CN109608903A - A kind of chemically-reactive dyes and preparation method thereof replaced containing benzsulfamide and its derivative - Google Patents
A kind of chemically-reactive dyes and preparation method thereof replaced containing benzsulfamide and its derivative Download PDFInfo
- Publication number
- CN109608903A CN109608903A CN201811327162.0A CN201811327162A CN109608903A CN 109608903 A CN109608903 A CN 109608903A CN 201811327162 A CN201811327162 A CN 201811327162A CN 109608903 A CN109608903 A CN 109608903A
- Authority
- CN
- China
- Prior art keywords
- reaction
- acid
- benzsulfamide
- condensation product
- triazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/51—Monoazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/507—Azo dyes
- C09B62/513—Disazo or polyazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/523—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl amido or hydroxyalkyl amino sulfonyl group, a quaternised or non-quaternised amino alkyl sulfonyl amido group, or a substituted alkyl amino sulfonyl group, or a halogen alkyl sulfonyl amido or halogen alkyl amino sulfonyl group or a vinyl sulfonylamido or a substituted vinyl sulfonamido group
- C09B62/527—Azo dyes
- C09B62/53—Monoazo dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
The present invention relates to chemically-reactive dyes fields, and in particular to a kind of chemically-reactive dyes and preparation method thereof replaced containing benzsulfamide and its derivative.A kind of chemically-reactive dyes replaced containing benzsulfamide and its derivative, the structure with general formula I:
Description
Technical field
The present invention relates to chemically-reactive dyes fields, and in particular to a kind of reactivity replaced containing benzsulfamide and its derivative
Dyestuff and preparation method thereof.
Background technique
Reactive dye can become cellulose fibre printing and dyeing with fiber covalent bond, wet colour fastness with higher
With dyestuff primary categories.Azo chromogen is since raw material is cheap and easy to get, synthesis is simple, bright in color light, the advantages that chromatography is complete,
About 80% dyestuff uses azo colour base, but because azo bond is easy by ultraviolet light, oxygen etc. in the environment
Influence, it is prone to redox reaction and cause its with lower fastness to light (Dyes and Pigments, 1988,9
(3):233-241；Surface and Coatings Technology,2014,253:185-193；Dyes and
Pigments,2003,59(3):269-275).The approach for improving dyestuff light fastness stability mainly has following two: first is that using
The higher chromogen of light fastness, such as: anthraquinone, phthalocyanine or other class chromogens；Second is that introducing ultraviolet light in dye molecule
Group is absorbed, or ultraviolet absorbing agent is added in dyeing assistant to reduce destruction of the ultraviolet light to dyestuff, is mentioned with reaching
Purpose (the Coloration Technology, 2016,132:107-113 of high light fastness stability；Advances in the
Dyeing and Finishing of Technical Textiles, 2013,138:47-77；Colourage,2010,7:
33-39；CN 201310664137).And the usual tone of the classes chromogen such as anthraquinone, phthalocyanine is relatively simple, cannot have both azo hair
The advantages of whole chromatogram that colour solid has (dyestuff and dyeing, 2007,3:10-13).And ultraviolet-absorbing group is introduced into dye
The solubility and molar absorption coefficient (US 5200511 of dyestuff would generally be reduced in material molecular structure again；EP 1860162).Benefit
It is introduced into dye structure with hindered amines molecule, can be improved half grade of light fastness to level-one (CN 101899225；CN
101914300), benzophenone molecule is introduced into reactive dye, dyestuff light fastness can be improved 1~2 grade of (Dyes and
Pigments,1988,9(3):233-241)。
Derivative of the sulfuryl amine group as sulfonic acid group, can retain sulfonic acid group helps color performance, can also eliminate sulphur
The strong water-soluble of acid groups, to improve adsorption capacity of the reactive dye on fiber.Once someone was using sulfoamido as connection
Base is introduced into chemically-reactive dyes molecule (Dyes and Pigments.1999,43 (5): 167-172；FR 1352275A；US
3029123A), they mainly utilize sulfoamido connection active group and chromogen, to substitute the arylamine with carcinogenicity.Also have
Sulfuryl amine group is introduced into disperse dyes by people, to improve dyestuff to hydrophobic fibres such as polypropylene, polylactic acid and terylene
Adsorption capacity (Chinese Chemical Letters.2007,18 (9): 1145-1147)；And more about by sulfoamido
The report being introduced into dye molecule then concentrates on the research for being introduced into para-ester or meta position ester, by change para-ester or
The molecular structure of meta position ester improves dyestuff to the substantivity of fiber, to achieve the purpose that the degree of exhaustion and degree of fixation that improve dyestuff
(Coloration Technology,2006,122(4):217-226；Dyes and Pigments,2000,47(1):151-
167).Benzsulfamide is introduced into halogenated s-triazine ring, Ke Yili as the raw material containing sulfonamide structure most easily obtained
Cloud density on triazine ring is reduced with the strong electron attraction of sulfoamido, improves the reactivity of carbon-halogen bond, while also reaching
To the purpose for improving dyestuff light fastness.It is introduced into benzsulfamide group as the blocking groups of triazine ring in chemically-reactive dyes,
And a kind of chemically-reactive dyes with higher fastness to light is made there is not been reported.
Summary of the invention
A kind of chemically-reactive dyes replaced containing benzsulfamide and its derivative, the structure with general formula I:
In Formulas I,
R is selected from-Cl or-F；
R1Selected from-H, methyl, itrile group, sulfonic group, trifluoromethyl, methoxyl group, hydroxyl, carboxyl, nitro ,-Cl ,-Br ,-F；
R2Selected from-H, methyl, aminomethyl, trifluoromethyl, methoxyl group, hydroxyl, nitro, cyano ,-Cl ,-Br ,-F；
R3Selected from-H ,-OCH3,-CH3,-CH2CH3；
L is selected from-SO2,-CO- ,-NHCO- ,-SO2NH- ,-CH2CH2SO2,-O-CH2CH2SO2,-NHCH2CH2SO2,-
NHCONHCH2CH2SO2,-SO2CH2CH2SO2Or-NXSO2Group, wherein X is selected from C1~C4Carbon atom is substituted or unsubstituted
Alkoxy, phenyl, substituent group can be-SO3H ,-COOH ,-OH, halogen, cyano, amino-sulfonyl (H2NSO2), ethoxy
Base, cyanogen methyl group；
M is selected from-Cl, or-OSO3R4, wherein R4Selected from-H ,-Na or-K；
A is selected from substituent group shown in II-a or II-b；
In Formula II-a,
The integer that n is 0~2；
Residue representated by Formula II-b is one of following radicals:
H acid residue, structural formula are as follows:
J acid residue, structural formula are as follows:
γ acid residue, structural formula are as follows:
K acid residue, structural formula are as follows:
Chicago acid residue, structural formula are as follows:
Further, R1、R2、R3Position with L is any position of place phenyl ring.
It is further preferred that R2Position be with sulfoamido in para postion, R1Position be and R2In face position or
Position；R3Position be position with-N=N- in ortho position or meta position；The position of L is with-N=N- in contraposition or meta position position.
It is yet another object of the invention to provide a kind of preparations of chemically-reactive dyes replaced containing benzsulfamide and its derivative
Method, the preparation method of the dyestuff include following two classes methods:
Method one: halogenated s-triazine and benzsulfamide, amino naphthol sulfonic acid class substrate carry out condensation reaction, must be condensed production
Object；Beta-sulfuric ester ethyl sulfonyl aniline passes through diazo-reaction, obtains diazonium salt solution；The condensation product and the diazonium salt is molten
Liquid passes through coupling reaction, and 0~5 DEG C of reaction temperature, pH7~8 obtain dyestuff described in claim 1；
Method two: beta-sulfuric ester ethyl sulfonyl aniline passes through diazo-reaction, obtains diazonium salt solution；H acid solution adds to dropwise
In above-mentioned diazonium salt solution, molar ratio 1:1, reaction temperature is 0~5 DEG C, reaction time 4h, pH < 3, anti-by being once coupled
It answers, obtains a coupling solution；Halogenated s-triazine and benzsulfamide, arylamine class substrate carry out condensation reaction, obtain condensation product；It will be above-mentioned
Condensation product passes through diazo-reaction, obtains condensation product diazo liquid；Above-mentioned condensation product diazo liquid is added dropwise to above-mentioned primary idol
It closes in liquid, 0~5 DEG C of reaction temperature, pH7~8 obtain the dyestuff through coupling reaction.
Preferably, the condensation product is the preparation method is as follows: halogenated s-triazine and benzsulfamide or derivatives thereof are carried out
First time condensation reaction；Second is carried out with amino naphthol sulfonic acid class substrate or arylamine substrate again to be condensed, and obtains condensation product；
It is 1:1~1:3 that the first time, which is condensed halogenated s-triazine and the molar ratio of benzene sulfonyl amine salt, and reaction temperature is 0~5
DEG C, time for adding 40min~50min, reaction time 120min obtain first time condensation product, first time condensation product and ammonia
Base naphtholsulfonic acid class substrate or arylamine substrate molar ratio are 1:0.9~1, and 15~30 DEG C of reaction temperature, pH6~7, thin-layer chromatography is examined
Reaction end is surveyed, condensation product is obtained.
Further, the beta-sulfuric ester ethyl sulfonyl aniline is the general designation to formula:
Further, beta-sulfuric ester ethyl sulfonyl aniline is p- (ethyl-beta-hydroxyethyl sulfone sulfate) aniline, 2- methyl, 4-
(ethyl-beta-hydroxyethyl sulfone sulfate) aniline, para-ester, meta position ester, 3- (β-chloroethyl sulfone) aniline, 4- sulfuric ester ethyl sulfonyl benzene
Amine, 3- methoxyl group, 4- sulfuric ester ethyl sulfonyl aniline, one of 4- methoxyl group -3- (beta-sulfuric ester ethyl sulfonyl) aniline.
Further, the halogenated s-triazine is dissolved in acetone, and the concentration of the acetone soln of halogenated s-triazine is 0.5mol/L.
Preferably, after stating halogenated s-triazine and benzsulfamide progress first time condensation reaction, unreacted benzene sulfonamide is precipitated
And its derivative, clear filtrate is obtained, clear filtrate carries out second with amino naphthol sulfonic acid class substrate or arylamine substrate again and is condensed,
The mode of the precipitation adds acid for adjusting pH < 3.
Further, pH value of solution < 3 is adjusted, unreacted benzsulfamide or substituted benzene sulfonic acid amide is precipitated, cooling makes to be precipitated
It is more thorough.
Further, the benzsulfamide and its derivative are first added in sodium hydroxide solution, the benzsulfamide and hydrogen
The molar ratio of sodium oxide molybdena is 1:1, concentration of sodium hydroxide solution 0.02g/L.
Preferably, the halogenated s-triazine is Cyanuric Chloride and cyanuric fluoride.
Preferably, the amino naphthol sulfonic acid class substrate be H acid, J acid, r acid, K acid, chicago acid.
Preferably, the arylamine class substrate be 2,4- diamino benzene sulfonic acid, 1,2- diaminobenzene, 1,3- diaminobenzene, 1,
4- diaminobenzene, 2,4- diaminostilbene, 5- disulfonic acid base benzene.
Preferably, the diazo-reaction is primary aromatic amine and sodium nitrite at 0~5 DEG C, and life is reacted under strong acid media
At the reaction of diazonium salt, primary aromatic amine and nitrous acid molar ratio are 1:1.03~1.1, and the strong acid media is that mass fraction is
37% concentrated hydrochloric acid, concentrated hydrochloric acid mole are 3 times of primary aromatic amine, and the primary aromatic amine is beta-sulfuric ester ethyl sulfonyl aniline
Or condensation product, the condensation product be after halogenated s-triazine and benzsulfamide are condensed for the first time again with amino naphthol sulfonic acid class bottom
Object condensation reaction obtains,
Whether the diazo-reaction Congored test paper and starch-KI test paper detection hydrochloric acid and sodium nitrite are enough, use
Ai Lixi reagent detects reaction end, at the end of diazotising, sulfamic acid is added and destroys extra sodium nitrite, obtains diazo liquid.
Preferably, the coupling reaction is reacted to terminal with the circle method monitoring of infiltration.
The invention has the benefit that the chemically-reactive dyes and its system provided by the invention containing benzsulfamide and its derivative
Preparation Method, in such chemically-reactive dyes molecule obtained, benzsulfamide and substituted benzene sulfonic acid amide group are directly with halogenated equal three
Piperazine molecule is connected, and sucting electronic effect reduces the cloud density of carbon atom on triazine ring, makes it easier to that nucleophilic displacement of fluorine occurs
Reaction, therefore the triazine structure reactivity is suitable with the reactivity of ethyl sulfonyl sulfate aniline, dyestuff is in 60 DEG C and 90 DEG C
Under reactivity quite, it can be achieved that energy-saving dyeing under temperate condition；And such dyestuff has higher light fastness, before
Scape is wide.
Detailed description of the invention
Fig. 1 is the dyeing curve of Examples 1 to 10 products therefrom；
Fig. 2 is the UV-Vis spectrogram of 1 products therefrom of embodiment；
Fig. 3 is the UV-Vis spectrogram of 2 products therefrom of embodiment；
Fig. 4 is the UV-Vis spectrogram of 3 products therefrom of embodiment；
Fig. 5 is the UV-Vis spectrogram of 4 products therefrom of embodiment；
Fig. 6 is the UV-Vis spectrogram of 5 products therefrom of embodiment；
Fig. 7 is the UV-Vis spectrogram of 6 products therefrom of embodiment；
Fig. 8 is 7 products therefrom UV-Vis spectrogram of embodiment；
Fig. 9 is 8 products therefrom UV-Vis spectrogram of embodiment；
Figure 10 is the UV-Vis spectrogram of 9 products therefrom of embodiment；
Figure 11 is the UV-Vis spectrogram of 10 products therefrom of embodiment；
Figure 12 is the FT-IR spectrogram of 1 products therefrom of embodiment；
Figure 13 is the FT-IR spectrogram of 2 products therefrom of embodiment；
Figure 14 is the FT-IR spectrogram of 3 products therefrom of embodiment；
Figure 15 is the FT-IR spectrogram of 4 products therefrom of embodiment；
Figure 16 is the FT-IR spectrogram of 5 products therefrom of embodiment；
Figure 17 is the FT-IR spectrogram of 6 products therefrom of embodiment；
Figure 18 is the FT-IR spectrogram of 7 products therefrom of embodiment；
Figure 19 is the FT-IR spectrogram of 8 products therefrom of embodiment；
Figure 20 is the FT-IR spectrogram of 9 products therefrom of embodiment；
Figure 21 is the FT-IR spectrogram of 10 products therefrom of embodiment；
Figure 22 is the MS spectrogram of 1 products therefrom of embodiment；
Figure 23 is the MS spectrogram of 2 products therefrom of embodiment；
Figure 24 is the MS spectrogram of 3 products therefrom of embodiment；
Figure 25 is the MS spectrogram of 4 products therefrom of embodiment；
Figure 26 is the MS spectrogram of 5 products therefrom of embodiment；
Figure 27 is the MS spectrogram of 6 products therefrom of embodiment；
Figure 28 is the MS spectrogram of 7 products therefrom of embodiment；
Figure 29 is the MS spectrogram of 8 products therefrom of embodiment；
Figure 30 is the MS spectrogram of 9 products therefrom of embodiment；
Figure 31 is the MS spectrogram of 10 products therefrom of embodiment.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Dye structure synthesized by 1. Examples 1 to 42 of table
Embodiment 1
Cyanuric Chloride condensation reaction: weighing 3.14g benzsulfamide, and 40mL water and 0.8g sodium hydroxide is added, is warming up to 20
DEG C stirring to dissolve, obtain mixed solution；Into mixed solution, middle dropwise addition 1.84g is dissolved in three in 20mL acetone at 0~5 DEG C
Polychlorostyrene cyanogen is added dropwise to complete in 40min.Reaction to a contracting reaction terminates at 0~5 DEG C, and the adjusting of 10% hydrochloric acid is added after a contracting
Unreacted benzsulfamide is precipitated in reaction solution pH < 3, filters to obtain clear filtrate.4.0g H is added to above-mentioned reaction filtrate when two contractings
Acid, controls 25 DEG C of reaction temperature, pH 6~7, and thin-layer chromatography detection control reaction to terminal, obtains condensation product.
Diazo-reaction: weighing 0.01mol para-ester solid, adjusts pH5~6 and is dissolved in 20mL water.It is sub- that 0.73g is added
Sodium nitrate dissolves wherein.The mixed solution is added to be cooled to 0~5 DEG C mass fraction containing 2.5mL be 37% dense salt
It is whether enough with Congored test paper and starch-KI test paper detection hydrochloric acid and sodium nitrite in the acidic aqueous solution of acid.After 30min,
Reaction end is detected with Ai Lixi reagent.At the end of diazotising, sulfamic acid is added into system and destroys extra sodium nitrite, obtains
Diazo liquid
Coupling reaction: above-mentioned diazo liquid is gradually added drop-wise to one contracting benzsulfamide of condensation product Cyanuric Chloride, two contracting H acid and is produced
In object solution, coupling pH 7~8 is adjusted with the sodium carbonate liquor of mass fraction 10%, obtains coupling reaction system solution,
0~5 DEG C of couple temperature of control, interval 10min detect diazo component and coupling component response situation, institute with circle method is seeped
State diazo component be above-mentioned diazo liquid, the coupling component be close reaction system solution, in combination with TLC detection reaction into
Journey.After coupling reaction, reaction pH to 7 or so is adjusted, buffer salt (Na is added thereto2HPO3-NaH2PO3, 1%, w/v),
Then the potassium acetate solid for being slowly added to about coupling reaction system quality 5% in batches is saltoutd, until seeping circle method has subject to hydrosphere appearance.
Continue stirring system 10min, filtered after standing system 20min, and wash filter cake by several times with 50mL ethyl alcohol, is drying to obtain dyestuff.
Embodiment 2~3
Respectively with benzsulfamide in P―Carboxybenzenesulfonamide and para toluene sulfonamide alternate embodiment 1, with identical synthesis side
Structure dyestuff shown in embodiment 2,3 can be made in method.
Embodiment 4
Cyanuric Chloride condensation reaction is identical as 1 reaction step of embodiment, replaces implementing with 2.15g J acid in two contracting steps
4.0g H acid in example 1.
Diazo-reaction: identical as 1 preparation method of embodiment.
Coupling reaction: above-mentioned diazo liquid is gradually added drop-wise in above-mentioned two contractings reaction mixture, with the carbon of mass fraction 10%
Acid sodium solution adjusts coupling pH 7~8, controls 0~5 DEG C of couple temperature, and interval 10min, which is used, seeps circle method detection diazo component and idol
It is combined a point response situation, in combination with the process of TLC detection reaction.After coupling reaction, reaction pH to 7 or so is adjusted, to
Buffer salt (Na is wherein added2HPO3-NaH2PO3, 1%, w/v), it is then slowly added to the second of about reaction system quality 5% in batches
Sour potassium solid is saltoutd, until seeping circle has subject to hydrosphere appearance.Continue stirring system 10min, filters, be used in combination after standing system 20min
50mL ethyl alcohol washs filter cake by several times, is drying to obtain dyestuff.
Embodiment 5~10
Respectively with P―Carboxybenzenesulfonamide, para toluene sulfonamide, to trifluoromethyl benzene sulfonamide, p-nitrophenyl sulfonamide,
P-chloro benzenesulfonamide, brosyl amine replace embodiment 4 in benzsulfamide, with same synthetic method can prepare embodiment 5~
Structure dyestuff shown in 10.
Embodiment 11
Cyanuric Chloride condensation reaction: weighing 3.14g benzsulfamide, and 40mL water and 0.8g sodium hydroxide, heating stirring is added
To dissolution；It is added dropwise at 0~5 DEG C Cyanuric Chloride (1.84g, dissolution is in acetone), is added dropwise to complete in 40min thereto.Constant temperature
Reaction to reaction terminates, and adjusts reaction system pH < 3 after a contracting and unreacted benzsulfamide is precipitated.Filter out precipitation not
Benzsulfamide is reacted, filtrate must be reacted.Above-mentioned reaction filtrate is warming up to 20 DEG C when two contractings, 2.15g γ acid, control reaction is added
25 DEG C of temperature, pH 6~7, control reaction is to terminal.
Diazo-reaction: identical as 1 preparation method of embodiment.
Coupling reaction: above-mentioned diazo liquid is gradually added drop-wise to one contracting benzsulfamide of Cyanuric Chloride, two contracting γ acid product solution
In, coupling pH 7~8 is adjusted with the sodium carbonate liquor of mass fraction 10%, controls 0~5 DEG C of couple temperature, interval 10min seeps
Circle method detects diazo component and coupling component response situation, in combination with the process of TLC detection reaction.After coupling reaction,
Reaction pH to 7 or so is adjusted, buffer salt (Na is added thereto2HPO3-NaH2PO3, 1%, w/v), it is then slowly added in batches about
The potassium acetate solid of reaction system quality 5% is saltoutd, until seeping circle method has subject to hydrosphere appearance.Continue stirring system 10min, stands
It is filtered after system 20min, and washs filter cake by several times with 50mL ethyl alcohol, be drying to obtain dyestuff.
Embodiment 12~17
Respectively with P―Carboxybenzenesulfonamide, para toluene sulfonamide, to trifluoromethyl benzene sulfonamide, p-nitrophenyl sulfonamide,
Benzsulfamide in p-chloro benzenesulfonamide, brosyl amine alternate embodiment 11, can be made with preparation method identical as embodiment 11
Obtain structure dyestuff shown in embodiment 12~17.
Embodiment 18
Diazo-reaction: it is identical as 1 preparation method of embodiment, obtain para-ester diazonium salt.
Coupling reaction: 4.0g H acid is weighed, 50mL water is added and adjusts pH 6 or so, this H- acid solution is gradually added dropwise
It in above-mentioned para-ester diazonium salt, is slowly added dropwise, controls time for adding in 4h or so.The primary coupling pH < 3 of control, temperature 0~5
DEG C, it seeps circle method and detects reaction end, add sodium carbonate liquor to adjust reaction pH to neutrality after coupling reaction, obtain and be once coupled
Liquid.
Cyanuric Chloride condensation reaction: weighing 3.14g benzsulfamide, and 40mL water and 0.8g sodium hydroxide is added, is warming up to 20
DEG C stirring to dissolve；It is added dropwise at 0~5 DEG C Cyanuric Chloride (1.84g, dissolution is in acetone), is dripped in 40min thereto
At.Isothermal reaction to terminal, after adjust reaction system pH < 3 unreacted benzsulfamide is precipitated.It will be above-mentioned anti-when two contractings
It answers filtrate to be warming up to 25 DEG C, 1.8g 2 is added, 4- diamino benzene sulfonic acid controls 25 DEG C of reaction temperature, pH 6~7, control reaction
To terminal.
Diazo-reaction: by above-mentioned one contracting benzsulfamide two of Cyanuric Chloride contract 2,4- diamino benzene sulfonic acid, two contracting reaction solution,
It is cooled to 0~5 DEG C, 0.72g sodium nitrite is added and is dissolved in above-mentioned reaction solution.The mixed solution is added to and is cooled to 0~5
DEG C the concentrated hydrochloric acid containing 2.5mL acidic aqueous solution in Congored test paper and starch-KI test paper detection hydrochloric acid and sodium nitrite be
It is no enough.After 30min, reaction end is detected with Ai Lixi reagent.At the end of diazotising, appropriate sulfamic acid is added into system
Destroy extra sodium nitrite.
Coupling reaction: above-mentioned diazo liquid is gradually added drop-wise in a coupling solution, molten with the sodium carbonate of mass fraction 10%
Liquid adjusts coupling pH 7~8, controls 0~5 DEG C of couple temperature, and interval 10min, which is used, seeps circle method detection diazo component and coupling component
Response situation, in combination with the process of TLC detection reaction.After coupling reaction, adjust reaction pH to 7 or so, thereto plus
Enter buffer salt (Na2HPO3-NaH2PO3, 1%, w/v), the potassium acetate for being then slowly added to about reaction system quality 5% in batches is solid
Body is saltoutd, until seeping circle method has subject to hydrosphere appearance.Continue stirring system 10min, is filtered after standing system 20min, and use 50mL
Ethyl alcohol washs filter cake by several times, is drying to obtain dyestuff.
Embodiment 19~22
Respectively with P―Carboxybenzenesulfonamide, para toluene sulfonamide, to trifluoromethyl benzene sulfonamide, p-nitrophenyl sulfonamide,
Benzsulfamide in alternate embodiment 18, structure shown in embodiment 19~22 can be made with identical preparation method shown in embodiment 18
Dyestuff.
Embodiment 23~25
With benzsulfamide in p-chloro benzenesulfonamide alternate embodiment 18, with 1,3- diaminobenzene, 1,2- diaminobenzene, 2,4-
Diamino, m-phenylene diamine (MPD) -4,6- disulfonic acid replaces 2,4- diamino benzene sulfonic acid in embodiment 18, with identical as shown in embodiment 18
Structure dyestuff shown in embodiment 23~25 can be made in preparation method.
Embodiment 26
With benzsulfamide in brosyl amine alternate embodiment 18, with 2,4- diamino, 1,5- disulfonic acid base benzene is replaced
2,4- diamino benzene sulfonic acid in embodiment 18, structure shown in embodiment 26 can be made with identical preparation method shown in embodiment 18
Dyestuff.
Embodiment 27
With Cyanuric Chloride in cyanuric fluoride alternate embodiment 1, with benzene sulfonyl in 4- sulfonic benzo sulfonamide alternate embodiment 1
Structure dyestuff shown in embodiment 27 can be made using identical preparation method shown in embodiment 1 in amine.
Embodiment 28~29
Respectively with 3- hydroxyl, 4- methyl benzenesulfonamide, 4- sulfonic group in 2,4- dimethyl benzene sulfonamide alternate embodiments 27
Structure dyestuff shown in embodiment 28~29 can be made using preparation method identical as embodiment 25 in benzene sulfonyl.
Embodiment 30
With 3- methyl, benzsulfamide in 4- trifluoromethyl benzene sulfonamide alternate embodiment 1, with p- (ethyl-beta-hydroxyethyl
Sulfone sulfate) aniline replace embodiment 1 in para-ester, corresponding construction dyestuff can be made using same preparation method.
Embodiment 31
Para-ester in embodiment 29 is replaced with p- (ethyl-beta-hydroxyethyl sulfone sulfate) aniline, uses same system
Corresponding construction dyestuff can be made in Preparation Method.
Embodiment 32
With 2- methyl, 3- methyl in 4- methoxybenzenesulphoismide alternate embodiment 29,4- trifluoromethyl benzene sulfonamide is used
Corresponding construction dyestuff can be made in same preparation method.
Embodiment 33
With 3- hydroxyl, benzsulfamide in 4- methyl benzenesulfonamide alternate embodiment 1, with 2- methyl, 4- (ethyl-β-hydroxyl second
Base sulfone sulfate) para-ester in aniline. Example 1, structure shown in embodiment 33 can be made using same preparation method and contaminate
Material.
Embodiment 34
With 3- carboxyl, benzsulfamide in 4- methyl benzenesulfonamide alternate embodiment 1, with 2- methyl, 4- (ethyl-β-hydroxyl second
Base sulfone sulfate) para-ester in aniline alternate embodiment 1, knot shown in embodiment 34 can be made using same preparation method
Structure dyestuff.
Embodiment 35
With 3- nitro, benzsulfamide in 4- methyl benzenesulfonamide alternate embodiment 1, with 2- methyl, 4- (acetyl group hydroxyl sulphur
Acid esters) para-ester in aniline alternate embodiment 1, structure shown in embodiment 35 can be made using same preparation method and contaminate
Material.
Embodiment 36
With 3- chlorine, benzsulfamide in 4- methyl benzenesulfonamide alternate embodiment 1, with 2- methyl, 4- (acetylamino hydroxyl sulphur
Acid esters) para-ester in aniline alternate embodiment 1, structure shown in embodiment 36 can be made using same preparation method and contaminate
Material.
Embodiment 37
With 3- bromine, benzsulfamide in 4- methyl benzenesulfonamide alternate embodiment 1, with 2- methyl, 4- (sulfoamido, β-hydroxyl
Ethyl sulfonyl sulfate) para-ester in aniline alternate embodiment 1, it can be made shown in embodiment 37 using same preparation method
Structure dyestuff.
Embodiment 38
With 3- fluorine, 3- carboxyl in 4- methyl benzenesulfonamide alternate embodiment 32,4- methyl benzenesulfonamide, use is same
Preparation method structure dyestuff shown in embodiment 38 can be made.
Embodiment 39
With 2,4-, 3- carboxyl in methyl benzenesulfonamide alternate embodiment 32,4- methyl benzenesulfonamide, use are same
Preparation method structure dyestuff shown in embodiment 39 can be made.
Embodiment 40
Respectively with 3- methoxyl group, benzsulfamide and H acid in 4- methyl benzenesulfonamide, K acid alternate embodiment 1, with meta position ester
Structure dyestuff shown in embodiment 40 can be made using identical preparation method in para-ester in alternate embodiment 1.
Embodiment 41
Respectively with 3- cyano, 5- methyl benzenesulfonamide, 1- amino, 8- naphthols, 2,4- bis- naphthalene sulfonic acids (chicago acid) substitution
Benzsulfamide and H are sour in embodiment 1, and para-ester in 3- (β-chloroethyl sulfone) aniline alternate embodiment 1, identical preparation method can obtain
Structure dyestuff shown in embodiment 41.
Embodiment 42
Respectively with 3- cyano, benzsulfamide and H acid in 5- methyl benzenesulfonamide, K acid alternate embodiment 1, with 3- ethyl, 4-
Para-ester in sulfuric ester ethyl sulfonyl aniline alternate embodiment 1, dyestuff shown in same procedure preparation structure 42.
Embodiment 43
With 3- cyano, 3- cyano in 4- methyl benzenesulfonamide alternate embodiment 40,5- methyl benzenesulfonamide, with 3- methoxy
Base, 2- methyl in 4- sulfuric ester ethyl sulfonyl aniline alternate embodiment 35,4- (sulfoamido, beta-hydroxyethyl sulfone sulfate) aniline,
Dyestuff shown in same procedure preparation structure 43.
Embodiment 44
Respectively with 3- cyano, 4- aminomethyl phenyl sulfonamide, 1- amino, 8- naphthols, in 2,4- bis- naphthalene sulfonic acids alternate embodiments 1
Benzsulfamide and H are sour, para-ester in 4- methoxyl group -3- (beta-sulfuric ester ethyl sulfonyl) aniline alternate embodiment 1, identical preparation method
Structure dyestuff shown in embodiment 44 can be obtained.
The test of dyeability
For the 10 by-reaction dyestuff exhaust dyeings synthesized by the Examples 1 to 10, Coloration experiment is carried out, such as Fig. 1 institute
Show dyeing curve dyeing, to obtain the dyeing cloth specimen of close color depth, each branch dyestuff dyes under different chrominance requirements.It is simultaneously
Facilitate and compare the dyeing activity of dyestuff at different temperatures, chooses 60 DEG C, 75 DEG C and 90 DEG C of color fixing temperature respectively.Take appropriate dye
Material, is configured to dye solution.It takes the 2g cotton fiber of precise to disseminate in 20mL dye liquor, obtains cloth specimen.After dyeing, cloth specimen
Raffinate is washed and collected, absorbance A is measured1.Cloth specimen after washing is placed in 0.1% soap lye, 95 DEG C of soap boiling 10min, is taken out
Cloth specimen is sufficiently washed again, is collected raffinate, is surveyed its absorbance A2.It separately takes former dye liquor 1mL to be diluted to 100mL, surveys its absorbance A0。
1. the measurement of degree of exhaustion, degree of fixation, reactivity
By Covalent bonding together, degree of exhaustion, degree of fixation, reactivity are calculated by following formula for dyestuff and fiber:
Wherein E, F, R are respectively degree of exhaustion, degree of fixation, reactivity (100%)；A0、A1、A2Respectively dye
The absorbance of stoste, dyeing residual liquid and raffinate of soaping；n0、n1、n2It respectively dyes stoste, dyeing residual liquid and soaps
The corresponding extension rate of raffinate.
2. the measurement of dyefastness
Colour fasteness to sunlight is measured using GB/T 8427-2008；Colour fastness to rubbing is surveyed using GB/T 3920-2008
It is fixed；Washing color fastness is measured using GB/T 3921-2008, and colorant dissolubility is measured using GB/T21879-2015.
According to above-mentioned dyeing condition, the coloration result of above-mentioned 10 dyestuffs be see the table below
Data are dyed under 2 dyestuff difference color fixing temperature of table
According to above-mentioned test condition, the fastness test result of above-mentioned 10 dyestuffs is shown in Table 3.
Table 3. dyes cloth specimen color fastness
Claims (9)
1. a kind of chemically-reactive dyes replaced containing benzsulfamide and its derivative, which is characterized in that the structure with general formula I:
In Formulas I,
R is selected from-Cl or-F；
R1Selected from-H, methyl, itrile group, sulfonic group, trifluoromethyl, methoxyl group, hydroxyl, carboxyl, nitro ,-Cl ,-Br ,-F；
R2Selected from-H, methyl, aminomethyl, trifluoromethyl, methoxyl group, hydroxyl, nitro, cyano ,-Cl ,-Br ,-F；
R3Selected from-H ,-OCH3,-CH3,-CH2CH3；
L is selected from-SO2,-CO- ,-NHCO- ,-SO2NH- ,-CH2CH2SO2,-O-CH2CH2SO2,-NHCH2CH2SO2,-
NHCONHCH2CH2SO2,-SO2CH2CH2SO2Or-NXSO2Group, wherein X is selected from C1~C4Carbon atom is substituted or unsubstituted
Alkoxy, phenyl, substituent group can be-SO3H ,-COOH ,-OH, halogen, cyano, amino-sulfonyl (H2NSO2), ethoxy
Base, cyanogen methyl group；
M is selected from-Cl, or-OSO3R4, wherein R4Selected from-H ,-Na or-K；
A is selected from substituent group shown in II-a or II-b；
In Formula II-a,
The integer that n is 0~2；
Residue representated by Formula II-b is one of following radicals:
H acid residue, structural formula are as follows:
J acid residue, structural formula are as follows:
γ acid residue, structural formula are as follows:
K acid residue, structural formula are as follows:
Chicago acid residue, structural formula are as follows:
2. the preparation method of the chemically-reactive dyes replaced described in claim 1 containing benzsulfamide and its derivative, which is characterized in that
The preparation method of the dyestuff includes following two classes methods:
Method one: halogenated s-triazine and benzsulfamide, amino naphthol sulfonic acid class substrate carry out condensation reaction, obtain condensation product；β-
Sulfuric ester ethyl sulfonyl aniline passes through diazo-reaction, obtains diazonium salt solution；The condensation product and the diazonium salt solution are passed through
Coupling reaction is crossed, 0~5 DEG C of reaction temperature, pH7~8 obtain dyestuff described in claim 1；
Method two: beta-sulfuric ester ethyl sulfonyl aniline passes through diazo-reaction, obtains diazonium salt solution；H acid solution adds to above-mentioned dropwise
In diazonium salt solution, molar ratio 1:1, reaction temperature is 0~5 DEG C, reaction time 4h, pH < 3, by a coupling reaction,
Obtain a coupling solution；Halogenated s-triazine and benzsulfamide, arylamine class substrate carry out condensation reaction, obtain condensation product；By above-mentioned contracting
It closes product and passes through diazo-reaction, obtain condensation product diazo liquid；Above-mentioned condensation product diazo liquid is added dropwise to above-mentioned primary coupling
In liquid, 0~5 DEG C of reaction temperature, pH7~8 obtain dyestuff described in claim 1 through coupling reaction.
3. method according to claim 2, which is characterized in that the condensation product the preparation method is as follows:
Halogenated s-triazine and benzsulfamide or derivatives thereof are subjected to first time condensation reaction；Again with amino naphthol sulfonic acid class substrate
Or arylamine substrate carries out second and is condensed, and obtains condensation product；
It is 1:1~1:3 that the first time, which is condensed halogenated s-triazine and the molar ratio of benzene sulfonyl amine salt, and reaction temperature is 0~5 DEG C,
Time for adding 40min~50min, reaction time 120min obtain first time condensation product, first time condensation product and amino naphthalenes
Phenol sulfonic acid class substrate or arylamine substrate molar ratio are 1:0.9~1, and 15~30 DEG C of reaction temperature, pH6~7, thin-layer chromatography detection is instead
Terminal is answered, condensation product is obtained.
4. according to the method described in claim 2, it is characterized in that, the halogenated s-triazine and benzsulfamide carry out first time contracting
After closing reaction, unreacted benzene sulfonamide and its derivative is precipitated, obtains clear filtrate, clear filtrate again with amino naphthol sulfonic acid class bottom
Object or arylamine substrate carry out second and are condensed, and the mode of the precipitation adds acid for adjusting pH < 3.
5. according to the method described in claim 2, it is characterized in that, the halogenated s-triazine is Cyanuric Chloride and cyanuric fluoride.
6. according to the method described in claim 2, it is characterized in that, the amino naphthol sulfonic acid class substrate is to be H acid, J acid, r
Acid, K acid, chicago acid.
7. according to the method described in claim 2, it is characterized in that, the arylamine class substrate be 2,4- diamino benzene sulfonic acid, 1,
2- diaminobenzene, 1,3- diaminobenzene, 1,4- diaminobenzene, 2,4- diaminostilbene, 5- disulfonic acid base benzene.
8. according to the method described in claim 2, it is characterized in that, the diazo-reaction is primary aromatic amine and sodium nitrite
At 0~5 DEG C, reaction generates the reaction of diazonium salt under strong acid media, primary aromatic amine and nitrous acid molar ratio be 1:1.03~
1.1, the strong acid media is the concentrated hydrochloric acid that mass fraction is 37%, and concentrated hydrochloric acid mole is 3 times of primary aromatic amine, the virtue
Fragrant race's primary amine is beta-sulfuric ester ethyl sulfonyl aniline or condensation product, and the condensation product is halogenated s-triazine and benzsulfamide first
It is obtained again with amino naphthol sulfonic acid class substrate condensation reaction after secondary condensation,
Whether the diazo-reaction Congored test paper and starch-KI test paper detection hydrochloric acid and sodium nitrite are enough, with an angstrom benefit
Western reagent detects reaction end, at the end of diazotising, sulfamic acid is added and destroys extra sodium nitrite, obtains diazo liquid.
9. according to the method described in claim 2, it is characterized in that, the coupling reaction is reacted to terminal with the circle method monitoring of infiltration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811327162.0A CN109608903B (en) | 2018-11-08 | 2018-11-08 | Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811327162.0A CN109608903B (en) | 2018-11-08 | 2018-11-08 | Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109608903A true CN109608903A (en) | 2019-04-12 |
| CN109608903B CN109608903B (en) | 2020-04-14 |
Family
ID=66003250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811327162.0A Active CN109608903B (en) | 2018-11-08 | 2018-11-08 | Reactive dye substituted by benzene sulfonamide and derivatives thereof and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109608903B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437278A (en) * | 2022-02-11 | 2022-05-06 | 大连理工大学 | Styrene maleic acid copolymerization macromolecular reactive dye and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871654A (en) * | 1987-05-29 | 1989-10-03 | Agfa-Gevaert, N.V. | Photographic element incorporating redox compounds for use in a dye diffusion transfer process |
| US5231172A (en) * | 1991-10-23 | 1993-07-27 | Hoechst Aktiengesellschaft | Fiber reactive dyes which contain a sulfonamido-triazinyl group and one or two groups or the vinyl sulfone series |
| US5359043A (en) * | 1991-05-17 | 1994-10-25 | Zeneca Limited | Reactive dyes having a sulphonamido group |
-
2018
- 2018-11-08 CN CN201811327162.0A patent/CN109608903B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871654A (en) * | 1987-05-29 | 1989-10-03 | Agfa-Gevaert, N.V. | Photographic element incorporating redox compounds for use in a dye diffusion transfer process |
| US5359043A (en) * | 1991-05-17 | 1994-10-25 | Zeneca Limited | Reactive dyes having a sulphonamido group |
| US5231172A (en) * | 1991-10-23 | 1993-07-27 | Hoechst Aktiengesellschaft | Fiber reactive dyes which contain a sulfonamido-triazinyl group and one or two groups or the vinyl sulfone series |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437278A (en) * | 2022-02-11 | 2022-05-06 | 大连理工大学 | Styrene maleic acid copolymerization macromolecular reactive dye and preparation method thereof |
| WO2023151118A1 (en) * | 2022-02-11 | 2023-08-17 | 大连理工大学 | Styrene-maleic acid copolymerized macromolecular reactive dye and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109608903B (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Ecofriendly synthesis and application of special disperse reactive dyes in waterless coloration of wool with supercritical carbon dioxide | |
| EP0252508B1 (en) | Water soluble disazo colorant and dyeing method using the same | |
| WO2020048018A1 (en) | Azo dye dedicated for water-free dyeing of natural fiber in supercritical co 2 fluid, and preparation method therefor | |
| Patel et al. | Synthesis of some heteropolyfunctional reactive dyes and their application on silk, wool, and cotton fibers | |
| EP0142863B1 (en) | Reactive pyridone azo dyestuffs | |
| US4230852A (en) | Triazinyl-antraquinone dyes | |
| CN109608903A (en) | A kind of chemically-reactive dyes and preparation method thereof replaced containing benzsulfamide and its derivative | |
| JPH0218349B2 (en) | ||
| US5976197A (en) | Dyeing process and dyes | |
| CN102504582B (en) | Reactive dark blue bisazo dye and preparation method thereof | |
| CN110066527B (en) | Red reactive dye and preparation method thereof | |
| CN104693836B (en) | Anthraquinone azo reactive dye | |
| CN105838107B (en) | The orange-yellow azoic dye of cyano-containing | |
| CN110054910A (en) | A kind of Black reactive dye composition and its preparation method and application | |
| CN110157216A (en) | A kind of dark blue reactive dye and its processing method | |
| JPH0860018A (en) | Reactive dye,its preparation and method of using same | |
| JPH06157931A (en) | Water-soluble disazo compound, its preparation and its use as dye | |
| CN114933818B (en) | Indoline disperse dye and preparation method thereof | |
| CN115386244B (en) | Double-color-body pH color-changing reactive dye and preparation and application thereof | |
| JPH02113073A (en) | Water-soluble azo compound, its preparation, and method of using it as dye | |
| Blus et al. | Reactive dyes for single-bath and single-stage dyeing of poliester-cellulose blends | |
| CN113150576B (en) | Ink-jet printing active red dye and preparation method and application thereof | |
| JPH0953019A (en) | Reactive aluminum phthalocyanine dye | |
| CZ35895A3 (en) | Water-soluble azo compounds, process of their preparation and their use as dyestuffs | |
| CN110041729B (en) | Orange-red reactive dye and preparation method thereof |
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 |