organic material, the application in the preparation organic electroluminescence device.
9, compound as claimed in claim 1 is as electroluminescent organic material, the application in preparation photovoltaic cell, message memory, thin film transistor.
10, electroluminescent organic material according to claim 1 is characterized in that this material is a kind of of following compound:
(1) compound 1, and its structural formula is:
(2) compound 2, and its structural formula is:
(3) compound 3, and its structural formula is:
Kind:
(1) compound 1, and its structural formula is:
(2) compound 2, and its structural formula is:
(3) compound 3, and its structural formula is:
(4) compound 4, and its structural formula is:
(5) compound 5, and its structural formula is:
(6) compound 6, and its structural formula is:
(7) compound 7, and its structural formula is:
(8) compound 8, and its structural formula is:
(9) compound 9, and its structural formula is:
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302049C (en) * | 2005-05-26 | 2007-02-28 | 复旦大学 | Hyperbranched high-molecular electroluminescent materials |
| CN104326980A (en) * | 2014-09-16 | 2015-02-04 | 武汉大学 | 9,9'- connected host material based on 4,4'-difluorene structure and application thereof |
-
2004
- 2004-09-01 CN CN 200410054196 patent/CN1613961A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302049C (en) * | 2005-05-26 | 2007-02-28 | 复旦大学 | Hyperbranched high-molecular electroluminescent materials |
| CN104326980A (en) * | 2014-09-16 | 2015-02-04 | 武汉大学 | 9,9'- connected host material based on 4,4'-difluorene structure and application thereof |
| CN104326980B (en) * | 2014-09-16 | 2016-03-30 | 武汉大学 | Based on 4,4 '-Lian two fluorene structured 9, the material of main part that 9 '-position connects and application thereof |
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