CN105541648B - A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma - Google Patents
A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma Download PDFInfo
- Publication number
- CN105541648B CN105541648B CN201510918478.7A CN201510918478A CN105541648B CN 105541648 B CN105541648 B CN 105541648B CN 201510918478 A CN201510918478 A CN 201510918478A CN 105541648 B CN105541648 B CN 105541648B
- Authority
- CN
- China
- Prior art keywords
- disperse dyes
- reaction
- supercritical
- chloroanthraquinones
- presoma
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention belongs to technical field of dye, and in particular to a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, the present invention is with 1 chloroanthraquinone and 2, and 5 diaminotoluene sulphates are raw material, K2CO3For acid binding agent, CuI is catalysts, is heated to reflux 6~14h under nitrogen protective condition in reaction medium, and reaction temperature is 80~140 DEG C, and reaction handles after after terminating and obtains the solid powder of dye precursor.Catalyst amount of this method in building-up process is few, and reaction condition is gentle, and yield is higher, and cost is relatively low, and obtained presoma application is strong, except being suitable for supercritical CO2With the synthesis of anthraquinone type reactive disperse dyes, the synthesis of conventional water-bath dyeing reactive disperse dyes is also suitable for.
Description
Technical field
The invention belongs to technical field of dye, and in particular to a kind of supercritical CO2With anthraquinone type reactive disperse dyes forerunner
The synthetic method of body.
Background technology
The appearance and development of reactive disperse dyes can trace back to the sixties in last century five, but because it is by use condition
Having a great influence, be difficult to accomplish to contaminate on uniformly when being dyed to polyester/cotton blended fabric, application is poor, thus in evolution
Encounter bottleneck (bibliography:The significant progress of reactive dye and fundamental research achievement [J] dyestuffs and dye in 50 years
Color, 2008,2:1-9,44.).And utilize supercritical CO2Fluid staining technique can realize that reactive disperse dyes is knitted to polyester cotton blending
The dyeing of thing and natural fiber, new vitality (bibliography is filled with for its development:One-bath dyeing of
polyester/cotton blends with reactive disperse dyes in supercritical carbon
Dioxide [J] .Textile Research Journal, 2004,74 (11):989-994;Technical Progress in Modem Reactive Dyestuffs
[J] prints and dyes, and 2004,2:37-42;Dyeing [J] of reactive disperse dyes to natural fiber is external in supercritical carbon dioxide
Textile technology:Weaving knitted dress chemical fibre dyeing and finishing, 2003,9:22-27.).
In terms of reactive disperse dyes synthesis, the report on anthraquinone ring is less, and method is also more single, usually exists
Active group is introduced on the basis of existing disperse dyes, it is of less types.
Reacted using Ullmann and carry out the synthesis of dyestuff or dyestuff intermediate before this it has been reported that but the dyestuff master that is related to
If reducing dye, it can be common that amino anthraquinones carries out condensation reaction with chloroanthraquinone under catalyst action, so as in anthraquinone core
Upper introducing imino group generation anthraquinone group with imine moiety, or by generating carbon-carbon bond, prepare some condensed ring reducing dyes;
Ullmann reaction also have important application in acid dyes, usually using bromamine acid as raw material, in alkaline aqueous solution with substitution
Arylamine reacts (bibliography:Application [J] the dye industries of ullmann reaction in Dyestuff synthesis, 1984,3:1-7.),
And it does not have been reported that in terms of water-insoluble active disperse dyes.
Thus, how to make the synthetic method diversification of reactive disperse dyes, solution reactive disperse dyes species is few, application
The problems such as not strong, turn into the key of breakthrough bottleneck, and can be supercritical CO2The non-aqueous dyeing of natural fiber provides wider in fluid
Wealthy development prospect.
The content of the invention
In order to solve the above technical problems, the present invention by Ullmann reactive applications in supercritical CO2With anthraquinone type active dispersal
The synthesis of dye precursor, catalyst amount is few in course of reaction, reaction condition is gentle, and yield is higher, and cost is relatively low, and obtains
Presoma application it is strong, except being suitable for supercritical CO2With the synthesis of anthraquinone type reactive disperse dyes, conventional water-bath is also suitable for
The synthesis of dyeing reactive disperse dyes.
A kind of supercritical CO proposed by the present invention2With the synthetic method of anthraquinone type reactive disperse dyes presoma, including with
Lower step:
(1) with 1- chloroanthraquinones and 2,5- diaminotoluene sulphate for raw material, K2CO3For acid binding agent, CuI is catalytic reaction
Agent, 6~14h is heated to reflux under nitrogen protective condition in reaction medium, reaction temperature is 80~140 DEG C, wherein 2,5- diaminos
The mol ratio ratio of base toluene sulfate and 1- chloroanthraquinones is 1~2, acid binding agent K2CO3Mol ratio ratio with 1- chloroanthraquinones is
The mol ratio ratio of 1.5~4, catalyst CuI and 1- chloroanthraquinones is 0.056~0.333;
(2) after reaction terminates, the reaction solution of step (1) is cooled to 35 DEG C, it is 2 to add volume ratio:1 water and dichloro
Methane, using filter aid, pressure filtration, to remove the black flocculent deposit in mixed liquor, then extracted, washed, being rotated, very
Sky is dried, so as to obtain the solid powder of dye precursor.
Further, the reaction medium in the step (1) is one kind in DMF, dimethyl sulfoxide (DMSO)
Or the two arbitrary proportion mixture.
Further, the dosage of the reaction medium is 6mL/mmol 1- chloroanthraquinones.
Further, the filter aid in the step (2) is neutral silica gel, the mesh of specification 200~300.
Chemical equation of the present invention is as follows:
Oxidative addition first occurs with 1- chloroanthraquinones for catalyst CuI in the present invention, and generation carries the intermediate of [Cu], with
Nucleopilic reagent 2,5- diaminotoluene sulphates are (in acid binding agent K afterwards2CO3Under the conditions of existing, nucleophilicity increase) sent out with intermediate
Raw nucleophilic substitution simultaneously sloughs [Cu] (bibliography:Catalytic C-C,C-N, and C-O Ullmann-Type
Coupling Reactions[J].Angewandte Chemie International Edition,2009,48(38):
6954-6971.), so as to obtain dye precursor, operating procedure is simple, easily controllable.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, it is below presently preferred embodiments of the present invention, and coordinate accompanying drawing, describes in detail such as
Afterwards.
Brief description of the drawings
Fig. 1 is LC-MS spectrogram in the embodiment of the present invention 1;
Fig. 2 is hydrogen nuclear magnetic resonance spectrogram in the embodiment of the present invention 1;
Fig. 3 is FTIR spectrum figure in the embodiment of the present invention 1.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
Supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, comprise the following steps:
(1) in 100mL three-necked flasks (thermometer, condenser pipe and dropping funel is housed, protected above condenser pipe with nitrogen
Device) in add 0.005mol 2,5- diaminotoluene sulphates and 0.0075mol K2CO3, nitrogen is passed through, and add rapidly
0.556mmol CuI.0.005mol 1- chloroanthraquinones are weighed, add 30mL N, N- dimethylformamides are dissolved (if there is trace solid
Insoluble, it is extremely in yellow transparent shape that can use supersonic oscillations), and be quickly adding into dropping funel, open to stir and simultaneously slowly drip
Add and (drip off within about 10 minutes), start timing when being warming up to 100 DEG C, flow back 12 hours.
(2) after reaction terminates, reaction solution is naturally cooled to 35 DEG C, adds water and dichloromethane (volume ratio 2:1), with
Neutral silica gel is filter aid, pressure filtration, to remove the black flocculent deposit in mixed liquor, then extracted, washed, rotated,
The operation such as vacuum drying, so as to obtain the solid powder of dye precursor, yield 44.34%.
The solid powder of dye precursor to being obtained in embodiment purifies, and carries out the structure carry out table of product
Sign, its method include:
1. with column layer chromatography silicone rubber (200~300 mesh) for stationary phase, dichloromethane and n-hexane (volume ratio 1:1) it is
Mobile phase, dry column-packing, pressurized operation;Tlc silica gel plate G-254, solvent are acetone and n-hexane (volume ratio 1:
2)。
2. utilize LC-MS (positive ion mode, ESI sources), proton nmr spectra (400MHz, DMSO-d6) and Fu in
The measuring technologies such as leaf infrared spectrum carry out structural characterization to the product obtained in the present embodiment, and its result is as shown in Figures 1 to 3.
Shown by Fig. 1, LC-MS (positive ion mode, ESI sources) can detect molecular ion peak [M+H]+=
329.1286 it is consistent with the molecular weight of dye precursor.
In Fig. 2:
1H NMR(400MHz,DMSO-d6):δ the 11.05,10.85 (- NH of s, 1H, 8-NH, 8 '), 8.24 (t, J=6.5Hz,
1H, Ar-1H, Ar-1 ' H), 8.15 (d, J=7.3Hz, 1H, Ar-4H, Ar-4 ' H), 7.99-7.81 (m, 2H, Ar-2H, Ar-2 '
H, Ar-3H, Ar-3 ' H), 7.56 (dd, J=10.6,5.0Hz, 1H, Ar-6H, Ar-6 ' H), 7.48 (d, J=7.0Hz, 1H, Ar-
5 H, Ar-5 ' H), 6.92 (dd, J=17.1,8.4Hz, 2H, Ar-7H, Ar-7 ' H, Ar-11H, Ar-9 ' H), 6.70 (d, J=
8.2Hz, 1H,Ar-9H,Ar-10’H),6.60-6.45(m,1H,Ar-10H,Ar-11’H),5.16,4.98(s,2H,12’-
NH2,12-N H2), 2.08 (d, J=11.9Hz, 3H, 13-CH3,13’-CH3).It is indicated above gained dye precursor and its same
In isomer structure, respectively1H ownership is consistent with theoretical construct.
Fig. 3 is shown, in 3465.43cm-1、3373.64cm-1And 1624.42cm-1Place is respectively present NH2Antisymmetry stretch
Vibration peak, symmetrical stretching vibration peak and flexural vibrations peak, in 3242.83cm-1Secondary amine N-H stretching vibration peak be present in place,
2920.94cm-1、2856.30cm-1And 1368.50cm-1Place is respectively present CH3Antisymmetric stretching vibration peak, symmetrical flexible shake
Dynamic peak and symmetric deformation vibration peak, in 1657.66cm-1C=O stretching vibration peak be present in place.It is indicated above on 1- chloroanthraquinones
Chlorine atom is substituted by the amino in 2,5- diaminotoluene sulphates.
The testing result of Fig. 1~3 shows that the structure of gained dye precursor is consistent with desired design structure.
Embodiment 2
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.Reaction medium wherein in step (1) is 30mL dimethyl sulfoxide (DMSO)s;Precursor dye in step (2)
The yield of body is 37.03%.
Embodiment 3
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.2,5- diaminotoluene sulphates and K wherein in step (1)2CO3Dosage be respectively
0.0075mol and 0.015mol, reaction temperature are 110 DEG C, reaction time 6h;The yield of dye precursor is in step (2)
38.79%.
Embodiment 4
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 3.Reaction time wherein in step (1) is 14h;The yield of dye precursor is in step (2)
67.84%.
Embodiment 5
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.2,5- diaminotoluene sulphates, K wherein in step (1)2CO3Dosage with CuI is respectively
0.0075mol, 0.020mol and 1.667mmol, reaction temperature are 80 DEG C, reaction time 10h;Dye precursor in step (2)
Yield be 33.80%.
Embodiment 6
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.2,5- diaminotoluene sulphates and K wherein in step (1)2CO3Dosage be respectively
0.0075mol and 0.015mol, reaction temperature are 140 DEG C;The yield of dye precursor is 62.67% in step (2).
Embodiment 7
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.2,5- diaminotoluene sulphates and K wherein in step (1)2CO3Dosage be respectively
0.010mol and 0.0125mol;The yield of dye precursor is 62.99% in step (2).
Embodiment 8
The present embodiment provides a kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, this method
Other steps with embodiment 1.2,5- diaminotoluene sulphates, K wherein in step (1)2CO3Dosage with CuI is respectively
0.0075mol, 0.015mol and 0.278mmol, reaction temperature are 100 DEG C, reaction time 8h;Precursor dye in step (2)
The yield of body is 68.03%.
Shown by embodiments of the invention 1~8:Each reaction condition has an impact to dye precursor yield, wherein tiing up acid
The effect of agent dosage is most obvious, increases K2CO3Dosage can increase the nucleophilicity of 2,5- diaminotoluene sulphates, be advantageous to anti-
The progress answered, the yield of dye precursor significantly improve;When the mol ratio ratio of catalyst CuI and 1- chloroanthraquinones is 0.056
When, other reaction conditions are controlled, can making yield, catalyst amount is few, and cost is relatively low more than 65%;When reaction temperature is 110
DEG C, when return time is 8h, the dosage of each reactant is controlled, yield can be made to can reach more than 85%, reaction condition is gentle, yield
Height, application are strong.Meanwhile testing result also demonstrate that the structure of gained dye precursor is consistent with expected structure.
In summary, the present invention by Ullmann reactive applications in supercritical CO2With anthraquinone type reactive disperse dyes presoma
Synthesis in, provide a kind of new way, and catalyst amount during the course of the reaction for the synthesis of anthraquinone type reactive disperse dyes
Less, reaction condition is gentle, and yield is higher, and cost is relatively low, and application is strong.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (1)
- A kind of 1. supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma, it is characterised in that including following step Suddenly:(1) with 1- chloroanthraquinones and 2,5- diaminotoluene sulphate for raw material, K2CO3For acid binding agent, CuI is catalysts, nitrogen It is heated to reflux under the conditions of gas shielded in reaction medium 8 hours, reaction temperature is 100 DEG C, wherein 2,5- diaminotoluene sulphuric acids The mol ratio ratio of salt and 1- chloroanthraquinones is 1.5, acid binding agent K2CO3Be 3 with the mol ratio ratio of 1- chloroanthraquinones, catalyst CuI with The mol ratio ratio of 1- chloroanthraquinones is 0.056;Reaction medium in the step (1) is N,N-dimethylformamide;It is described anti- The dosage for answering medium is 6mL/mmol 1- chloroanthraquinones;(2) after reaction terminates, the reaction solution of step (1) is cooled to 35 DEG C, it is 2 to add volume ratio:1 water and dichloromethane, Using filter aid, pressure filtration, to remove the black flocculent deposit in mixed liquor, then extracted, washed, being rotated, vacuum is done It is dry, so as to obtain the solid powder of dye precursor;Filter aid is neutral silica gel, the mesh of specification 200~300.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510918478.7A CN105541648B (en) | 2015-12-11 | 2015-12-11 | A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510918478.7A CN105541648B (en) | 2015-12-11 | 2015-12-11 | A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105541648A CN105541648A (en) | 2016-05-04 |
CN105541648B true CN105541648B (en) | 2018-03-06 |
Family
ID=55821266
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510918478.7A Active CN105541648B (en) | 2015-12-11 | 2015-12-11 | A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105541648B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107057401B (en) * | 2017-04-21 | 2019-03-15 | 苏州大学 | Dichloro s-triazine type reactive disperse dyes based on anthraquinone and preparation method thereof |
WO2019223016A1 (en) * | 2018-05-25 | 2019-11-28 | 苏州大学张家港工业技术研究院 | Blue anthraquinone active disperse dye and preparation method therefor |
WO2019223015A1 (en) * | 2018-05-25 | 2019-11-28 | 苏州大学张家港工业技术研究院 | Precursor of blue anthraquinone active disperse dye and preparation method therefor |
CN108586274B (en) * | 2018-05-25 | 2020-04-03 | 苏州大学 | Precursor of blue anthraquinone reactive disperse dye and preparation method thereof |
CN111424444A (en) * | 2020-05-21 | 2020-07-17 | 浙江爱利斯染整有限公司 | Composition for supercritical dyeing and application thereof |
CN111635647A (en) * | 2020-06-08 | 2020-09-08 | 浙江越新印染有限公司 | Red dyeing composition and application thereof in supercritical carbon dioxide anhydrous dyeing |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR203095A1 (en) * | 1973-01-08 | 1975-08-14 | Bayer Ag | 1-PHENYLAMINE-NITROANTRAQUINONES COLORS FOR APPLICATION FOR THE HOLDING AND PRINTING OF SYNTHETIC FIBERS AND PROCEDURE TO PREPARE THEM |
JPS5137921A (en) * | 1974-09-27 | 1976-03-30 | Nippon Kayaku Kk | ANSURAKINONKEIKAGOBUTSUNO SEIZOHO |
WO1989003819A1 (en) * | 1987-10-20 | 1989-05-05 | Otsuka Pharmaceutical Co., Ltd. | Phenylcarboxylic acid derivatives |
JP2001187844A (en) * | 1999-12-29 | 2001-07-10 | Ciba Specialty Chem Holding Inc | New pigment coloring agent for kneading-coloring of synthetic material |
CN103509370B (en) * | 2012-06-25 | 2015-11-18 | 浙江舜龙化工有限公司 | A kind of Active green dye |
CN104341794A (en) * | 2013-08-09 | 2015-02-11 | 中国中化股份有限公司 | Reactive brilliant blue dye and preparation method thereof |
CN104312193B (en) * | 2013-10-14 | 2016-06-15 | 大连理工大学 | The method of bromamine acid aryl amination elbs reaction oxyketone dye or color base |
CN104327532B (en) * | 2013-10-14 | 2016-08-24 | 大连理工大学 | The preparation method that bromine ammonia is blue |
US9512315B2 (en) * | 2013-10-31 | 2016-12-06 | Dkc Corporation | Quenching dye for labeling biomolecules and method for preparing the same |
-
2015
- 2015-12-11 CN CN201510918478.7A patent/CN105541648B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN105541648A (en) | 2016-05-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105541648B (en) | A kind of supercritical CO2With the synthetic method of anthraquinone type reactive disperse dyes presoma | |
Xiao et al. | Eco-friendly approaches for dyeing multiple type of fabrics with cationic reactive dyes | |
Zhang et al. | Ecofriendly synthesis and application of special disperse reactive dyes in waterless coloration of wool with supercritical carbon dioxide | |
CN108504136B (en) | A kind of blue anthraquinone reactive disperse dyes and preparation method thereof | |
CN103936660B (en) | The preparation method and application of N-methyl-2-phenyl-3, the 4-soccerballene base tetramethyleneimine of a kind of micron of acicular structure | |
Yan et al. | Development of a special SCFX-AnB3L dye and its application in ecological dyeing of silk with supercritical carbon dioxide | |
CN106436278B (en) | A kind of ammoniation modified method of ramee and its application process in liquefied ammonia solvent dyeing | |
CN103952007A (en) | Crosslinking modification method of azo-disperse dye | |
CN103319379A (en) | Process for synthesizing anthraquinone compound | |
CN104231659A (en) | Red thiazole heterocyclic disperse dye compound containing benzoate group and preparation and application thereof | |
CN105440726A (en) | Supercritical CO2 dyeing special-purpose azo-type active disperse dye | |
CN102219747A (en) | Synthesis method of aromatic diamine containing double imidazole rings | |
CN103435492B (en) | Method for synthesizing 1-nitroanthraquinone by nitration of nitrogen pentoxide | |
CN102731318A (en) | Method for preparing 3,5-dimethyl aniline | |
CN101709051A (en) | Preparation method of 2-amino-3-chloro-5-(trifluoromethyl) pyridine | |
CN103769211A (en) | Preparation method of organic-inorganic hybrid material ruthenium-loaded catalyst for synthesizing L-alaninol | |
CN113666869B (en) | Naphthoimide dye containing amino group in supercritical CO 2 In (a) synthesis and dyeing method | |
CN106957233B (en) | A method of 3,3 '--4,4 '-diamino-dicyclohexyl methanes of dimethyl of synthesis | |
CN110054582A (en) | A kind of preparation method of 3- amino-N- ethyl carbazole | |
CN105484020A (en) | Dyeing and finishing process for knitted fabric | |
EP3434735A1 (en) | Reactive black dye composition and method for dying fibers using the same | |
CN205974922U (en) | Weaving machine with floricome adjustment function | |
CN102485719A (en) | Preparation method of Imatinib amine | |
CN108586274B (en) | Precursor of blue anthraquinone reactive disperse dye and preparation method thereof | |
CN109206943B (en) | High-color-fastness blue disperse dye mixture and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |